Physical Properties of Materials

PHYSICAL PROPERTIES OF MATERIALS
THE MODERN UNIVERSITY PHYSICS SERIES
This series is intended for readers whose main interest is in physics, or who
need the methods of physics in the study of science and technology. Some of
the books will provide a sound treatment of topics essential in any physics
training, while other, more advanced, volumes will be suitable as preliminary
reading for research in the field covered. New titles will be added from time
to time.
Clark: A First Course in Quantum Mechanics (Revised Edn.)

Littlefield and Thorley: Atomic and Nuclear Physics (2nd Edn.)
Lothian: Optics and Its Uses
Lovell, Avery and Vernon: Physical Properties of Materials
Tritton: Physical Fluid Dynamics
PHYSICAL PROPERTIES OF
MATERIALS
M. C. LOVELL, A. 1. A VERY, M. W. VERNON
VAN NOSTRAND REINHOLD COMPANY
New York - Cincinnati - Toronto - London - Melbourne

© M. C. Lovell, A. J. Avery, M. W. Vernon, 1976
Reprinted with corrections 1977

Reprinted 1981
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Library of Congress Cataloging in Publication Data
Lovell, M. C.
Physical properties of materials.
Bibliography: p. 292
Includes index.
1. Solids. 2. Materials. I. Avery, A. J., joint
author. II. Vernon, M. W., joint author. III. Title.
QC176.L66 530.4'1 75-35836
ISBN-l3: 978-0-442-30097-5 e-ISBN-13: 978-94-011-6065-0

DOl: 10.1007/978-94-011-6065-0
University Press, Cambridge

Preface
Materials Science has now become established as a discipline in its own right as well as
being of increasing importance in the fields of Physics, Chemistry and Engineering. To
the student meeting this subject for the first time the combination of disciplines which
it embraces represents a formidable challenge. He will require to understand the lan-
guage of the physicist and chemist as well as appreciate the practical uses and limita-
tions of solid materials. This book has been written as an introduction to the Physical
Properties of Materials with these thoughts in mind. The mathematical content has
been limited deliberately and emphasis is placed on providing a sound basis using
simplified models. Once these are understood we feel that a mathematical approach
is more readily assimilated and for this purpose supplementary reading is suggested.
While the authors are deeply aware of the pitfalls in attempting such a treatment this
is meant to be an essentially simple book to point the many avenues to be explored.
We anticipate that the book will appeal to first and second year degree students in
a variety of disciplines and may not prove too difficult for those studying appropriate
Higher National Certificate and Diploma courses. Electrical engineers working in the
field of materials applications may well find it useful as a guide to modern thinking
about materials and their properties.
The book begins with an introduction to some basic ideas of modern physics. The
following three chapters discuss the structure of ideal and imperfect solids. They des-
cribe the techniques whereby samples of pure materials may be prepared in single
crystal or amorphous forms and their structure determined. The mechanical properties
of materials are surveyed in Chapter 5 and thermal properties in Chapter 6. Chapter 7
is devoted mainly to semiconducting materials but the usual introduction to semi-
conductor physics which is found in most texts on semiconductor devices has been
omitted. Here much more emphasis has been placed on a survey of the physical
properties of semiconducting materials including recent ideas and applications. The
basic classical ideas of dielectrics are introduced in Chapter 8 followed by a discussion
of piezoelectric, pyroelectric and ferroelectric materials. These materials are proving to
have many varied and interesting possibilities for applications. A similar treatment is
afforded to the magnetic and optical properties of solids in Chapters 9 and 10. New
developments, for example magnetic bubbles and electro-optics are included and the
relevant material properties presented. The final chapter is concerned with Super-
conductivity and attention is focused on materials which are being or may be used for
superconducting devices.
For the materials scientist the aim of scientific theory is to predict new develop-
ments as well as explain experimental results, and a text such as this must point the
way to new possibilities for materials. For this reason some exciting prospects for
new materials are mentioned as well as new ideas which have not yet developed into
vi PREFACE
practical applications. By introducing the reader to the frontiers of the subject at one
or two points his appetite may be whetted for scientific discovery in a rapidly develop-
ing field.
Throughout the book the MKS(SI) system of units has been used. References to
appropriate review articles in the literature are cited so as to give the reader an oppor-
tunity to pursue a given topic. Examples are given at the end of most chapters and
numerical answers are provided. These questions are designed to test and assist the
student's understanding of the text.
We wish to thank Dr A. J. Woodall who gave us the opportunity to undertake the
task of writing this book and to express gratitude to our colleagues who have helped
in many and various ways. Particular thanks are due to Mr C. G. Wilson for his careful
reading of the manuscript and helpful comments, and to Mr D. Carter for expert
assistance with the illustrations. Finally we thank the Dean of the Royal Military
College of Science for permission to publish.
October 1975 M. C. LOVELL
A.J.AVERY
M.W.VERNON
Acknowledgements
We wish to thank the publishers of the following journals and books for permission to
reproduce the items specified:
Physical Review (Figs. 7.10, 7.l4c, 7.17,10.8,10.14,10.24 and some data in Fig. 10.9);
Annalen der Physik (Figs. 7.3, 7.4); Journal of Physics C (Fig. 7.14b); Journal of Non-
Crystalline Solids (Figs. 7.19, 7.20 and some data in Fig. 10.10); Comptes Rendus (Fig.
7 .14d); Proceedings of the Institution of Electrical Engineers (Fig. 9.22); Proceedings of
the International Conference on Magnetism (Nottingham 1964) (Fig. 7.16); McGraw
Hill for Fig. 8.8 and data of Tables 8.1 and 8.3; Academic Press for Fig. 10.22 and
some data in Tables 8.8, 8.9, 10.4; Wiley for some data in Table 10.4.
Acknowledgements are also due to E.M.1. Valve Division, Hayes, Middlesex for per-
mission to reproduce data of Table 10.21, to Chance-Pilkington Glass Co. for the data
on optical glasses in Table 10.1, and Mr. D. A. James for material on the microwave
properties of ferrites.
Contents
Page
Preface v
CHAPTER 1 FUNDAMENTALS
1.1 Introduction 1
1.2 Wave mechanics 1
1.2.1 The hydrogen atom 3
1.3 Many-electron atoms and the Pauli Principle 6
1.3.1 Electron states in multi-electron atoms 7
1.4 Transition elements 9
1.5 Atomic magnetism 10
1.5.1 Diamagnetism 12
1.5.2 Paramagnetism 13
1.5.3 Exchange 13
1.6 Electrons in solids 16
CHAPTER 2 STRUCTURE OF SOLIDS

2.1 Introduction-atomic bonding 19
2.1.1 Ionic bonding 20
2.1".2 Covalent bonding 21
2.1.3 Metallic (unsaturated covalent) bonding 22
2.1.4 Van der Waals bonding (molecular bonding) 23
2.2 Crystal structure 23
2.3 Lattice planes and directions 26
2.4 Atomic packing 28
2.5 Covalent solids 30
2.6 Ionic solids 31
2.7 Summary 33
2.8 Lattice imperfections 34
2.9 Lattice vibrations 34
2.10 Point defects 35
2.11 line defects 36
2.11.1 The edge dislocation 37
2.11.2 The screw dislocation 37
2.11.3 The Burgers vector 38
2.12 Plane defects 39
2.13 Amorphous materials 40
viii CONTENTS
CHAPTER 3 PREPARATION OF MATERIALS Page

3.1 Introduction 42
3.2 Mechanism of crystal growth 42
3.3 Growth from the melt 46
3.3.1 Growth from crucibles 46
3.3.2 Non-crucible methods 48
3.3.3 Zone refining 50
304 Non-melt techniques 52
304.1 Fluxed-melt technique 53
304.2 Chemical transport 53
3.4.3 Gel growth 54
3.5 Thin films 54
3.6 The origin of dislocations during crystal growth 56
3.6.1 Collapse of vacancy discs 56
3.6.2 Strain resulting from thermal stress or impurities 56
3.6.3 Dendritic growth 57
3.7 Non-crystalline materials 57
3.8 Amorphous semiconductors 59
3.9 Plastic materials 60
3.9.1 Polymerization 61
3.9.2 Structure of polymers 62
3.9.3 Thermoplastic and themosetting plastics 64
CHAPTER 4 PRACTICAL DETERMINATION OF STRUCTURE

4.1 Introduction 65
4.2 Theoretical X-ray diffraction 65
4.3 Practical X-ray diffraction 69
4.3.1 The Laue technique 70
4.3.2 The rotating crystal technique 71
4.3.3 The powder technique 73
4.4 Other applications of X-ray diffraction 75
4.4.1 Preferred orientation in polycrystalline metals 75
4.4.2 X-ray topography 75
4.4.3 Study of polymer materials 76
4.5 Neutron diffraction 76
4.6 Electron diffraction 78
4.7 Structure of amorphous materials 80
4.8 Other techniques 84
4.8.1 Field-ion microscopy 84
4.8.2 Infra-red spectroscopy 84
4.8.3 Observation of dislocations 85
CHAPTERS MECHANICAL PROPERTIES OF MATERIALS

5.1 Introduction 87
5.2 Mechanical testing 87
5.3 Elastic behaviour 89
5.4 Plastic behaviour 90
504.1 Dislocation multiplication 94
504.2 Additional dislocation motion and dislocation
interactions 95
CONTENTS ix
Page
5.4.3 Behaviour of polycrystalline materials 96
5.5 Fracture 96
5.5.1 Brittle fracture 96
5.5.2 Ductile fracture 98
5.5.3 Fatigue failure 99
5.6 Strengthening of materials 99
5.6.1 Strain (or work) hardening 99
5.6.2 Solution hardening 101
5.6.3 Precipitation and dispersion hardening 101
5.7 Creep 102
5.8 Mechanical properties of plastics 103
CHAPTER 6 THERMAL PROPERTIES

6.1 Introduction 106
6.2 Thermal statistics 106
6.3 Heat capacity 108
6.4 Specific heat anomalies 112
6.5 Thermal expansion 114
6.6 Thermal conductivity 115
6.7 Thermoelectricity 117
6.7.1 Thermoelectric power 117
6.7.2 Seebeck effect 119
6.7.3 Thomson effect 119
6.7.4 Peltier effect 120
CHAPTER 7 ELECTRICAL PROPERTIES

7.2 Metals 125
7.2.1 Impurities 128
7.2.2 Pressure 130
7.3 Semiconductors 130
7.3.1 II-VI compounds 134
7.3.2 III-V compounds 135
7.3.3 The Gunn diode 137
7.3.4 Other semiconducting compounds 139
7.3.5 V-VI compounds 139
7.4 Transition metal compounds 139
7.5 Polarons 140
7.6 Magnetic semiconductors 142
7.6.1 The metal-insulator transition 144
7.7 Amorphous materials 146
7.8 Switching 149
7.8.1 Ovonic threshold switch 150
7.8.2 Ovonic memory switch 150
CHAPTER 8 DIELECTRICS
8.2 Mechanisms of polarization 156
8.2.1 Induced polarization 156
x CONTENTS
Page
8.2.2 Orientational polarization 157
8.3 The local field 158
8.4 The Clausius-Mosotti relation 161
8.5 Dielectric relaxation 161
8.6 Applications 165
8.7 Piezoelectric, pyroelectric and ferroelectric materials 166
8.8 Piezoelectricity 168
8.8.1 Electromechanical coupling coefficient 170
8.8.2 Ceramic piezoelectrics 172
8.8.3 Piezoelectric materials and their applications 172
8.9 Ferroelectricity 173
8.10 Classification of ferroelectric materials 175
8.11 Barium titanate 176
8.12 Ferroelectric ceramics 177
8.13 Ferroelectric domains 179
8.13.1 Observation of domains 180
8.14 Pyroelectricity 180
8.14.1 Applications of pyroelectric materials 183
CHAPTER 9 MAGNETIC PROPERTIES

9.2 Classification of magnetic materials 185
9.3 Diamagnetism 186
9.4 Paramagnetism 187
9.4.1 Pauli paramagnetism 188
9.5 Ferromagnetism 188
9.6 Magnetic anisotropy 190
9.7 Magnetostriction 192
9.8 Ferromagnetic domains 192
9.8.1 Origin of domains 193
9.8.2 Domain walls 194
9.8.3 Domain patterns 195
9.9 Microscopic explanations of ferromagnetism 195
9.1 0 Applications of ferromagnetic materials 196
9.11 Antiferromagnetism 197
9.12 Antiferromagnetic compounds 199
9.13 Antiferromagnetic domains 200
9.13.1 Observation of anti ferromagnetic domains 201
9.14 Ferrimagnetism 201
9.14.1 Normal spinel 201
9.14.2 Inverse spinel 201
9.15 Ferrimagnetic domains-magnetic bubbles 205
9.16 Magnetic ceramics 206
9.17 Applications of ferrimagnetic materials 207
9.17.1 Permanent magnets 207
9.17.2 Soft ferrites 207
9.17.3 Rectangular loop ferrites 208
9.17.4 Microwave ferrites 212
CONTENTS xi
CHAPTER 10 OPTICAL PROPERTIES Page
10.2 Refractive index 219
10.2.1 Birefringence 220
10.2.2 Dispersion 221
10.3 Absorption 223
10.3.1 Ionic materials 224
10.3.2 Semiconductors 224
10.3.3 Metals 228
10.3.4 Impurities 228
10.3.5 Colour centres 230
10.3.6 Excitons 231
10.4 Reflection 232
10.5 Natural birefringence 233
10.5.1 Double refraction 235
10.6 Induced birefringence 237
10.6.1 Linear electro-optics 237
10.6.2 Intensity modulation 237
10.6.3 Quadratic electro-optics 240
10.6.4 Blasto-optics 240
10.7 Non-linear optics 241
10.8 Secondary processes 241
10.8.1 Photoelectric emission 242
10.8.2 Photoconductivity 244
10.8.3 Photoluminescence 247
10.9 Lasers 250
10.9.1 Principles oflaser action 250
10.9.2 Solid state lasers 251
10.9.3 Gas lasers 252
10.9.4 Semiconductor diode lasers 252
CHAPTER 11 SUPERCONDUCTIVITY
11.2 Resistanceless and superconducting states 257
11.3 Superconductivity 258
11.4 Penetration depth 260
11.5 The two-fluid model 262
11.6 The intermediate state 262
11.7 Coherence length 263
11.7.1 Coherence length and surface energy 264
11.8 Type II superconductors 265
11.8.1 The mixed state 266
11.8.2 Critical currents 267
11.9 Theory of superconductivity 269
11.9.1 The energy gap in superconductors 270
11.9.2 Electron interactions 271
11.9.3 Zero resistance 273
11.10 Superconducting materials and their applications 274
11.1 0.1 Superconducting magnets 274
xii CONTENTS
Page
11.10.2 A.c. applications 275
11.1 0.3 Other applications 276
11.1 0.4 The future 276
APPENDIX I ELECTRONS IN SOUDS

Al.l The free electron model 278
Al.2 The band model 282
Al.3 Electrons and holes-effective mass 284
APPENDIX II PERIODIC CHART OF THE ELEMENTS 286
APPENDIX III UST OF THE ELEMENTS 287
Bibliography 292
Table of Physical Constants 294
Answers to Questions 295
Index 297
1 Fundamentals
1.1 Introduction
In a treatment of the structure and properties of materials some basic ideas are needed
concerning the properties of electrons in isolated atoms and in solids. In this chapter a
few of these concepts are introduced briefly and simply. They include the wave
mechanical picture of the atom, the idea of quantum numbers and the magnetic
properties of atoms. Finally the energy band model for electrons in solids is introduced.
1. 2 Wave mechanics [1]
In the period between 1900 and 1927 a number of critical experiments involving both
the interaction of light with matter and the behaviour of electrons were successfully
interpreted in a new language, that of quantum mechanics. Ught and electrons are now
regarded as playing a dual role as wave and particle. A beam of light of frequency v
can be thought of as a stream of 'particles' or photons of energy hv where h is a con-
stant. The intensity of the light ig given by the density of photons, or in terms of
the probability of finding a photon at a particular point. These probabilities are
calculated by wave theory on the assumption that the probability is proportional to
the square of the amplitude of the wave. Wave theory becomes a mathematical
technique for calculating photon densities. A wave aspect can also be ascribed to
particles with mass through the de Broglie relation. This suggests that a particle of
mass m and velocity u has an associated wavelength A given by
A =h/mu =h/p, (Ll)

where p is the particle momentum and h is Planck's constant. This constant, having
the value 6 x 10- 34 J s is the same as that occurring in the Planck relation linking the
energy E of a photon with its frequency v
E=hv. (1.2)
The method of solving problems on an atomic scale through the wave aspects of par-
ticles (wave mechanics) was achieved by Schrodinger with his wave equation which in
time dependent form is
-h2- (a a -1/1 +a -1/1) =--+V1/I

h a1/l
2 2
1/1 + 2 2
-- (1.3)
81T m ax 2 ay2 az 2 21Tj at .
2 PHYSICAL PROPERTIES OF MATERIALS
This equation can be looked upon as a standard recipe for describing the wave aspects
of a particle in terms of the amplitude of a wave function 1/1 of its coordinates in
space and time x,y, z and t. In many cases the time can be separated as a trivial phase
factor leaving the time independent form of the equation appropriate to a standing
wave
81T 2 m
v2 1/1(xyz) + T (E - V)1/I(xyz) = 0, (1.4)
where E is the total energy and V is the potential energy of the particle. The use of
eqn (1.4) can best be illustrated by considering its application to one electron as in
the hydrogen atom. The problem is defined by the forces acting on the electron des-
cribed through the potential V, generally a function of the spatial coordinates x, y
and z. The solution provides a knowledge of the energy E of the electron and the
corresponding wave function 1/1 which is a mathematical function in space describing
the three-dimensional wave pattern. Knowing 1/1, the probability of finding the electron
at a point is proportional to 1/1 2 • Wave mechanics indicates that in the hydrogen atom
or any other atom, it is no longer permissible to think of an electron as describing an
orbit in which its motion can be followed in detail. Only probabilities of finding the
electron are significant and wave mechanics allows us to calculate these probabilities
through a knowledge of 1/1 and hence 1/1 2 • In dealing with wave motion of light or
sound the ideas of an amplitude and its square, the intensity of the wave, are familiar.
A 1/1 pattern in one dimension could be just the simple one shown in Fig. 1.1 as a
~-----------\------------~----------~~----------~x
Fig. 1.1 Wave function IJi as a function of distance x.
function of coordinate x. This 1/1 has both a positive and negative part and so if it is
to be interpreted as a probability it makes sense to take the square, since a negative
probability has no meaning. If referred to a single particle, the value of 1/1 2 (x) dx given
by the figure for any range dx is a measure of the probability of finding the particle
in that range. Clearly if we sum 1/1 2 over the range of x from 0 to 00 the result must be
unity if one particle is involved.
For most purposes, it is justifiable to regard an atom as consisting of a stationary
nucleus of charge +Ze surrounded by a cloud of negative charge whose density at any
point is proportional to the probability 1/1 2 of fmding an electron at that point. This
description of an electron cloud still allows the energy of an electron state, a stationary
state, to be computed exactly. Just as a vibrating string can give rise to stationary
vibrations or standing waves only if the wavelengths are related by whole numbers n
FUNDAMENTALS 3
Fig. 1.2 Standing waves on a string of length L fixed at both ends.
to the length of the string (Fig. 1.2), so the wave equation (eqn (1.4)) for the motion
of an electron around a nucleus can give rise to stationary states only if whole numbers
are characteristics of the solution. The whole numbers are quantum numbers reminiscent
of those in the work of Planck and Bohr which now turn up naturally from the solutions
of the wave equation.
1.2.1 The hydrogen atom

Since the proton is so much heavier than the electron it can be considered as a fIxed
centre and the potential energy of the electron is therefore that due to a point charge
+e. Instead of Cartesian coordinates, since the potential has a spherical symmetry, it is
more convenient to use spherical coordinates r, e, cf> (Fig. 1.3).
The potential energy V is a function only of the distance r between the electron and
the nucleus
(1.5)
~---------I-----~~Y
x
Fig.1.3 Spherical polar coordinatesr, 11, cPo
and eqn (1.4) becomes
'i/21/1(r, 0, l/J) + h2 e2 ) 1/I(r, 0, l/J) =0,

2m ( E + 41Tfor (1.6)
where the standard abbreviation h =h/21T has been introduced. In polar coordinates
the full expression looks formidable.
1 a (r2 -a1/1 ) + -1- - a

'i/21/1=-- - ( sinO a1/l)
- + 1 - a2-1/1 (1.7)
r2 ar ar r2 sin 0 ao ao r2 sin2 0 al/J2'
but the full equation can be solved exactly because 1/1 can be expressed as products of
functions of the three variables r, 0 and l/J and these can be solved for separately. So
1/I(r, 0, l/J) = R(r)F(O)4J(l/J) , (1.8)
where R is a function of r only, F of 0 only and of l/J only. Each of these functions
mirrors a motion of the electron in terms of the corresponding coordinate and each
solution throws up its corresponding quantum number n, 1and m,. These quantum
numbers are not independent since although n can be any positive integer, 1can
only have one of the values 0, 1, ... , (n - 1) for each n, and m, can only have one of
the values
m,=-I, -(/- I),' ... ,0, ... , (1- 1),1
for each L Thus, for n = 1, only 1 =0 and m, = 0 are permitted while for n = 2, 1=0 (in
which case m, = 0) or 1= 1 when m, can be either -I, 0 or +1. These rules result from the
general boundary conditions imposed on 1/1 and do not arise from special assumptions for
each particular problem.
The quantization which gives rise to m,
is the simplest case, since there is only one
term in eqn (1.7) which involves l/J. The solution of the resulting differential equation is
4J(l/J)=Ae imlfP , (1.9)

where A is a constant.
Now must have a deflnite unique value for a given l/J and so if that l/J is increased
by any integral multiple of21T, must remain the same. This is only so ifm, is an
integer. Thus it is the mathematical condition on the uniqueness of which quantizes
m, and the same idea applies to n and I.
The quantum number n is called the principal or radial quantum number and 1/n 2
measures directly, in appropriate units, the energy of the electron in its orbit. 1is the
orbital or azimuthal quantum number and measures the angular momentum of the
electron motion. The state for which 1 =0 is not one for which the electron is at rest
but rather one in which the motion is as likely to be in one direction as another,
leading to an angular momentum which on the average is zero. Electron angular
momentum has the value Ih, ti being the basic quantized unit.
For historical reasons, states for which 1=0, 1,2,3,4, 5, etc. are called s, p, d,f, g,
h, etc. The third or magnetic quantum number m, measures the component m,h of
angular momentum in a specifled direction and describes the distribution of 1/1 about
the z axis (Fig. 1.4). As long as the z axis remains undeflned, states of different m, are
indistinguishable.
If however a specific direction is imposed on the atom from outside by application
of a magnetic field, a direction is pointed in space and m,
becomes significant. This
signposting by a magnetic field is possible because of the magnetic properties of the
electron in its orbit. It acts like a small magnet which interacts with the magnetic field
FUNDAMENT ALS 5
(see below, section 1.5). Thus every possible allowed motion of an electron in a
hydrogen atom is described by a specific wave function 1/1, a representation of the
wave pattern in space, itself characterized by three quantum numbers as 1/1 n, l, mr To
each 1/1 there corresponds an energy E which also emerges from the solution of eqn
(1.6). The set of 1/Is and corresponding energies for a given problem represent the
available energy states (or levels) for an electron. An electron in a given atomic state
can jump to another by emitting or absorbing radiation depending on whether the
new state is lower or higher in energy. Observed spectral lines for hydrogen can then
be correlated with electronic transitions between energy levels of the theory. But in
some cases, for example the familiar yellow doublet in the sodium spectrum, it was
clear that the theory should predict transitions from a double level. It was therefore
z
z y
---I~--x x
mr= ± 1
m, = 0
Fig. 1.4. Electron cloud patterns for I = 1 state showing how the limits of significant charge
density (ex",2) depend onml.
necessary to postulate the existence of yet another quantum number which was
attributed by Uhlenbeck and Goudsmit in 1925 to the 'spin' of the electron about
its own axis. This fourth quantum number is called the spin quantum number sand
can only have two components ms = ± ! corresponding to angular momentum !Ii. It
is sufficient to think of this as a motion, not in ordinary space, but in a new spin
space, a necessary corollary to some surprising experimental results. It is comforting
that having invented a fourth quantum number the list is now complete. In a hydrogen
atom, then, an electron state is now described by four quantum numbers n, I, ml and
ms and each state has its own characteristic electron cloud pattern 1/1. The electron
clouds of s states are spherically symmetrical since I and ml are zero and so 1/1 does not
depend on 8 and cpo The state oflowest energy, known as the ground state, is the (IS)l
state (superscript 1 indicating one electron in that state). The electron cloud for this
state is a spherically symmetrical ball of negative charge whose density becomes
negligibly small at distances from the nucleus greater than 2 A. When l*-O the F(8)
function multiplies the R(r) function to give complex shapes to the electron cloud. A
few of the simpler examples are given in Fig. 1.5.
For any given value of n, the general effect of increasing I is to increase the mean
distance of the electron from the nucleus. In the n = 3 quantum states, for example,
the electron is, on the average, closest to the nucleus in the 3s state, and farthest away
in the 3d state.
Note that on this simplified wave mechanical model the energy of any atomic
state is determined only by n. This is a consequence of assuming a strict Coulomb
z z
y y
~--x ----E---x
Fig. 1.5 Typical electron cloud patterns.
potential between the nucleus and the electron. When this assumption breaks down
either through the need to consider interactions involving electron spin, because of
the presence of more than one electron in the atom, or because of the presence of an
external magnetic or electric field, the energy levels are split according to the par-
ticular I, m[ and ms values; in general the lowest I values have the lowest energy for a
particular value of n (see below).
1.3 Many-electron atoms and the Pauli Principle
The problem of the electronic structures of atoms containing more than one electron
is extremely complicated, and accurate calculations exist only for helium. The com-
plications arise from the fact that each electron moves in the field, not merely of the
nucleus, but of all the other electrons. For atoms of low atomic number, it is some-
times a reasonable approximation to assume that each electron moves in the field of
the nucleus, and of a spherically symmetrical negative charge resulting from the
smeared out motions of the remaining electrons. In this case wave mechanics still
gives solutions in which the electronic states are dermed by the quantum numbers
n, I, m[ and ms. The same is assumed to apply to the heavier elements. It is
customary to call electrons in states for which n = 1,2,3, . . ., the K, L, M, ... ,
electrons.
It might at first be thought that the lowest energy of an atom would result from
placing all the electrons in the lowest or (Is) state but this is not so. The distribution
of electrons is governed by the Pauli Exclusion Principle, according to which not more
than one electron can be in a given energy state as defined by all four quantum num-
bers. As the spin quantum number ms can only equal ± !, the Exclusion Principle is
FUNDAMENTALS 7
sometimes expressed by saying that a given energy state, as defmed by the quantum
numbers n, I and m" can contain not more than two electrons and that when it is fully
understood from the following argument. The three quantum numbers n, I and
completely determine the shape of the wave function and hence also the charge
m,
occupied, these must be of opposite spin. The origin of this principle may be partly
distribution. If two electrons have the same values for these quantum numbers their
charge distributions are thus directly superimposed on one another, or in other words
the electrons are 'in the same place' . Now this is energetically a very unfavourable
situation, since the two electrons must repel one another strongly. The repulsion can
be minimized if the electron spins are opposed; their quantum numbers, ma are then
different. It seems that two electrons with counter-rotating spins do not repel one
another very strongly. On the other hand, if their spins are parallel the repulsion is so
strong that they cannot occupy the same position and therefore they must have a
different set of values for n, I and mi.
A combination of the Exclusion Principle with the restrictions on the values of I,
m, and ma leads to the following conclusions:
(a) The maximum numbers of electrons that can be contained in states character-
ized by principal quantum numbers 1, 2, 3, ... , n are equal to 2, 8, 18, ... , 2n2
respectively.
(b) For a given value ofn, the maximum numbers of electrons that can be con-
tained in s,p, d and/states are 2,6,10 and 14 respectively, i.e. 2(21 + 1).
The Pauli Principle is of importance because, by placing a limit on the number of
electrons in a given state, it leads to the concept of completed groups and subgroups
of electrons, and this explains a periodic repetition of properties with increasing
atomic number. The Exclusion Principle applies to molecules and to other assemblies
of atoms in which the electrons occupy quantized energy states, and in all such cases
no state can contain more than one electron as defined by all the quantum numbers,
including the spin quantum number.
1. 3.1 Electron states in multi-electron atoms

The Exclusion Principle may now be used to assign quantum numbers to electrons in
their lowest energy states for different atoms. This procedure leads quite naturally to
the construction of a table which reflects the chemical similarities and differences
between the elements.
Helium has an atomic number of two and so at least one of the quantum numbers
of the second electron must differ from those of the first. On the other hand both
electrons must have the lowest possible energy and both these requirements are met
if the electrons have the following quantum numbers:
first electron n =1 I =0 m, =0 ma =+ !
second electron n =1 1=0 m, =0 ma =-!
This places both the electrons in states with the same wave function, but with opposite
spins.
Atomic number Z = 3 corresponds to lithium. Two of the three electrons will have
the sets of quantum numbers given above for helium. The third electron must have
n =2 I =0 m, =0 ma =+ 1.
This electron can be removed more readily from the atom than either of the electrons
in the helium atom, since less energy is needed to take the electron away to infinity.
While helium is an inert gas, lithium is a reactive metal which readily emits electrons
when heated in a vacuum. In assigning the value 1= 0 to the third electron we have
made use of another rule; in a multi-electron atom the levels with lowest 1 fill up first.
The influence of 1 on the energy is illustrated schematically in Fig. 1.6.
The electronic structure of the elements can now be built up assuming that the
levels are filled sequentially with rising values of n and I. Table 1.1 shows the number
of electrons in each subshell for each of the first 18 elements.
Electron
energy
t- - ----------------------::---::- : -
---------------------------
-~--{=2-===:~=~
i=1=
L-O
l: 0
i=3
----- --- ---- ------- ----,i=1

----L=O
Hydrogen I n=1 n=2 n=3 n=4

Many electron atom
Fig. 1.6 Comparison of lowest energy levels in hydrogen and many-electron atoms.
TABLE 1.1
Atomic number Element K L M

Is 2s 2p 3s 3p 3d
1 H 1
2 He 2
3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 0 2 2 4
9 F 2 2 5
10 Ne 2 2 6
11 Na 2 2 6 1
12 Mg 2 2 6 2
13 AI 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 a 2 2 6 2 5
18 A 2 2 6 2 6
FUNDAMENTALS 9
Certain interesting features arise in Table 1.1. The elements with atomic numbers
2, 10 and 18 are the rare gases which are not merely stable but are exceedingly inert
chemically. Thus we may equate inert characteristics with completely filled shells or
subshells of electrons as is illustrated by the variation of ionization energy. This is
the first indication, as we move down the list of elements, that similar arrangements
of outer electrons appear periodically and that this periodic variation is reflected in
the chemical properties. In fact the periodicity of chemical properties was noted
before the electronic structure of the elements was known ana as long ago as 1870
the chemist Mendeleev devised a way of tabulating the elements which demonstrated
it very effectively. This is now known as the Periodic Table of the Elements.
To construct the Periodic Table the elements listed in Table 1.1 are placed in
horizontal rows so that the outer electron structure changes stepwise along the row.
A new row is begun whenever a p shell has just been fIlled with electrons. Ignoring for
the moment elements one and two this means that each row finishes with a rare gas,
for example, neon with its full2p shell or argon with its full 3p shell. In this way
elements with identical numbers of electrons in their outermost shells appear directly
beneath one another. Thus lithium, sodium and potassium, each with one electron
outside closed p shells, appear in the first column or Group. More remarkably, these
elements all display very similar behaviour-they all are very reactive, are metals with
a valency of unity, and they all form similar compounds with, for example, fluorine
or chlorine. This last point may be amplified by noting the properties of the chlorides;
they all form transparent, insulating crystals, which are readily cleaved to form regular
and similar shapes. They all dissolve, to a greater or lesser extent, in water and they
all have fairly high melting points (about 700°C).
Corresponding similarities also occur between the elements in the second group;
beryllium, magnesium and calcium are all light metals with a valency of two; they
form very stable oxides which have higher melting points than the alkali halides and
they tend to be reactive although not to the same degree shown by the alkali metals.
This unity of chemical behaviour is common to all groups of the Periodic Table
and not just those discussed above.
1.4 Transition elements
So far the discussion has been carefully limited to the first three rows of the Periodic
Table plus potassium and calcium. The reason is that although the periodicity of
properties continues beyond this point it is not exemplified in such a simple fashion.
The arrangement of the electrons for the elements of Z = 19 to 29 are shown in
Table 1.2, and an anomaly is immediately apparent. The rule concerning the order of
filling the various levels has been broken and instead of the outermost electrons of
potassium and calcium entering the 3d shell, they go into the 4s shell. Only when the
4s shell is full do electrons begin to enter the 3d shell-there is one 3d electron in
scandium, two in vanadium, etc. Elements which possess a partially filled 3d shell are
termed transition elements and constitute the first transition series.
The reason for this oddity is that the 4s levels have lower energy than the 3d levels
and so they fill first in keeping with the minimum energy principle. This is illustrated in
Fig. 1.6 where it can be seen that the 4s level is below the 3d level. Further irregularities
occur at Z =24, chromium, and Z = 29, copper, each of which contains only one 4s
electron instead of two. This is due to the fact that the exactly half-f!lled 3d shell and
the filled 3d shell are particularly stable configurations compared to the neighbouring
occupancies of four and nine electrons respectively.
TABLE 1.2
Atomic number Element Electron configuration

(Filled K and L shells)
19 K 3s 2 3p6 Jdo 4s 1
20 Ca 3s 2 3p6 Jdo 4s 2
21 Sc 3s 2 3p6 Jd1 4s 2
22 Ti 3s 2 3p6 3d 2 4s 2
23 V 3s 2 3p6 Jd3 4s 2
24 Cr 3s 2 3p6 3dS 4s 1
2S Mn 3s 2 3p6 Jds 4s 2
26 Fe 3s 2 3p6 Jd6 4s 2
27 Co 3s 2 3p6 Jd7 4s 2
28 Ni 3s 2 3p6 Jd8 4s 2
29 Cu 38 2 3p6 Jd10 4s 1
These transition elements, with their incomplete 3d shells do not fit quite so neatly
into the Periodic Table and so they are left on their own as illustrated in the periodic
chart of Appendix II.
Having dealt with the first series of transition elements, it is not surprising to fmd
another series in the fifth row of the table, and also in the sixth. The latter series, how-
ever, is more complicated owing to the filling of the two inner sub shells (4f and Sd-see
Appendix III) before the 6p shell begins to fill. Here the series of elements from Z =57
to 71, in which the 4f shell is being filled, have almost identical chemical properties
and as a group they are called the rare earth metals or the lanthanide series. The reason
for their chemical similarity is that these atoms differ only in the number of electrons
in a shell which is far removed from the outermost electrons while it is the latter which
determine the chemical behaviour. Their almost indistinguishable qualities place them
all into one pigeon-hole in the Periodic Table.
Another group of elements similar to the rare earths is found in the seventh row of
the Periodic Table, although the majority of these elements do not occur in nature-
because their nuclei are unstable-they have, however, been manufactured artificially.
The elements in this last series are often referred to as the actinide elements because
they have properties similar to actinium, the first of the series.
1.S Atomic magnetism
The orbital and spin magnetic moments of an electron are a consequence of the orbital
and spin angular momenta. It is a relatively easy matter to deduce the magnitude of
the magnetic moments in terms of the appropriate quantum numbers and the results
are
Jlorb =- m,(eh/41rm) (LlO)
and
Jlspin =- gm,(eh/41rm). (Lll)
The factor g is a multiplying factor which is found to be necessary to bring the relation
for spin moment into line with that for orbital moment. It has the value of almost
exactly 2 and is called the Lande splitting factor. Since m,
is an integer, the quantity
FUNDAMENT ALS 11
eh/41Tm can be regarded as a natural unit of magnetic moment, the Bohr magneton,
/lB, and has the value 9.27 x 10-24 amp m2 .
The magnetic moments of single atoms will be considered before the magnetic
properties of a lattice of atoms are discussed. To obtain the total magnetic moment
of an atom we have to add up the magnetic moments of the electrons in it taking into
account the fact that the direction of the moments is given by the sign of ml and ms.
Thus closed shells of electrons having equal numbers of electrons with positive and
negative values of ml and ms have no net magnetic moment since each electron cancels
another. This is illustrated for a p state in Table 1.3, where the dipole moment of
each electron is represented by an arrow. Therefore, the first important rule to note
is that a net magnetic moment comes only from incomplete electron shells.
TABLE 1.3
Electron 1 2 3 4 5 6
ml - 1 - 1 0 0 +1 +1
Moment due to ml t t t t
ms +.!2 1
-1" +.!2 1
-1" +.!2 1
-1"
Moment due to ms t t t t t t
Now the valence electrons together form an incomplete shell so that one might
expect all but the rare gases to exhibit net magnetic moments. However, this is true
only for atoms in isolation, i.e. in the gaseous state, for when solids are considered only
a few elements are found which are permanently capable of retaining a magnetic
moment at room temperature. If all the elements are studied at very low temperatures
many more are found to be magnetic, and if compounds are included yet more
materials are found to be strongly magnetic. However, with one or two exceptions,
all the permanent magnetic materials (including compounds) contain at least one
transition element.
The distinguishing feature of a transition element is that one of the inner electron
shells is incomplete and this suggests immediately that the inner incomplete shell is
the one which gives rise to the atomic magnetic moment while the valence electrons
are of no importance. This characteristic of the valence electrons is just a reflection of
the properties of atomic bonding since atoms bond together in such a way as to form
closed shells of electrons which have no magnetic moment.
Before calculating the magnetic moment of an atom due to an incomplete inner
shell the values of ml and ms for the electrons in the unftlled shells must be considered
because, in the filling of energy levels in multi-electron atoms earlier, no indication was
given as to the sequence of ftlling energy levels in a subshell. The rule governing this
was first deduced from the emission spectra of such elements, and it is known as
Hund's rule after its discoverer. Hund deduced that the different m1levels are filled
first with electrons having the same ms value, that is ms = ~. The electrons arrange
themselves among the levels to give the maximum possible total spin angular momentum
consistent with Pauli's Principle. Thus there must be some form of interaction between
electrons when they have different wave functions which tend to make their spin axes
parallel.
As an example consider the second element in the first transition series, namely
titanium, which has two 3d electrons, with, according to Hund's rule, quantum numbers
ml =-2, ms =! and ml =-1, ms =~. The total orbital magnetic moment is the sum of
these two electron contributions, i.e.
Il orb = IlB + 21lB = 31lB (1.12)

and the total spin magnetic moment is similarly given by
. = IlB
11 spm + IlB = 21lB· (1.13)
Nothing has been said about the way in which the orbital and spin magnetic moments
combine to give a total magnetic moment for an atom. In general this combination is
too complicated for consideration here, and it is unnecessary if attention is confined to
the 3d transition series because the orbital magnetic moment disappears in the solid
state. This is because each atom in the crystal experiences an electric field due to the
charges on all the neighbouring ions. The electric field alters the shape of the wave
functions, and makes the total orbital angular momentum process in such a complicated
way that, on average, there is no net component of orbital magnetic moment along
any direction. The spin magnetic moment, on the other hand, is not affected by the
electric field. Hence the magnetic effect is attributable to the effective spin moment
per atom. This so-called 'crystal field' does not affect the orbital motion of the magnetic
electrons in the 4ftransition metals because these electrons are deeper inside the atom
and are shielded by the 5d and other electrons. The spin direction and net spin magnetic
moments in the 3d transition series are shown in Table 1.4.
TABLE 1.4
Element K Ca SC Ti V Cr Mn Fe Co Ni Cu
No of 3d
electrons 0 0 2 3 5 5 6 7 8 10
Spin directions - tt ttt ttttt ttttt tttttj, tttttH ttttttH tttttHtH
Magnetic
moment in
Bohr
magnetons 0 0 2 3 5 5 4 3 2 0
The experimental values for the magnetic moment per atom are less than the
theoretical values in Table 1.4 because the broadening and resulting overlap of the
3d and 4s energy bands in the solid state affects the electron distribution between the
various levels.
1.5.1 Diamagnetism
Diamagnetism is a property of all atoms because of the influence of an applied magnetic
field on the motion of electrons in their orbits. It is a very weak effect and in solids is
often masked by other kinds of magnetism.
Consider an electron moving around a proton in an orbit of radius r (Fig. 1.7) with
angular frequency w in the absence of a magnetic field. There is a magnetic moment 11
associated with the motion of the electron
J1 = current x area
(1.14)
= (-we/2rr) x rrr2.
When an external magnetic field H is applied there is a flux change through the orbit
and by Lenz's law an electric field is set up to oppose this change. Note that this
FUNDAMENTALS 13
happens only while the magnetic field is changing from its zero value to the steady
value H The electric field affects the motion of the electron by exerting a force on
it which changes its angular momentum. The change in angular frequency thus effected
Fig. 1.7 Electron orbit around a proton and the associated magnetic moment iJ..
is called the Larmor frequency and has the value eB/2m where B is the flux density
appropriate to Hand m is the electron mass. The corresponding induced magnetic
moment is opposed to the original magnetic moment /l of the electron in its orbit
when H = O. Since this behaviour is a property of electrons in all materials it leads to
a diamagnetic susceptibility which is very small and negative (Chapter 9).
1.5.2 Paramagnetism
As discussed above, each electron in an orbit has an orbital magnetic moment /lorh and
a spin magnetic moment /lspin. In atoms with filled electronic shells there is no net
magnetic moment but where shells are unfilled there is such a moment. In the absence
of a magnetic field the net moments of the atoms usually point in random directions
because of thermal fluctuations, producing no macroscopic magnetization. When a
field is switched on, there is a tendency for the dipoles to align with the field giving
an induced positive dipole moment which is proportional to the field. The component
of each individual electronic moment in the field direction is governed by the rules of
quantum mechanics and a theoretical calculation of the net moment where both orbit
and spin are contributing can be complicated. The induced magnetisation is the
source of paramagnetism and materials whether gases, liquids or solids, show a
paramagnetic susceptibility (Chapter 9) whenever the paramagnetic atoms can
respond individually to an external field without interaction with their neighbours.
1. 5. 3 Exchange
So far the discussion of the magnetic moments of atoms has assumed that each atom
behaves quite independently of its neighbours with no interaction between them.
However, the electron clouds of two neighbouring atoms of a solid can overlap to some
extent on a wave mechanical picture. If, for example, two adjacent transition metal
atoms are considered, the wave functions of the 3d electrons in the unfilled shells have
characteristic lobes which assist overlap (Fig. 1.8). It is important in these cases to
consider what influence the overlap of charge has on the energy of the system of two
adjacent atoms. Suppose there is one 3d electron on atom A and one on atom B (Fig.
1.9). The energy of interaction depends directly on the Coulomb forces acting between
the charge clouds and this is expressed in wave mechanical language as an integral
involving the wave functions of electron 1 and electron 2. But these wave functions
z z
,.c;....,_ _ _ _ X
.!I.IWIr---X
Fig. 1.8 Typical d wave functions.
Electron 1 Electron 2
Overlap
• •
region
Atom A Atom B
Fig. 1.9 Overlap of charge clouds of d electrons on adjacent atoms.
also intimately involve the spin of the electron and so the expression for the energy
is found to involve both Coulomb effects and spin inextricably bound together. So to
minimize one involves some restriction on the other. The details of the theory show
that the new term in the energy which appears because of the intermingling of the
wave functions can be written in a simple way as
(1.15)
where Eex is the contribution to the energy from the exchange interaction as it is
called, J represents an integral which involves the wave functions of the electrons and
the potential and in principle is known either through calculation or measurement,
and SA and SB are the spins associated with the electrons in question, but written in
quantum mechanical language as vectors.
As always, the favoured situation is the one with the lowest energy and it turns out
that because there are two ways in which the wave functions can combine there are
two possibilities for lowering the energy by Eex. These are:
(a) If J is positive and the spins are parallel (tt). This is the situation leading to
ferromagnetism because if two neighbouring spins are held parallel by the
exchange interaction, then their neighbours in turn will also be parallel by the
FUNDAMENTALS 15
same kind of pair interaction even though it does not extend beyond nearest
neighbours. In this way a whole line of spins can be parallel even though the
interaction acts only between nearest neighbour pairs (Fig. 1.10).
(b) If J is negative and the spins are antiparallel (t "'). This situation leads to anti-
ferromagnetism (Fig. 1.11). (See also Chapter 9.)
Fig. 1.10 Lining up of successive spins by pair interaction (J> 0).
Fig. 1.11 Antiparallel arrangement of spins (J < 0).

I
A graph of J against interatomic distance rAB (Fig. 1.12) shows how delicate is the
balance between ferromagnetism and antiferromagnetism and why there are so few
ferromagnetic metals. All others have the wrong value of J. If r AB is too big there is
no overlap of charge clouds and negligible exchange interaction. If rAB is too small J
tends to become negative. A proper calculation of J is extremely difficult and the
assumptions made in the derivation of the curve of Fig. 1.12 have been criticized.
Fig. 1.12 Variation of exchange constant J with interatomic distance.

Subsequent calculations have cast doubt on the exact form of the radial dependence
of J. Without quantum mechanics there would be no explanation for ferromagnetism
even though a detailed understanding of the phenomenon has not yet been achieved.
The same idea leads to Hund's rules for spins in unfilled shells of the same atom where
the preference is for parallel alignment as far as the Exclusion Principle allows.
1.6 Electrons in solids
The task of determining the behaviour of electrons in a solid reduces essentially to the
determination of the quantum mechanical states of the solid and the way in which
these states are occupied by electrons. For electrons numbering about 1028 1m3 , all
interacting with one another, the exact solution of this problem is at present impos-
sible to achieve. However, the use of simple models and approximate methods can
help considerably. Here a simple introduction is given to the energy band model of a
crystalline solid. In Appendix I the same model is derived from a different starting
point using the wave picture of the electron and with the aid of some mathematics.
The ideas developed in this appendix are of fundamental importance for a proper
understanding of the behaviour of electrons in crystalline solids.
Energy
~
:
:, ,.....------
~::==~~!!!~_
,,
Outer
electron
levels
,
I
I
Inner
electron
levels
RO Atomic spacing
Fig. 1.13 Energy level splitting as a function of atomic spacing.
Consider a small number of widely separated identical atoms which are gradually
brought together to form a large molecule. At infinite separation the atoms are
independent and have electron energy levels appropriate to single atoms. As the atoms
move closer together the electrons and nucleus of each begin to be increasingly
influenced by those of neighbouring atoms. In a hypothetical six-atom molecule, for
example, a single atomic energy level becomes one which contains six components,
one from each atom, and this can be occupied by six electrons. But the interactions
within the molecule slightly modify the level structure so that the single sixfold level
is broadened into six separate levels spread over a range of energy. The disturbance of
the atomic level structure and degree of broadening depends on the atomic spacing.
Figure 1.13 illustrates the situation for a typical inner electron and outer electron
level as a function of atomic spacing. The outer electron levels split at larger separa-
tions because their charge clouds have a greater radial extent. On average the energy
FUNDAMENTALS 17
levels must move down on the energy scale as the atoms are brought together because
the energy of the solid must be less than that of the individual atoms for stability of
the molecule. The spacing Ro represents that for a stable structure in this case.
In a crystal of N atoms, where N -1 026 the same effects take place, each atomic
level splitting into N levels. The average energy decreases with interatomic spacing
until the atoms are at their equilibrium separation. The N associated levels in any
group lie close together and form a 'band of allowed energies'. In general each band is
separated from neighbouring bands by a 'forbidden band of energies'. The energy
range of these bands at the equilibrium separationRo is shown in Fig. 1.14. Note that
the outer or valency electron levels form the broadest highest energy bands.
Figure tI.1S shows the actual situation for sodium metal. Electron charge clouds of
electrons in the deeper atomic levels overlap hardly at all and so lead to very narrow
bands with N levels packed into a very narrow energy range. Usually these electrons
are not of great interest as they do not partake in thermal and electrical phenomena.
Energy ",",,"7"7"7"7"7"7""7"7"7"7"7"7""7"7"7"7"7'7"
Allowed
bands
Fig. 1.14 Energy bands in a solid.
'~--
Energy
• I •• -- ••••• 3P
.' 3s
,
,
I
~----r----- 2p
Atomic
spacing
Fig. 1.15 Band structure for sodium.
Since the Exclusion Principle applies to the crystal as a whole, only two electrons of
opposite spin can be in any given energy level in the band and the levels are filled from
the lowest state upwards. At the absolute zero of temperature all the electron states
will be m.led to an energy known as the Fermi level. At higher temperatures some
electrons near the Fermi level may be thermally excited into levels just above it. The
uppermost partially filled band is called the Conduction band because the electrons
in it are able to receive energy from an applied electric field and give rise to an electric
current. The highest filled band, at the absolute zero of temperature, is referred to as
the valence band because the electrons then filling it are valency electrons involved in
bonding. As an example consider lithium in which the outer band will correspond to
the broadened 28 level so that a crystal of N atoms could accommodate 2N electrons
in this band. But each lithium atom contributes only one electron to the band so that
N electrons only fill half of the available states in the outer band lithium is therefore
a good conductor because the electrons at the Fermi level have empty states above
them immediately available for occupation under the influence of an applied electric
field. In some conductors the valence band is full but overlaps a higher empty band
so that electrons are still free to absorb energy and move into higher states.
E"·~'l
Empty
conduction
band
Empty
T
rEmptybandl
, overlaps I
'valence band,
conduction
band 1
Forbidden gap Eg
Forbidden
gap
,.------.,
1
Eg>2eV
Partially
valence orfilled Empty
_____levels Ferml. IL _ _ _ _ _ J'
Full T Full
conduction Occupied level Valence valence valence
band levels band band band
(I) Conductor (II) Conductor (III) Semiconductor (IV) Insulator

e.g. lithium e.g. magnesium e.g. silicon e.g diamond
Fig. 1.16 Simplified energy band diagrams for conductors, semiconductors and insulators (inner
electron bands not represented).
When a forbidden energy gap separates a filled valence band from an empty con-
duction band, no electronic activity will be observed unless electrons in the lower
band are supplied with sufficient energy to enable them to surmount the gap. Thus
the width in energy of the gap is critical in determining the electrical or optical
properties of the material. If the gap is a few electron volts wide the material is an
electrical insulator for moderate electric fields and ordinary temperatures. If the gap
is sufficiently small the effect of thermal excitation may transfer a few electrons into
the conduction band creating a few vacant states (holes) in the valence band. Such a
material is a semiconductor, the difference between this and an insulator being simply
the width of the gap. Typically, materials with an energy gap ofless than 2 eV would
be regarded as semiconductors. Silicon is a semiconductor with an energy gap of 1.1 eV
while diamond is an insulator with a 7 eV gap. Fig. 1.16 illustrates the situation in
several cases.
Reference
1. Mott, N. F. Elements of Wave Mechanics, Cambridge University Press (1952).

2 Structure of Solids
2.1 Introduction-atomic bonding
From experience one knows that solids are usually moderately strong, slightly elastic
structures. Thus the individual atoms must be held together in solids by interatomic
forces or bonds. However, in addition to these attractive forces there must be a
repulsive force because solids are not easily compressed.
The attractive forces between the atoms are basically electrostatic in origin and the
classification of the different types of bonding is strongly dependent on the electronic
structure of the atoms concerned, and hence directly related to the Periodic Table.
There are basically four classes into which these attractive bonds can conveniently be
divided, although the boundaries between them are not always distinct:
(i) ionic bonding,

(ii) covalent bonding,
(iii) metallic, or unsaturated covalent bonding, and
(iv) van der Waals bonding.
The attraction between the atoms brings them closer together until the individual
electron clouds begin to overlap and a strong repulsive force arises to comply with
Pauli's Exclusion Principle. When the attractive force and the repulsive force between
any two atoms are equal, the two atoms should be in a stable situation with a minimum
potential energy.
Consider two atoms in their ground states with an infinite separation, and con-
sequently an interaction potential energy equal to zero. As the atoms are brought
closer together, the potential energy of either atom will be given by
V ={decrease in potential energy} + ( increase in potential energy}

due to attraction due to repulsion
and in the case of a simple type of interatomic potential this can be written as
A B
V=--+- (2.1)
r" ,m'
where A , B, n and m are constant in any specific case. In order to give a minimum
potential energy condition at the equilibrium separation '0, m must be greater than
n so that 3 2 Vj3,2 is positive. The resultant force of interaction, F, is given by
F=- avia" (2.2)
so that
nA mE
F = - - +-_. (2.3)
rn+ 1 r m + 1
Equations (2.1) and (2.3) can be represented graphically as shown in Fig. 2.1.
At the equilibrium separation the net force is zero, i.e.
nA/r~+1 = mB/r[['+l. (2.4)
F V
I I
Force Energy
I I
I I
I Repulsive energy
\ /"" Repulsive force
\/
\ \
k
\
Resultant force
\
X .... ----- Resultant energy

....
, ,
.... -- ---
'0
0 0
I
, .... .... "" ,;-

.... .....
""
;
,"
;
, / ........... Attractive force

/, ............... Attractive energy
I
I
,
I ,
I
Fig. 2.1 Force and potential energy as a function of distance between two atoms.
The minimum value of the energy Vo , is the bonding energy of the system and is
approximately equal to the heat of dissociation of the molecule. Typical values are
given in Table 2.3.
The four classes of atomic bonding will now be discussed in more detail.
2.1.1 Ionic bonding

An ionic bond can only be formed between two different atoms, one electropositive
and the other electronegative. Electropositive elements readily give up electrons and
are usually Group I or II elements, e.g. Na, K and Ba, whereas electronegative elements
readily take up electrons and are typically Group VI or VII elements, e.g. CI, Br and 0.
As an example of the ionic bond consider a molecule of common salt, NaCl. When
Na and CI atoms are brought together it is easy for the outer valence electron of the
sodium atom to be transferred to the chlorine atom making both more stable rare gas
electronic configurations and lowering the overall energy (Fig. 2.2). There is then an
electrostatic attraction between the two ions, since the sodium cation carries a positive
charge and the chlorine anion a negative charge.
Other typical ionic compounds include MgO, CuO, Cr02 and MoF 2 . In MgO the
ions are doubly ionized leading to a stronger interatomic bond and hence a higher
melting point, 28000 C compared with 8000 C for NaCl.
STRUCTURE OF SOLIDS 21
(a)
(b)
Fig.2.2 (a) Individual atoms (denoting the inner closed shells as a solid sphere). (b) Ionic molecule
(force of attraction = -e 2 /4,"EOr02).
2.1.2 Covalent bonding

Elements from the central groups of the Periodic Table, notably Group IV, are not
readily reduced to a closed shell electronic configuration because the energy required
to remove all the valence electrons is too large, and so ionic bonding is unlikely. How-
ever, it is still possible for each atom to effectively complete its outer electron shell
by sharing electrons with its neighbours. This sharing of electrons gives rise to covalent
bonding. As an example consider germanium which has four electrons in the outer
shell. Four more electrons are required to fill this shell and this can be done by sharing
an electron with each of four neighbours as shown schematically in Fig. 2.3. Electrons
of opposite spin pair up in these bonds so there is no violation of Pauli's Exclusion
Principle and the attractive force arises from the interaction of these anti-spin electrons.
The electrostatic repulsion between the four electron clouds means that they try to
concentrate themselves in space as far away as possible from one another, so that the
four bonds arrange themselves pointing towards the corners of an imaginary tetra-
hedron. This directional nature of the bonds plays an important role in the resulting
crystal structure as will be seen later. Although the outer electron structure of Ge is
48 2 4p2, four and not two bonds are formed because there is a rearrangement of
orbitals called hybridization and four identical (sp) hybrid orbitals result.
The other Group IV elements, notably silicon and carbon are bonded in a similar
manner and some compounds of elements from Group III and Group V, e.g. GaAs
and InSb form similar tetrahedrally coordinated covalent bonds, although the bonding
in these latter cases may be partially ionic.
Inner
closed
shells
• electron spin = + 1/2
o electron spin = - 1/2

Fig. 2.3 Schematic representation of covalent bonding in two dimensions. In anyone atom the
four outermost electrons are all unpaired and have the same spin, e.g. t; these electrons pair up
with electrons from other atoms with spin -to
2.1.3 Metallic (unsaturated covalent) bonding

In the case of elements from Group I of the Periodic Table, e.g. sodium with just one
outer valence electron, at least eight atoms must be brought together before there are
sufficient outer electrons available to form one closed shell. However, there would
then be insufficient electrons to fIll all the possible orbits around the eight atoms and
each atom would, in effect, only contribute one-eighth of an electron to each bond.
Covalent bonds of this type are unsaturated. One representation of the metallic bond
is of a time averaged fluctuating covalent bond, i.e. the valence electron of each atom
spends only part of the time forming a bond between any two given atoms, since it
must form bonds with other atoms during the rest of the time. Thus no valence
electron can be associated with a specific atom and these valence electrons are free
to move throughout the structure. Materials bound in this manner are good conductors
of electricity and heat, and are invariably metals; hence the term metallic bonding.
The positively charged ions that are left behind by these migrating valence electrons
are held together by their attraction to this cloud of negative electrons in which they
are embedded rather like ball-bearings in a liquid glue. These metallic bonds are not
directional unlike the covalent bond. Theoretically it can be shown that the wave
functions of the valence electrons are so spread out that these electrons can no longer
'belong' to anyone nucleus in the solid but are a property of the solid as a whole.
This delocalization of the valence electrons leads to a decrease in both kinetic and
potential energy and it is this energy decrease that is responsible for metallic bonding.
This is the basic type of bonding in all elements of Groups I, II and III of the Periodic
Table, although as the number of valence electrons increases the bonding tends to
become partially covalent.
2.1.4 Van der Waals bonding (molecular bonding)
The rare gases, for example argon and helium, condense to form solids at sufficiently
low temperatures, although their closed shell electron configurations eliminate all
three of the types of bonding discussed so far. There must therefore be another kind
of bond in which no major modification of the electronic structure takes place. This
bond is often referred to as a secondary bond because it is so weak.
In a single atom, the electrons are continually moving around the positive nucleus
and at any given instant of time the centre of the negative charge distribution may not
coincide with the centre of the nucleus. Hence the atom may have an instantaneous
electric dipole moment, although the average dipole moment over a period of time will
be zero. When two atoms approach one another the rapidly changing dipole moment of
each will affect the motion of the electrons in the other atom. A lower potential
energy, i.e. attraction, results if the changes occur in sympathy with one another.
Obviously this type of interaction can occur over comparatively large distances
since there is no need for the electron clouds to overlap one another. Hence it is
apparent even in the gaseous state where it causes deviations from the perfect gas laws.
The modified gas equation proposed by van der Waals incorporates its effects and
thus the force takes his name. Van der Waals forces are present to some extent in
all solids, for example in ionic solids the primary electrostatic attraction between
the ions varies as l/r2 but there is also a small van der Waals force which varies
approximately as l/r7 .
In organic solids the molecules comprising the solid may also have permanent
dipoles and the interaction between these dipoles accounts for the cohesive force.
One type of permanent dipole interaction deserves a special mention and that is
the so called hydrogen bond which occurs only when a hydrogen atom is present in
the dipole. Consider, for example, the water molecule, H2 0, where the electrons
shared between the oxygen and hydrogen atoms tend to stay closer to the oxygen
atom than the hydrogen atoms because of the greater electronegativity of the oxygen.
As a result, the oxygen atom acts as the negative end of the dipole and the hydrogen
atoms act as the positive end. The positive end can then attract the negative end of
another water molecule and therefore bond the molecules together. Since the proton
in the hydrogen atom is not shielded by other surrounding electrons it can be attracted
quite strongly to the negative end of another dipole, and so the bond is relatively
strong compared with other dipole-dipole interactions. The hydrogen bond is important
in many biological molecules such as DNA, where it helps to control the possible pair-
ings between the strands of the molecule, and in certain ferroelectric crystals.
2.2 Crystal structure [1]
Historically the study of crystal structures began in about 1700 with the study by
metallurgists of the external form or morphology of crystals. Even before the applica-
tion of X-rays to crystallography it was assumed that the geometrical regularity of
many crystals (e.g. the cubic form of sodium chloride) was the result of a correspond-
ing regularity of atomic structure within it. X-ray studies have confirmed this and
enabled a very detailed picture of the arrangement of the atoms in most materials to
be deduced. The technique of X-ray crystallography will be discussed in more detail
in the next chapter.
Before discussing the possible crystal structures the meaning of crystalline order
will be made clear. In a crystal it is possible to choose a small group of atoms or
molecules which can be assumed to be contained in a regular-sided 'box' or unit cell.

If many such 'boxes' are stacked together all in the same orientation, like bricks, the
atoms are automatically placed in their correct position in the crystal. This regular
array may be continuous throughout the whole specimen, i.e. a single crystal, or the
specimen may be split up into regions or grains in each of which the order is complete,
but the orientation is different in the various grains, i.e. a polycrystalline specimen. If
the atoms are arranged randomly with respect to each other the material is termed
amorphous, e.g. glass, where the ordering is only very slight.
Crystals of minerals were originally classified according to their external symmetry
into seven crystal systems (six in the USA). The allocation of a crystal to one of the
seven systems was determined by the equality or inequality of the lengths of the unit
cell edges (a, b, c) and according to whether or not the angles (a, (j, 1) between
the edges were, or were not, right angles. Before the advent of X-ray crystallography
the unit cell was inferred from measurements of the crystal angles and the anisotropy
of various physical properties. The characteristics of the seven systems are summarized
in Table 2.1.
TABLE 2.1
Crystal system Unit cell Examples
Triclinic a -4=b-4=c CuS04·SH20

Q-4=(j-4='Y
Monoclinic a -4=b-4=c CaS"04· 2H 20
Q ="1 = 90° -4= (j
Orthorhombic a -4=b-4=c KN03
Q = (j = "1 = 90°
Tetragonal a =b-4=c Sn, Ti0 3
Q = (j ="1 = 90°
Cubic a =b =c Au, NaCI
Q = (j = "1 = 90°
Trigonal (rhombohedral) (note: trigonal a =b =c
can be regarded as a class of hexagonal) Q=(j='Y-4=90°
Hexagonal a=b-4=c Zn, graphite
Q = (j = 90° "1 = 1200
b
L~---
As a result of pure symmetry considerations Bravais showed that corresponding
to these there were only fourteen different types of fundamental network, or unit
cell, which could be built up to form an extended three-dimensional lattice, in
which the surroundings of each of the lattice points are identical.
These fourteen different unit cells include the seven so-called primitive unit cells
which have lattice points only at the corners. Translational repetition in space of each
of the unit cells constructs a Bravais lattice. The repeat distances are the unit cell
edges a, band c and are called the lattice parameters. The unit cells of the fourteen
Bravais lattices are illustrated in Fig. 2.4. Although the symmetry of these lattices
varies considerably they all have one element of symmetry in common in that they
all possess a centre of symmetry. This is defined as a point in the interior of the lattice
through which every lattice point can be taken to an equidistant lattice point on the
other side of the lattice.
Turn no)V from these purely geometric networks of lattice points to the actual
crystal structure exhibited by materials. In general each lattice point is associated with
a group of atoms or molecules rather than just one atom, and the many different
geometric arrangements possible mean that there are far more than just fourteen
different types of crystal structure. In many cases the resulting crystal structure does
not show the full symmetry associated with the basic crystal structure. For example,
in cases where complex molecules with asymmetric shapes are associated with the
lattice points the resulting crystal structure may no longer have a centre of symmetry.
P - primitive -only lattice

points at the corners
I -lattice point at the centre
F -lattice points in centre
of every face
Primitive Body centred Face centred C -partially face centred

F
[jJ ~ CWfJ]
Cubic: P I
/
I "' /
... 1 __ /~_:::
P C
P
Tetragonal Orthorhombic:
Trigonal
P C
Monoclinic: (Rhombohedral)
Hexagonal Triclinic
Fig. 2.4 The unit cells of 14 Bravais lattices. (The lattice points are represented by dots.)
This has important consequences, because the absence of a centre of symmetry is a

necessary requirement for such phenomena as pyroelectricity, piezoelectricity and
optical activity.
2.3 Lattice planes and directions
Although the description of atom positions in a unit cell is a complete description of

the crystal structure, it is useful to have a means of describing a plane, such as the
cube faces in the face centred cubic (f.c.c.) structure, and specific directions in a
crystal. For this purpose, a system of crystallographic indices known as Miller indices
has been developed. Since primary interest in lattice planes is confined to the major
planes in the unit cell of a crystal they are defined in terms of their intercepts on the
three translation vectors.
Any plane A 'B' C' (see Fig. 2.5) can be defined by its intercepts OA', OB' and OC'
on the three principal axes of the unit cell OA, OB and OC. The usual notation is given
by taking the reciprocals of the ratios of these intercepts to the unit cell parameters.
D ~---Rr-----r,
8
+"'---- Y
Unit cell
OA = a
A~-------------' OB = b
OC = c
x
Fig. 2.5 Designation of a crystal plane by Miller indices.
Thus the planeA'B C' is denoted by (OA/OA' OB/OB' OC/OC') which in general is
written as (hkl). If OA' = a12, OB' = bl4 and OC' = cl2 then the plane A 'B' C' is the
(1/1 II! liD or the (242) plane.
Similarly a plane (ABC) with intercepts OA, OB and OC is the (OA/OA OB/OB
OC/OC) or (111) plane, and the plane DFBA is the (OA/OA OB/OB OCloo) or (110)
plane, Le. a plane parallel to an axis is taken to intercept that axis at infinity. If the
intercept is negative then the corresponding Miller index is also negative and is denoted
by placing a bar over the numerical value, e.g. 2. The indices of the sides of a unit cell
of a cubic lattice are (100), (100), (010), (010),(001) and (001) and these are equiva-
lent planes of the same form and are collectively represented by {100}. Further examples
of planes in the cubic system are illustrated in Fig. 2.6.
(a) (020) (b) (110) (c) (210) (d) (132)

Fig. 2.6 Lattice planes in the cubic system.
In the hexagonal system an alternative indexing system, which has four numbers in
each set of indices, is often used because it more readily shows the hexagonal symmetry.
The four axes used to define the indices are the vertical axis of the hexagonal prism
and the three axes in the base, the latter being 1200 apart as illustrated in Fig. 2.7.
Fig. 2.7 Four axes in the hexagonal system.
The indices of a plane are denoted by h, k, i and I where these indices are the
reciprocals of the intercepts on the a, b, d and c axes respectively. Since only three
noncoplanar axes are necessary to specify a plane in space, these four indices cannot
be independent and they must satisfy the additional condition that h + k = - i. Thus
the base plane in a hexagonal unit cell is the (0001) plane and the vertical prism planes
belong to the {lOlO} family.
It should be noted that all these indices represent a set of equidistant parallel
planes since our reference unit cell could be chosen anywhere in the crystal. In X-ray
crystallography (see Chapter 4) interest lies in the interplanar spacing of these planes,
which is defined as the perpendicular distance from the origin to the plane, i.e. a
similar imaginary plane is assumed to pass through the origin. The indices (nh, nk and
nl) where n is an integer, therefore represent a family of planes which lie parallel to
the family (hkl) but with an interplanar spacing lin of that of the latter. Note that as
far as the external morphology of the crystal is concerned the (111) and (222) planes,
for example, are identical and so it is common in this case to reduce the indices to
their lowest form.
The direction of a line in a lattice with respect to the unit cell vectors can be des-
cribed using a similar notation. The indices of a direction are simply the vector com-
ponents of the direction resolved along each of the coordinate axes,expressed as

multiples of the unit cell parameters and reduced to their simplest form. They are
denoted by [hkl]. For example several common directions are illustrated in Fig. 2.8.
In the cubic system all the directions and planes with identical indices are perpen-
dicular but this is not true in any other system.
-r---b
[110]
a
Fig. 2.8 Lattice directions.
2.4 Atomic packing
The role of interatomic bonding forces in the structure of materials will now be con-
sidered. The atoms in a solid state may be regarded for most purposes as rigid spheres
with all the atoms of one element having identical size. An obvious starting point is,
therefore, the consideration of the kinds of structure that can be built up by packing
identical spheres together as closely as possible. This is especially valid for metallic
and van der Waals bonded solids of identical atoms where the bonding is non-
directional.
A single layer of spheres, pushed together, arrange themselves in a hexagonal close
packed network with six nearest neighbours as illustrated in Fig. 2.9. This layer offers
recesses into which additional spheres can rest to form a second layer. It can be seen,
however, that this second layer will occupy all the X sites or all the Y sites ( occupation
of the X sites is illustrated in Fig. 2.9). A third layer is again presented with alter-
natives, either the spheres can be placed directly over those in the first layer or over
the previously unoccupied Y sites. If the spheres in the third layer are positioned
vertically above those in the first layer a hexagonal lattice is formed which is known
as the hexagonal close packed structure (h.c.p.) with a stacking arrangement
ABABAB . ... This is illustrated in Fig. 2.10.
Placing the third layer of spheres in the Y sites necessitates the fourth layer lying
directly over the first layer. Thus the stacking arrangement is now ABCABCABC ... ,
etc. and a face centred cubic structure is built up. The axes of the cube, however, are
neither in, nor perpendicular to, the plane of the close packed layers and actually the
layers are (I 11) planes. Note the face centred cubic lattice illustrated in Fig. 2.11 is
not the simplest building unit but it is taken as the unit cell because it shows the
maximum symmetry.
x X sites
• Y sites
Fig. 2.9 Close packing of identical spheres.
Note:- The lattice is

simple hexagonal with
,I
two atoms (000) and
I (2'3 1/3 1/2 ) associated
with each lattice point.
II
II •
.... -,
II I
(Spheres represented
by lattice points)
Actual close packing

of spheres.
Fig.2.10 The hexagonal close packed structure.
Each atom has twelve nearest neighbours in both of these close packed structures;
six in the close packed plane and three in each of the adjacent close packed planes
above and below. The number of nearest neighbours is called the coordinatio n number.
As mentioned earlier these two close packed structures should be favoured by solids
with non-directional forces, i.e. metallic or van der Waals bonding, and indeed many
metals do crystallize in the f.c.c. structure, as do all the solid rare gases except helium which
adopts the h.c.p. structure. Among the metals the h.c.p. structure is exemplified by
cobalt and zinc.
Although these are the only two ways in which identical spheres can be closely
packed together, a very important structure, where the packing is slightly looser, is the
body centred cubic (b.c.c.) structure. In this case each atom has only eight nearest
neighbours and this is indicative of the relatively loose packing. In fact the packing
fraction, or the fraction of the unit cell occupied by the spherical atoms is 0·74 for
both f.c.c. and h.c.p. but only 0·68 for b.c.c.ln spite of this looser packing many metals
crystallize in the b.c.c. form including all the alkali metals, and iron below 910°C. Two
possible reasons for the formation of this structure rather than the close packed
structures are (a) the thermal energy of the atoms (e.g. alkali metals tend to change to
the f.c.c. phase at low temperatures) and (b) partial covalent bonding.
Close
'_--0-- packed
planes
Fig. 2.11 Face centred cubic lattice showing the close packed planes.
2.5 Covalent solids
Covalent solids do not form close packed structures because the covalent bonds are
very strong and rigid and their directional nature must be maintained. The simplest
covalent structure is that of diamond (and germanium and silicon) which is a fairly
open, or 'empty' structure and far from close packed (packing fraction 0'34). One-
eighth of the unit cell is shown in Fig. 2.12 illustrating the tetrahedral bonding, i.e.
the coordination number is 4. It is a complicated cubic lattice with two atoms, e.g.
situated at (000) and (Hi), associated with each of the cubic lattice points.
The low pressure crystal form of carbon is graphite which differs in many respects
from diamond. It is a layer structure in which the atoms are covalently bonded to
only three nearest neighbours in the layer, and the layers themselves are only weakly
bonded by van der Waals forces (Fig. 2.13). Since there is one electron per atom that
is not employed in the covalent bonding there is an abundant supply of free electrons,
and so graphite is a good electrical conductor whereas diamond is an almost perfect
insulator. However, the free electrons cannot cross easily from layer to layer and so the
resulting conductivity is highly anisotropic (approximately 106 n-
l m- l parallel to the
layers and 40 n- l m- l perpendicular to the layers). For a long time it was believed
that graphite owed its lubricating properties to the weak van der Waals bonds between
adjacent layers. More recently it has been established that lubrication is associated with
adsorbed gas layers such as oxygen or organic molecules.
T--------~
/ 1 / 1
/ I / I
// I I
/ I
f~-~~- I
1 I
1 I
I I
I I
I J
I /
I //
I / //
1/ 1/
~----------v
Fig.2.12 The diamond structure.
Fig. 2.13 The layer structure of graphite.
2.6 Ionic solids
Ionic solids cannot form close packed structures because they do not normally consist
of ions of identical size (see Table 2.2), and the charge on the ions requires an alternat-
ing arrangement of anions and cations. The type of crystal structure is mainly deter-
mined by the packing of the larger ions which are normally the negative anions. Two
simple, common ionic crystal structures are the sodium chloride and caesium chloride
structures illustrated in Fig. 2.14. The main factor determining which structure is
adopted is the ratio of the ionic radii re/ra' since like ions must not touch because of
the large electrostatic repulsion.
o CI- o CI-
• Na+ • Cs+
(a) (b)
Fig. 2.14 (a) NaCI structure. (b) Cs Cl structure.
The NaCl structure can be regarded as two interpenetrating f.c.c. lattices and each
ion has six nearest neighbours of opposite charge, Le. the coordination number is 6.
It is favoured by ions having an ionic radii ratio re/ra of approximately 0·5. The CsCI
structure, on the other hand is two interpenetrating simple cubic lattices. It has a co-
ordination number of 8 and re/ra is about 0.9.
TABLE 2.2
Ionic radii
Ion Radius (A) Ion Radius (A)
Na+ 0·98 CI- 1·83

K+ 1·33 Br- 1·96
Cs+ 1·69 1- 2·16
Li+ 0·60 F- 1·36
The bonding of ionic crystals is the simplest to analyse quantitatively because the
force of attraction between the ions is the Coulombic force - (e2j41Tfor02) where ro
is the equilibrium separation. Using this value for the force in the analysis of section
2.1 the potential energy for a single molecule is given by
(2.5)
However, in an ionic crystalline solid, each ion has a number of neighbours rather than
a single neighbour as in the case of the isolated molecule, and both terms in the above
expression for the energy will be affected by the presence of these other neighbours.
In the case of NaCI reference to Fig. 2.14a shows that a given ion within the crystal
(e.g. the central Na ion) is surrounded by six nearest neighbours of unlike sign at a
distance TO, twelve next nearest neighbours of like sign at a distance ..;2To and eight
second nearest neighbours of unlike sign at a distance 0To, etc. Thus, the total energy
of a single ion will be
(2.6)
where e is another constant representing the net repulsion due to all the overlapping
electron clouds.
The potential energy can be rewritten as
Vo =(Me 2 /47r€oTo) +elTo m, (2.7)
where M is a constant known as the Madelung constant which is simply a geometric
term. The Madelung constant for the NaCI structure is
6 12 8 6 24
.,ff-..;2+0-.[4+...[5-
and although this series converges slowly it can be shown to equal 1·747558 (for the
CsCI structure M = 1·76267).
Equating the attractive and repulsive forces at To (by analogy with eqn (2.4)) leads
to an expression for C, and enables eqn (2.7) to be rewritten as
Vo=---
47r€OTO m
2
Me ( 1 - - . 1) (2.8)
As explained in section 2.1 this is the bonding energy (b.e.) of the ion. Thus if N is
Avogadro's number the bonding energy per mole will be
NMe
b.e./mol = - -
2
- (1- - ,
47r€oTo m
1) (2.9)
where Nand e are fundamental constants, To can be determined by X-ray diffraction

experiments and M can be calculated in simple cases. Hence the experimental value of
the bonding energy, which is equal to the latent heat of sublimation, can be used to
calculate values for m. Typical values of m for the alkali halides are 9.1 for NaCI, 5.9
for LiF.
2.7 Summary
The previous sections have shown that the type of atomic bonding plays an important
role in determining the possible crystal structures of solids. In addition the type of
bonding considerably influences the physical properties of the resulting material, as
will be apparent in later chapters. The data in Table 2.3 illustrates in a very general
manner, since many are temperature dependent, some of the properties typical of the
various types of bonding, although it must be stressed again that many solids show
more than one type of bonding. Thus, a classification of solids into the four classes
(i) ionic, (ii) covalent, (iii) metallic and (iv) van der Waals or molecular, is extremely
valuable.
Some of the materials to be met in later chapters, e.g. typical ferrimagnetic and
ferroelectric materials, have much more complicated crystal structures than the simple
examples discussed in this chapter. However, the general principles of packing different
size anions and cations and the directional nature of covalent bonds is still valid.
TABLE 2.3
Gassification of solids
Property Ionic Covalent Metallic Molecular
(i) Typical examples NaO, LiF, Diamond, Si, Na,Fe,Cu Ar, Ne, I
Ca02 Ge, SiC (C6 H 12 0 6h
sugar
(ii) Bonding energy 6-10 x 104 2-10 x 104 1-4 X 104 10 3
(J mole- 1)
(iii) Melting point (K) 700-3300 500-3700 230-4150 < 600
(iv) Electrical resistivity 10 12 _10 20 10-10 20 10- 3 -10- 6 10 12 _10 20
(Om)
(v) Thermal conductivity 2-20 4-600 40-400 0·04-4
(Wm-1K-1 )
(vi) Hardness hard but hard malleable
cleavable
2.8 Lattice imperfections
The perfect crystal so far considered is built up by repeated translation of the basic
unit cell along the three crystallographic axes. In practice, however, the real crystal is
not quite this regular and there are a variety of imperfections or defects present in all
crystals. These imperfections playa major role in explaining many of the physical
phenomena exhibited by solids; for example electrical conductivity, mechanical
strength and ferromagnetic hysteresis. Since the effects of the imperfections will be
met many times in the subsequent chapters, it is appropriate to deal with them
collectively at this stage.
Lattice imperfections can be broadly classified into four major classes, namely:
(a) lattice vibrations, or phonons,
(b) point defects,
( c) line defects, and
(d) plane defects.
In addition there may be defects in the electronic configuration of individual
atoms, and, although these have a major influence on electrical and optical properties,
they are not strictly lattice imperfections. Hence, further discussion of these will be
left to the relevant chapters.
2.9 Lattice vibrations
At all temperatures the atoms are not stationary in their designated lattice positions
as has been assumed so far, but instead they are vibrating about their mean positions
with a set of characteristic frequencies, v. fhere is a wide range of vibrational
frequencies in solids, with values as high as 10 12 Hz at room temperature, and the
amplitude of vibration may be as much as 10 per cent of the interatomic spacing.
According to quantum theory, the energies of these lattice vibrations are quantized
and for a particular frequency v are given by
En = (n + !)hv, (2.10)
where n is an integer and h is Planck's constant. If energy, in the form of heat, for
example, is supplied to a crystal the energy of the lattice vibrations will increase in
integral steps of hv and similarly if the crystal cools the vibrational energy will decrease
in steps of hv. The similarity between this process and the absorption or emission of
light photons is very close and so the name phonon is used for the quanta of vibrational
energy absorbed or emitted by a solid. Even at absolute zero, where n is zero, the atoms
are not stationary but still possess an energy of !hv, which is called the zero point
energy. The total vibrational energy of the crystal will be given by the sum of the
energies of the individual atoms taking into account the complete vibrational frequency
spectrum of the material.
As well as playing a fundamental role in determining the thermal properties such
as the specific heat of solids, interaction between electrons and phonons partly explains
the electrical resistance of materials.
2.10 Point defects
Point defects refer to those irregularities in the crystal structure which occur over a
region of only a few lattice points. All the atoms in a solid possess vibrational energy
and at all temperatures above absolute zero there will be a fmite number of atoms
which have sufficient energy to break the bonds which hold them in their equilibrium
position. Once free from their lattice sites there are two possible situations that can
occur:
(a) the atom may simply occupy a nearby interstitial position leaving a vacancy at
the original lattice site; the associated vacancy and interstitial is termed a
Frenkel defect, or
(b) the atom may migrate to the surface of the crystal or be trapped at a line or
plane defect in the crystal; vacancies of this type are referred to as Schottky
defects.
These two situations are illustrated diagrammatically in Fig. 2.15.
0000000 0000000
OO~~tOO 0000000
o OO&,? 0
0 000 000
0000000 0000000
0000000 0000000
(a) (b)
Fig.2.15 (a) Frenkel defect. (b) Schottky defect.
If the energy of formation of a Schottky vacancy is Es then the number at any

temperature T will be given by
n =N exp{ -(Es/kT)}, (2.11)
where N is the total number of atoms in the crystal. Es is typically one or two eVand
n/N is only of the order of 10-14 _10- 12 at room temperature, although it is as high as
10- 3 in solid metals close to their melting points. In ionic crystals it is energetically
favourable to form roughly equal numbers of positive and negative ion vacancies to
keep the crystal electrostatically neutral on a local scale. Similarly if the energy of
formation of a Frenkel defect is E Fr the equilibrium number at a temperature Tis
given by
n = (NN1) 1/2 exp{-(EFi'/2kT)}, (2.12)
where N is defmed as above and NI in the number of possible interstitial sites in the
crystal. In general Schottky imperfections are more likely to form than Frenkel
imperfections in relatively close packed structures because the lattice holes or 'inter-
stices' are too small to accommodate the displaced atoms.
It is important to realize that vacancies are a naturally occurring phenomena in all
crystals above the absolute zero of temperature. The occurrence of vacancies is very
important in accounting for the small but finite electrical conductivity in ionic solids
since the presence of vacancies permits other ions to migrate under the action of an
applied field. The occurrence of these lattice defects can be studied by density measure-
ments, since the presence of Schottky defects increases the volume without changing
the mass whereas Frenkel defects leave the density unchanged. Defect studies in ionic
crystals may be made by ionic conductivity measurements. Considerable experimental
work has been done on point defects in ionic crystals and it appears that in pure alkali
halides Schottky defects are the most common. In the silver halides the most common
vacancies are Frenkel defects.
Apart from these purely structural imperfections there are additional point defects
due to the unavoidable presence of impurity atoms in the crystal, since no material can
be prepared in an absolutely pure state. These impurity atoms can occupy two possible
positions in the lattice. Either they can substitutionally replace one of the host atoms,
as for example in germanium doped with arsenic, or they can occupy interstitial
positions in the lattice as in the case of carbon in iron. In the former case the impurity
atoms are of similar radii to that of the atoms they replace, whereas in the latter situa-
tion they are of much smaller radii; typical interstitial impurities include hydrogen,
oxygen and carbon.
The solubility limit, or the extent to which impurity atoms can be accommodated
in the basic matrix varies drastically from system to system, but when the solubility
limit is exceeded a new phase appears which may consist of the solute itself or an
intermediate phase or compound. Usually, of course, care is taken to remove as much
chemical impurity as possible but in certain circumstances the presence of precipitates
of a second phase is very useful as for example in the preparation of the so-called hard
magnetic materials.
2.11 Line defects [2]
line defects, or dislocations were initially introduced independently by Taylor, Orowan

and Polanyi in 1934 to explain the observed mechanical behaviour of solids. Since then
dislocations have been observed directly and they have proved useful in explaining
STRUcrURE OF SOLIDS 37
other phenomena, such as crystal growth, as well. Their role in explaining the mech-
anical properties of solids will be discussed more fully in Chapter 5 and at this stage we
will simply limit ourselves to an explanation of their nature.
Two basic types of dislocation can be distinguished: (a) the edge dislocation and
(b) the screw dislocation.
2.11.1 The edge dislocation

This can be regarded as the insertion of an extra half plane of atoms above (positive)
or below (negative) the dislocation line. Fig. 2.16 illustrates a positive edge dislocation,
in which there is one more vertical plane of atoms above the dislocation line than below;
~--- Lattice in compression

rr-}~-?---y;---yr----"'HJlf
/ .J.(...---_ Lattice in tension

&-......,+----e~!F====r,-.
I
Line of the edge dislocation

Fig. 2.16 A positive edge dislocation.
a dislocation of this nature is denoted by the symbol 1. The dislocation line is a region
of higher energy than the rest of the crystal lattice because, as can be seen in the dia-
gram, the lattice above the dislocation line is in a state of compression, whereas below
the dislocation line the lattice is in tension. The abnormal interatomic spacing below
the dislocation line provides a ready 'sink' for both interstitial atoms and chemical
impurities.
2.11. 2 The screw dislocation

A screw dislocation can be thought of as being produced by cutting the crystal part way
through with a knife and then shearing one half of the crystal parallel to the cut (Fig.
2.17). The name screw dislocation arises because it transforms successive atomic planes
into the surface of a helix around the dislocation line. There are no compressive or
tensile stresses associated with a screw dislocation but there are shear stresses, and so
again there is considerable energy accompanying it.
In general, dislocations are more complicated than suggested by these two simple
examples but they can always be resolved into a combination of edge and screw com-
ponents. Dislocations can be inherently introduced into the crystal during growth, as
will be discussed in Chapter 3 and a typical dislocation density, which is defined as the
number of dislocation lines intersecting unit area anywhere in the crystal, is of the
Screw dislocation line
Fig. 2.17 A screw dislocation.
order of 10 10 lines m -2. Although dislocations are associated with regions of excess
lattice energy, once formed relatively little energy is required to move them; hence
their importance in mechanical behaviour.
2.11.3 The Burgers vector

These dislocations can also be described by means of a closed loop surrounding the
dislocation line. The loop, or Burgers circuit, is formed by taking equal integral lattice
translations in each pair of parallel sides of a right handed circuit around the direction
of the line of the dislocation. Such a circuit would close upon itself in a perfect region
of the crystal, but in the vicinity of a dislocation it fails to do so by an amount known
as the Burgers vector, b, of the dislocation. The diagrams of Fig. 2.18 show that the
Burgers vector is normal to the dislocation line in the case of an edge dislocation but
(a) (b)
Fig. 2.18 Burgers vector of edge and screw dislocations. (a) Edge dislocation. (b) Screw
dislocation.
parallel to it in the case of a screw dislocation, and in the case of the 'perfect' dis-
locations shown, the Burgers vector is an integral of the atomic spacing. Thus it is
possible to distinguish the two fundamental types of dislocation by the direction of
their Burgers vector relative to the line of the dislocation.
2.12 Plane defects
Plane, or surface, imperfections arise from a change in the orientation or stacking of

atomic planes at an interface. Even in a single crystal specimen the atomic packing may
not be completely regular throughout the entire crystal and different regions or grains
may be separated by low-angle boundaries of a few degrees or less. These boundaries
may be described in terms of a linear array of dislocations, as in the case of the low-
angle tilt boundary shown in Fig. 2.19 which is formed by a linear array of edge dis-
locations. The tilt angle, (), across the boundary is equal to biZ where b is the Burgers
vector and Z the average vertical separation of the edge dislocations. Similarly a low-
angle twist boundary can be associated with a network of screw dislocations.
Fig. 2.19 A low-angle tilt boundary.
Naturally the grain boundaries which separate the randomly orientated grains in a
polycrystalline specimen cannot be explained in this way because the misorientations
are much too large. In this case the grain boundaries are a few atomic spacings wide
and in the boundary region almost all semblance of regular ordering is absent and
quite abnormal interatomic spacings can be found. This explains the ability of these
boundaries to act as sinks for defects such as lattice interstitials or impurity atoms.
Plane defects of a more regular nature can occur in many crystal structures either
by introduction during growth or by subsequent mechanical deformation. One example
is the twin boundary in which the boundary acts as a mirror in that the two crystal
orientations on either side of the boundary are mirror images of one another (Fig.
2.20). These two orientations are called twins and they are especially common in
metals with b.c.c. or h.c.p. structure.
Finally, another example is the stacking fault which can arise in the close packed
f.c.c. or h.c.p. structures as a result of an accidental fault in the stacking sequence.
Fig. 2.20 A twin plane.
For example, in the f.c.c. structure the stacking sequence of the close packed planes
should be ABCABCABC ... , however a fault may arise leading to a sequence of the
form ABCABABCABC ... so that a thin h.c.p. region is included in the basic fc.c.
structure.
2.13 Amorphous materials
In conclusion it should be stressed that the discussion in this chapter has been con-
cerned exclusively with the structure and imperfections of crystalline material and no
mention has been made of the structure of amorphous materials. Polymers are a very
important class of material in modern technology and their structure has a very
important influence on their properties. Although some simple polymers may
be prepared as small single crystals, most polymers consist of randomly orientated
long chain molecules. Their basic structure is amorphous although crystalline regions
are by no means uncommon. However, because of their unusual structure, which is so
dependent on their preparation and the nature of the molecules themselves, their
preparation and structure will be dealt with collectively in Chapter 3 (see section 3.9).
Many inorganic materials of interest, although usually encountered in crystalline
form, may also be prepared in the amorphous state. The structure of these materials
in considered in section 4.7.
References
1. Cracknell, A. P. Crystals and Their Structures, Pergamon (1969).

2. Hull, D. Introduction to Dislocations, Pergamon (1965).
Questions
1. Deduce the nature of the chemical bonding in the following crystals from the
position of their constituent atoms in the Periodic Table.
(a) gallium arsenide, GaAs
(b) neon, Ne
(c) potassium, K
(d) nickel oxide, NiO.
2. Show why (a) F face centred tetragonal and (b) C face centred tetragonal are not
included in the list of Bravais lattices.
3. How many atoms are there in the f.c.c. and b.c.c. unit cells? Calculate the packing
efficiency for these two structures.
4. Calculate the theoretical cia ratio for the h.c.p. lattice and compare this value with
actual values for h.c.p. elements.
S. Calculate the limit of the ionic radius ratio for stability in the NaCI structure, and
compare this with the actual radius ratio for as many ionic crystals with the structure
as you can find.
6. Show that, for any cubic lattice, the separation of the planes corresponding to the
Miller indices (hkf) is given by
d =(h
hk1 2 +:2 + [2 y12.
7. Draw diagrams to illustrate the meaning of the following Miller indices: (a) (121);
(b)(212);(c)(II0);(d) [121];(e) [212] and(f) [110].
8. Platinum (atomic mass 195.1) crystallizes in the f.c.c. form and has a density of
21·4 x 103 kgm- 3 • Calculate the length of the edge of the unit cell. [Avogadro's
number = 6'02 x 1026 k mol-I.]
9. The concentration of Schottky defects in an f.c.c. ionic crystal is 1 in 10 10 at a
temperature of 300 K. Estimate the average separation in terms of the lattice spacings
between the defects at 300 K and calculate the value of the concentration to be
expected at 1000 K.
10. A single crystal of copper contains a low-angle tilt boundary on (001) with a tilt
axis parallel to [010]. Calculate the tilt angle if the spacing of the dislocation in the
boundary is 3 x 10- 6 m and their Burgers vector is 0·4 x 10- 9 m. Give a sketch of the
arrangement.
3 Preparation of Materials
3.1 Introduction
It was seen in the last chapter that materials can occur in a variety of forms, namely,
single crystal, polycrystal and amorphous. Cooling from the liquid state usually
results in polycrystalline material and the common engineering metals and alloys cast
from the melt are composed of numerous crystalline grains. The grain size may vary
from micro metres to millimetres and depends on many factors, such as the casting
temperature and the impurity content. Subsequent mechanical working and heat
treatment produces changes in the grain structure.and this in turn alters the mechanical
properties. As yet little or no attempt has been made by the structural engineer to
utilize single crystal material, but in the field of electronics immense progress has
been made through the increased use of single crystals in solid state devices.
Prior to the Second World War the growth and study of single crystals was some-
thing of a novelty and largely restricted to crystals that could be grown easily from
solution, e.g. common salt and copper SUlphate, and crystal growth was regarded more
as an 'art' than a 'science'. However, in the last twenty years or so synthetic single
crystals of various substances have gained much more practical importance, often for
pure scientific investigation but increasingly for technological and industrial applica-
tions. To date, metal and alloy single crystals have not found much use outside
scientific research, but the current technological applications of single crystals range
from the semiconductor field with silicon and gallium arsenide to the laser field with
doped sapphire, yttrium aluminium garnet and zinc tungstate. More recently, several
niobates and tantalates have found application in non-linear optical devices such as
frequency doublers and parametric amplifiers.
Bulk single crystals can be grown by various methods, including growth from the
melt, from solution or by chemical transport. Thin film single crystals can be grown
epitaxially by vapour deposition onto a single crystal substrate. These various tech-
niques will be described in greater detail in the subsequent sections but initially the
mechanism of the growth process itself is briefly discussed [1, 2].
3.2 Mechanism of crystal growth
Consider growth occurring on a crystal surface as shown in Fig. 3.1. When an atom
from the surroundings (Le. from solution, melt or vapour) strikes the surface the
collision will decrease the energy of the atom so that it becomes partially bound to
the crystal surface. Thus any further motion of the atom is restricted to the surface.
Isolated nuclei are then formed from groups of such atoms coming together by chance
PREPARATION OF MATERIALS 43
through their thermal motion (Fig. 3.1a). Of the groups shown in Fig. 3.1 b a mobile
'new' atom is most easily built into the crystal structure at a point such as X, since at
this point the atom will be strongly attracted by three neighbouring atoms and the
local surface energy of the surface due to the unsaturated bonds will be decreased.
Another convenient position will be sites such as Y(Fig. 3.1c) and in this way a con-
tinual supply of atoms will lead to completion of the entire crystal plane.
(a) (b) (e)
Fig. 3.1 Development from a nucleus of a step on a crystal surface.
Once this situation arises continuation of the growth process will rely on the forma-
tion of a new stable nucleus (depicted schematically as a thin cylinder in Fig. 3.2) on the
plane surface. In this new nucleus or seed there will be an increase in free energy due to
the atoms at the edge and a decrease of free energy due to the atoms in the interior.
Fig. 3.2 Nucleus on a crystal surface.
Thus the stability of the seed will depend upon the ratio of volume to surface, and
there will be a critical radius of the nucleus, rc such that if r > rc the nucleus is stable
and growth can continue whereas if r < rc the nucleus is unstable. Since the lateral
growth mechanism discussed above is a very rapid process the rate of formation of
the new nuclei on the completed planes will be the decisive factor in controlling the
overall growth rate.
The probability of formation of stable nuclei in growth from the melt will obviously
depend on the difference between the melt temperature and the normal melting point
of the solid, i.e. the degree of supercooling of the melt. In vapour growth it will depend
on the relative excess of the pressure of the vapour over the vapour pressure of the
solid (degree of supersaturation), and in solution growth on the analogue in tenus of

solute concentration. If the degree of supercooling or supersaturation is high then the
probability of forming stable nuclei increases and in fact may become so high that
additional unwanted nuclei are formed in the melt or solution as well as on the grow-
ing surface. However, if the degree of supercooling or supersaturation is very low then
the probability of formation of stable nuclei is almost zero and crystal growth should
cease. In practice this is not observed and crystals can be grown under almost any
value of supercooling or supersaturation.
To overcome this apparent dilemma Frank [3] proposed that growth could occur
continuously on the deformed surface produced by an emergent screw dislocation.
Since the tangential growth velocity is the same all along the surface step produced by
the screw a growth spiral originates as shown in Fig. 3.3. The observation of growth
(a)
(b)
Fig.3.3 Screw dislocation growth. (a) Emergent screw dislocation. (b) Formation of growth
spirals.
spirals in the surfaces of crystals grown from solution or vapour provided one of the
earliest pieces of direct evidence for the occurrence of dislocations.
These two theories of crystal growth differ markedly in their predictions for the
magnitude of the growth rate and its dependence on supercooling (t.T). For example,
nucleation controlled growth predicts a variation with t.T of the form exp {-(B/kt.T)}
where B is a constant, whereas growth on screw dislocations predicts a variation pro-
portional to (t.T)2. However, although some experimental data exhibits the correct
dependence on t::.T for one or other of these models, there is still a lack of quantitative
agreement on the magnitude of the growth rate. Moreover this is also true for more
detailed models of growth which treat the interface between the growing crystal and
the surroundings in varying degrees of complexity and, as yet, there is no unified
quantitative theory of crystal growth.
Another important criterion in the case of crystal growth from the melt is the tem-
perature variation in the vicinity of the interface between solid and liquid; two possible
temperature distributions are illustrated in Fig. 3.4. If a projection is formed for any
Solid
Liquid
Interface Distance
(a)
Solid
Liquid
Interface Distance
(b)
Fig. 3.4 Temperature distribution near an interface.
reason on the interface during crystallization then, for the temperature distribution
shown in (a) the projection passes into a region of higher temperature and melts,
whereas in case (b) the growth of the projection is enhanced until the evolution of the
latent heat produces a temperature distribution similar to (a). In the latter case, there-
fore, a rapid growth of 'needles' or dendrites may occur in specific crystallographic
directions ahead of the main interface. Dendritic growth is generally a nuisance and is
apt to occur when the rate of cooling is excessive.
3.3 Growth from the melt
This is by far the most common method of growing large single crystals of a wide range
of materials. Usually growth occurs from a high temperature melt but, before the
various experimental techniques are considered in detail, the growth of single crystals
of gallium will be discussed. Gallium is a most unusual metal in that it melts at 29·7°C
and therefore presents no difficulties as regards melting or containment of the melt,
but the growth technique is a simple example of the more complicated methods to
be described later.
Strain-free crystals can be grown very easily in sectioned perspex moulds or perspex
tubes containing a small seed crystal, maintained at 28° C, at one end of the mould
(Fig. 3.5). Clean liquid gallium at 35°C is poured into the mould and this melts the tip
Fig. 3.5 Mould for growth of gallium single crystals.
of the seed crystal thus ensuring intimate contact between the seed and the growing
crystal; subsequent growth occurs at a rate of a few cm/hr. The use of sectioned moulds
enables crystals of predetermined shape to be grown, as for example a dumb-bell shaped
crystal for tensile testing as shown in Fig. 3.5; alternatively crystals up to several feet
in length can be grown in perspex tubing. Seed crystals nucleate readily in the super-
cooled liquid and the subsequent position of the seed crystal in the mould enables
crystals of any desired orientation to be grown, so that the anisotropy of the physical
properties can be studied.
This process of melting the charge and subsequent growth onto a seed crystal is
typical of all techniques of growth from the melt, but the high temperature melts
usually encountered produce many additional complications and a variety of different
techniques have been developed. These techniques fall into two general classes depend-
ing upon whether the complete charge is melted and contained in a crucible, as above
in the case of gallium, or whether only part of the charge is molten at anyone time and
this molten charge is not contained in a crucible.
3.3.1 Growth from crucibles

The two major techniques of growth involving crucibles are the Bridgeman or Stock-
barger, and Czochralski (or crystal-pulling) methods. In the Stockbarger method the
whole charge (usually) is melted in a pointed crucible and the crucible is then lowered
through a temperature gradient (Fig. 3.6). Growth initially occurs at the pointed end
of the crucible and with a correctly shaped crucible only one crystal nucleates; alter-
natively a seed crystal may be inserted at the pointed end, and this tip maintained
below the melting point Tm.
To ensure homogeneous growth, and good quality crystals, the temperature must be
carefully controlled and the movement of the crucible must be uniform. Apart from
the obvious limitation on size of the crystals due to the size of the furnace, there is a
further limitation due to thermal strains which are induced in the grown crystal due
to the radial temperature gradient (parallel to the solid-liquid interface) which cannot
be eliminated since the growth interface is always in contact with the crucible.
Crucible - - - - - - ' 1 f - - - - - l " -
,,~'I---_+-_Molten
charge
_ _ _ Furnace
windings
Direction
of
motion
Fig. 3.6 Stockbarger method.
The crystal-pulling technique overcomes this latter problem, and is the only way of
growing large perfect crystals from the melt, since the solid-liquid interface is no
longer in contact with the crucible. The essential components of a crystal puller are
(i) a heat source to melt the charge; (ii) a crucible to hold the melt; (iii) a seed crystal;
and (iv) a means of producing relative motion between the seed crystal and the melt.
These essential components are illustrated in Fig. 3.7. The seed holder or chuck is
attached to a shaft that can be raised, or lowered, and rotated. If necessary the entire
arrangement can be contained in a silica enclosure so that growth can take place in a
controlled atmosphere, this is essential if the melt is very volatile. Doped crystals can
be grown by incorporating the impurity in the melt and convection currents provide
adequate stirring to distribute the dopant in the melt. Pulling rates vary between 1 mm
hr- 1 to 2 cm hr- 1 and crystals several cm in diameter and more than 10 cm long have
been grown.
The most common form of heating in both these techniques is electrical since this
type of heating is easily controlled. It may be direct heating (1 2 R) in furnace windings
or r.f. induction heating in which either the crucible and/or the charge, or a graphite
susceptor absorbs the r.f. power. The choice of crucible material is of fundamental
importance in both these techniques for it must not only withstand high temperatures
but it must not react with the melt. In addition, to eliminate strain the coefficient of
expansion of the crucible should be less than that of the crystal. Typical crucible
materials are silica (maximum temperature -1200°C), graphite (2600°C), molybdenum
Shaft---
'1 _ _ _ _ _ _ Seed holder

or chuck
Seed
crystal
Grown
- - - - t - - crystal
Melt Crucible
Fig. 3.7 Crystal-pulling method.
(2400° C) and platinum (1600° C). In general metallic crucibles are used for the growth
of non-metallic crystals and non-metallic crucibles for metallic crystals; the choice of
insulating or conducting crucibles may well determine the type of heating needed.
However satisfactory the choice of crucible material there will always be some strain
and/or risk of impurity being introduced in the crystal and this places some limitation
on these techniques.
13.2 Non-crucible methods

These are basically two methods of growth from the melt without containing the melt
in a crucible, namely the Verneuil method and the floating zone method [4]. Because
of the difficulty of providing crucibles, they are the only methods available for
materials with melting points in excess of 2200°C.
In the Verneuil method, powder falls from a hopper through a flame and arrives
molten on the surface of a growing crystal (Fig. 3.8), which is lowered at a rate of
about 1 cm/hr. Either an oxygen/hydrogen or oxygen/coal gas mixture can be burnt to
provide the source of heat. The flame conditions may have to be carefully controlled
to ensure that the charge material is neither oxidized nor reduced. The charge must be
in the form of a fine powder. Typically it must pass through a 300 mesh which allows
particles of diameter 53 pm or less to pass, and it must be dry so that it does not clog
the mesh or the narrow feed tube. Rotation of the alumina rod pedestal can average
out any lack of symmetry in the flame and a subsidiary furnace in the growth chamber
can be used to decrease the temperature gradient across the grown crystal and thus
reduce thermal strain. Although the disadvantages of the presence of a crucible are
eliminated there are two serious disadvantages of this technique in that controlled
doping of the crystal is difficult to achieve and the atmosphere in which growth takes
place cannot be controlled; in addition the control of feed material is difficult to keep
constant.
The second technique, the floating zone method, eliminates the crucible by using
surface tension to hold a molten zone in a bar. The molten zone is then moved up the
bar giving simultaneous growth and zone refining (Fig. 3.9). Single crystal growth can
be initiated by holding a seed crystal in one of the chucks and drawing the tip of the
seed into the molten zone at the end of the feed rod. The seed is then slowly with-
Charge
Mesh - -
- - Hopper
Feed tube - - -
: .../ Flame
Gas ---.., 1.--:::::::--- G
- - _.... I - - - - as
- - - Seed crystal
Alumma
pedestal
Fig. 3.8 VerneuiJ method.
_ _ Upper
chuck
Seed
crystal
Grown
- - - crystal
o o
Molten _--,-
0 __ o _ _ Induction
zone 0 o coil
o o
_ _ _ Feed
rod
lower _ _
chuck
Fig. 3.9 Floating zone method.
drawn and the feed rod simultaneously raised. Thus the two chucks must be capable
of separate translational motion and rotation to provide adequate stirring of the melt.
Again after-heaters can be used to prevent excessive thermal strain in the growing
crystal. The use of r J. heating is almost universal for this technique but other heat
sources including arc-image furnaces using radiant heating from a tungsten filament
lamp or carbon arc have been used [5] . Plate 1 shows a molten zone in a sintered rod
of nickel oxide-the heat source in this case was a carbon arc. This latter heating
method suffers from the limitations that if growth in a controlled atmosphere is

required the containing vessel must remain transparent and that, if a carbon arc is
used, it has a finite running time of about ~ hr. This necessitates high growth rate or
the switching from one heat source to another, which almost certainly leads to changes
in the growth rate. With care, this technique can be used to grow crystals with quite
uniform dopant concentration.
Table 3.1 shows a few examples of the wide range of crystals that can be grown
from the melt, together with the technique or techniques that are commonly used for
their growth.
TABLE 3.1
Crystal Melting point Technique
GaAs 123S0C Stockbarger, Czochralski, floating zone

Ge 937°C Stockbarger, Czochralski
PbS 1114°C Stockbarger
AI 660°C Stockbarger, Czochralski
Cawo4 1600°C Czochralski
Si 1420°C Czochralski, Verneuil, floating zone
Ti0 2 I640°C Czochralski
Zr02 2700°C Verneuil
Al 2 0 3 2050°C Verneuil, Czochralski
NiO 1990°C Verneuil, floating zone
W 3400°C Floating zone
Mo 2500°C Floating zone
LiNb03 1253°C Czochralski, Stockbarger
Y3 A1 S012 1970°C Czochralski
Ba2Na Nbs01S 1500°C Czochralski
3.3.3 Zone refining

The purity level of germanium and silicon required for semiconductor devices is
extremely high and the as-grown crystals are usually too impure for practical use.
Fortunately they can be further purified by a method of zone melting refining
developed by Pfann [6]. The application of this process depends on the fact that
most impurities depress the melting point of a solvent and thus prefer to remain in
the liquid phase rather than freeze out. Since the concentrations of the impurities in
the solid and liquid phases are very small in those cases of interest the liquidus and
solidus curves can be approximated by two straight lines Fig. 3.1 O. The ratio of
the impurity concentrations in the solid and liquid is then a constant, i.e.
(3.1)
where k is called the segregation coefficient and in this case is less than 1.
Hence if a molten section is progressively passed along a single crystal rod the
initial uniform impurity content can be altered. In practice the rate of solidification
is such that there is no diffusion in the solid state, whereas the stirring by convection
currents and the high diffusion rate in the liquid ensures that the latter is homogeneous.
When the molten zone starts at the end of the crystal the impurity concentration in
the melt is the same as that of the initial material, i.e. Co, and as the zone passes along
the ingot this initial region re-solidifies with an impurity concentration of kC o. How-
ever, this loss of material from the molten region is compensated for by further material
melting, and thus increasing the impurity content in the liquid until it reaches a con-
stant value Colk. Thus the impurity concentration in the re-solidified material increases
liquid
I
I
I
I
I
Solid
I
I
I
I
I
o Co C,
Percentage impurity le%)
Fig. 3.10 Effect of a solute which lowers the melting point.
as the molten zone passes until the constant region is reached, as illustrated in Fig.
3.11. Of course the final region solidifies with the impurity concentration in the final
zone. This variation of impurity concentration in all but the final region can be rep-
resented by the following equation:
Cs =Co{1-(I -k) exp(-kx/l)}, (3.2)
where I is the length of the molten zone.
Co - - -- - -'-=-:;.;--....---------.-:.---- ---
kCo
Length of re-solidified material x
Fig. 3.11 Effect of a single pass of a molten zone.
Further purification results from repeated passes of the molten zone, as is illustrated
by the curves shown in Fig. 3.12, with subsequent discarding of the final region. In
practice this is carried out by using a multipass technique as illustrated for the case of
germanium contained in a graphite crucible in Fig. 3.13. Using this technique impurities
which can cause large changes in the electrical properties, i.e. elements from Group III
or Group V can be reduced to as little as 10- 8 per cent. In the case of silicon, zone
refining is equally valuable, but the high reactivity of molten silicon places greater
restrictions on the crucible material. Thin-walled quartz can be used but a valuable
Cs __ -::::::=;::: nn == 21
~o n '" 3
n =4
n =5
~ 10 '
n =6
~c
CIl
(.)
g 10- 2
(.)
CIl
.~
Ri
Qj
a:
Distance in zone lengths (x;' )
Fig.3.12 Curves illustrating the solute distribution for n passes (k =0'25) (after W. G. Pfann).
Molten
zones
o o o
Direction
of travel
•
o 0'-..,/0 o
Ge ingot r.f. heater
coils
Fig. 3.13 Multipass zone rerming of germanium.
alternative is to use the floating zone technique. Zone refining is not only limited to
the purification of semiconductor material but can also be used for metals although
the degree of improvement is much less and is typically only two orders of magnitude.
3.4 Non-melt techniques
Despite the successes of the various melt techniques discussed in section 3.3 there are
a wide range of compounds which, either cannot be grown as single crystals at all by
these techniques, or cannot be grown to a sufficiently high degree of perfection. There-
fore considerable attention is being paid to several other growth techniques which
permit growth to occur at temperatures well below the normal melting point. These
are especially valid for many high melting point materials such as ferrites, which are
usually non-stoichiometric when prepared from the melt; i.e. the constituents will not
be in the exact proportions as indicated by the normal chemical formula, but will show
small deviations. They are also applicable to materials which dissociate below their
normal melting point and for materials which undergo phase transitions at elevated
temperatures. Progress with these techniques should improve on the perfection of crystals
grown by other ways and may lead to the production of completely new single crystal
materials with possible technological applications.
PREPARATION OF MATERIALS S3
3.4.1 Fluxed-melt technique
This is a solution growth process which is no different in principle from the growth of
common salt or copper sulphate crystals from aqueous solutions which may well have
been grown or observed by most readers. Relatively few materials of technological
interest are soluble in water. In the fluxed-melt technique, the solvent or flux is
generally a molten salt, such as lead fluoride or barium borate which melt in the range
600-1000°C. Typical materials which have been grown in this way are high melting
point ionic or covalent solids, for example yttrium iron garnet (YIG) from a lead
oxide-lead fluoride flux at 12S0°C, nickel Oxide, NiO, from lead fluoride at 1280°C
and magnesium aluminate spinel crystals (Mg Al2 0 4 ) from lead fluoride at 12S0°C.
The crucible material poses a critical problem in this technique because the high tem-
perature solutions may be highly reactive and platinum although very expensive is
commonly used. Crystal growth can be initiated by slowly decreasing the solution
temperature typically by 1-20°C/hr, or by slowly increasing the degree of super-
saturation leading to growth runs from one to three days. In general many crystallites
are nucleated and the resulting crystals are rather small, e.g. a few mm edge; however,
crystal pulling techniques are currently being applied to flux growth and much larger
crystals should result, although the pulling rates are usually very slow.
Oosely allied to this fluxed melt technique is the hydrothermal growth process [7]
which uses considerably lower melting point fluxes but, because these are relatively
volatile, elevated pressures are required to retain the flux as a solvent. Typical of this
latter process is the growth of quartz from aqueous solutions.
Unfortunately in both of these processes it is impossible at present to eliminate all
traces of solvent inclusion in the crystals and this imposes a rather severe limitation on
these techniques.
3.4.2 Chemical transport [8]

Many crystals have been grown successfully in a very high state of purity at relatively
low temperatures from the vapour phase. Experimentally chemical transport reactions
are usually carried out in a closed reaction chamber, in which there is a temperature
gradient. The constituents (M) of the required crystal are placed at one end of a
previously evacuated quartz ampoule and mixed with a low pressure gaseous transport
reagent (N), typically hydrogen chloride, iodine or chlorine. M and N react at the higher
(or lower) temperature to form a volatile species which diffuses along the tube and
decomposes at the lower (or higher) temperature to deposit materialM This principle
is illustrated in Fig. 3.14. As a specific example consider the growth of nickel oxide
using hydrogen chloride as the transporting agent:
At T1(-9S0°C) NiO(s) + 2HCI(g) -+ NiCh(g) + H20(g) ].

(3.3)
At T2 (-920°C) NiCI 2(g) + H20(g) -+ NiO(s) + 2HCI(g)
Initia.1 .......... ~.:>. N (gasL (}~ r, >'2

matenal _. _M 0c::! .......... Single
_ _ _ _ _ _ _ _ _ _ _ _ _ _-=0::,..
crystals
Fig. 3.14 Principle of the chemical transport process.
As with all non-melt techniques multiple nucleation is a major problem and the
individual crystal size is still quite small, although one possible solution is to periodically
reverse the temperature difference so that preferential evaporation occurs from the
smallest crystallites. Alternatively the material can be deposited onto a single crystal
substrate-see section 3.5. Rare earth compounds and complex niobates and tantalates
have been grown by this technique.
3.4.3 Gel growth [9]

Gel growth is by no means a new technique but it has only been in the last few years
that much attention has been paid to it as a practical means of growing crystals. The
method has many limitations but it may prove very useful for materials which cannot
be satisfactorily grown from the melt or from the vapour phase.
Crystals can be grown in gels in a variety of ways, all of which however, are varia-
tions of two basic and extremely simple methods which will be illustrated by the growth
of calcium tartrate, CaC 4 H4 0 6 • A solution of sodium silicate is mixed with tartaric
acid and allowed to gel in a test tube in a constant temperature bath at about 45°C.
A solution of calcium chloride is then placed on top of the gel to prevent the gel from
drying out and to supply one of the reaction components. In due course crystals of
calcium tartrate form in the gel. The rate of nucleation depends on the concentrations
involved and can vary from minutes to days. By using a V-tube and making the gel
concentration as weak as possible the reagents can be separated and the nucleation
rate slowed down. These two experimental arrangements are illustrated schematically
in Fig. 3.15.
Concentrated
CaCI 2 solution Concentrated
tartaric acid
Crystal
growth
Gel containing Gel containing
tartaric acid weak tartaric acid
Crystal growth
Fig. 3.1S Gel growth.
Once again the individual crystals produced so far are very small, although calcium
tartrate crystals of I cm edge have been grown in this way and further work may lead
to the growth of considerably larger crystals. Examples of other crystals that have been
grown from similar low temperature gels include gold, lead iodide, PhI 2 , calcium tung-
state, CaW0 4 , and zinc tartrate, ZnC 4 ~ 0 6 •
3.5 Thin films
In addition to the demand for bigger and better single crystals of a wide range of
materials the necessity for micro-miniaturized components in this modem space age
has led to a tremendous increase in the technological application of thin films. Thin
films can be deposited onto solid substrates by a variety of techniques including
(a) thermal evaporation by resistive or electron bombardment heating, (b) sputtering
by means of a glow discharge or ion beams, (c) chemical deposition, and (d) electrolytic
deposition. Depending upon the structure and temperature of the substrate the
deposited layers may be single crystal, polycrystalline or amorphous and all three are
finding increased applications in technology.
The growth of thin single crystal fllms on single crystal substrates is referred to as
epitaxial growth [10]. The term epitaxy (arrangement on)-was first introduced by
Royer in 1928 to describe the orientated growth of one crystal upon another. The
earliest examples of epitaxy were observed naturally in minerals but subsequently very
many examples of epitaxy have been observed in the laboratory. In almost all of the
observed cases of epitaxy there is a match oflattice symmetry at the substrate-deposit
interface, although the differences in actual lattice spacings may be relatively large
(>20 per cent). During the last decade or so epitaxial growth has been an active field
of interest both for fundamental studies and device applications. In the former case
the main emphasis has been aimed at understanding the nucleation and subsequent
growth of the deposited fllm and in this connection metal fllms deposited on freshly
cleaved surfaces of rocksalt and mica in ultra high vacuum systems have been studied
extensively.
The early work on the growth of epitaxial fllms of silicon and germanium for the
electronics industry was usually confmed to growth on single crystal substrates of the
same material (auto-epitaxy). However, recent developments in integrated circuits
which require individual devices to be electrically isolated from one another have
necessitated the growth of silicon, germanium and gallium arsenide, for example, on
insulating substrates such as sapphire followed by the isolation of neighbouring regions
by photolithographic techniques.
As a typical example of epitaxial growth we will consider the growth of silicon by
the hydrogen reduction of silicon tetrachloride at elevated temperatures, typically
ll50-1250°C, which involves the follOwing reaction:
SiCl4 + 2H2 ~ Si + 4HCl. (3.4)
Dry hydrogen gas is bubbled through the silicon tetrachloride causing it to vaporize,
and the mixture of vapour plus hydrogen is fed into a horizontal silica furnace tube
and over a substrate, which is usually placed on a conducting heat susceptor of
molybdenum or silicon carbide coated graphite, and heated externally by rJ. induction
heating (Fig. 3.16). The substrate temperature is an important parameter because it
tSilica
~~~ Substrate
Controlled /~_ _ _-,oUQl...JQ:L..P.Q..II.Q..IIQ..II~..II..II~/::"-----===~
/c: :::.(.1
gas inlet - - ' /'
-~ --=-'j~
Susceptor to
r.f. induction absorb the r.f. Gas
coil
outlet
Fig. 3.16 Epitaxial growth of silicon.
governs the surface mobility of the atoms once they are adsorbed onto the surface
and they must be suffiCiently mobile to attain a stable configuration. Control of the
dopant level in the inflowing gas stream results in thin fllms of required electrical
characteristics. Growth rates are typically a few Ilm/min. The quality of the substrate
surface has a direct effect upon the perfection of the epitaxial fllm and generally care-
fully prepared crystal slices from boules grown by the Czochralski or floating zone
techniques are used as substrates. In general the perfection of crystals grown on foreign
substrates is inferior to that obtained in the case of crystals grown on substrates of the
same material (see section 3.6).
In addition to the wide range of applications of thin fllm single crystals there are
many applications for thin polycrystalline fllrns. These can be deposited using the same
variety of techniques used for single crystal deposition, although there is no longer
any need for a single crystal substrate and glass, quartz or ceramic materials are often
satisfactory. Their uses cover a wide field ranging from the use of ferromagnetic fllms
as ~gnetic switches to optical fllms for mirrors and interferometers and to the
chemical deposition of a compound of niobium and tin, Nb 3 Sn, on foil for the windings
of superconducting magnets.
3.6 The origin of dislocations during crystal growth
As was seen in section 3.2, dislocations may play an important role in crystal growth
and, in addition, their presence is essential in explaining the mechanical properties of
materials. Therefore dislocations must be inherently introduced into crystals during,
or immediately following, crystal growth. One obvious source of dislocations is by the
propagation of those dislocations already existing in the seed crystal, but there are
several other mechanisms that can lead to the formation of further dislocations.
3.6.1 Collapse of vacancy discs

It was noted in section 2.10 that vacancies are a naturally occurring phenomena in
crystals at all temperatures and that their density may be very high at elevated tem-
peratures. During the cooling of the crystal from its freezing point these vacancies may
diffuse to the surface to maintain an equilibrium concentration. However, this is not
very significant in practice because the rate of cooling is usually too rapid to allow
sufficient time for adequate diffusion. Instead, these vacancies are more likely to be
captured at existing dislocations or collect and subsequently condense to form 'plates'
or 'discs' in definite lattice planes. The closing of such discs may lead to the formation
of a general dislocation loop with associated contraction of the vacancy disc as
illustrated schematically in Fig. 3.17.
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0.0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0-4 ... 0 0
0 0 0 0
t0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Fig. 3.17 Formation of a dislocation loop by construction of a vacancy disc.
3.6.2 Strain resulting from thermal stress or impurities

If the temperature gradient in the solidified crystal is excessive or is non-uniform con-
siderable thermal stress will be set up in the crystal and dislocations may be formed to
relieve this stress concentration. Similarly incorporation of impurity atoms into the
growing crystal leads to local changes in the lattice constant because the impurity
atoms are rarely the same size as the host atoms. If the incorporation of these impurity
atoms is non-uniform, either because of a non-uniform impurity content in the melt or
because of fluctuations in the growth rate, layers in the crystal will have different
lattice constants and dislocations may be formed to reduce the strain energy between
these layers.
3.6.3 Dendritic growth

If the melt is cooled too rapidly so that considerable supercooling occurs, dendritic
growth may result. The dendritic structure grows rapidly and solidification ends with
the dendrites branching on all sides. Eventually these separate dendrites must meet
and, almost certainly, there will be some slight misorientation between them at the
interface so that a complex dislocation network may arise to accommodate this lattice
mismatch.
Since the aim of all crystal growth techniques must be to produce crystals of as
high a structural perfection as possible it is obvious that slow, well controlled growth
at a constant rate is essential and that considerable care must be taken to eliminate
drastic thermal gradients in the cooling crystal. The techniques discussed in the
preceding sections vary considerably in their degree of control over these various
factors and so the structural perfection achieved differs from technique to technique.
In general the Czochralski, or crystal-pulling technique is the most easy to control and
provided other factors allow this is usually the best technique to use.
In crystals grown epitaxially on foreign substrates considerable stress, and hence
dislocations, may arise in two additional ways. In virtually all cases of epitaxy there
is a finite mismatch between the lattice constant of the substrate and the deposit,
and it has been shown theoretically that this misfit will be partly accommodated by
elastic strain in the growing crystal and partly by an array of misfit dislocations near
the interface. Furthermore, growth usually occurs on substrates at elevated temperatures
and extremely large stresses can be introduced during cooling back to room tempera-
ture because of the difference in thermal contraction between the substrate and over-
growth (Plate 2). For example silicon crystals grown on insulating sapphire substrates
have been shown to be highly strained and exhibit high densities of structural imper-
fections. Extremely large interfacial stresses can arise from this difference in thermal
contraction and they may be sufficiently large to produce plastic deformation and
even cleavage in the resulting crystals. Plate 3 shows a 100 Jlm film of nickel oxide,
NiO, grown on a magnesium oxide, MgO, substrate at 700°C. It is interesting to note
that the interfacial bond between the deposit and substrate is very high and there is no
tendency for the film to peel away from the substrate.
3.7 Non-crystalline materials
In addition to the use of polycrystalline metals and alloys cast from the melt the
metallurgist has made an increasing use of non-crystalline material. If a metallic powder
is subjected to a sufficiently high pressure a degree of bonding takes place between the
particles even at room temperature and a coherent mass of material is produced. Heat-
ing, or sintering the compacted mass improves the coherence between the particles by
promoting intergranular grain growth and diffusion.
Originally powder metallurgy techniques were used to replace castings for those
metals which were difficult to melt industrially because of their high melting points;
for example, the sintered carbides of tungsten and titanium used in cutting tools and
drawing dies. However, they have now been extended beyond the treatment of re-
fractory materials into many other branches of metallurgy. Practical alloys cannot be
produced from the liquid phase unless the metals concerned are mutually soluble in
the liquid state and the powder technique is of particular interest to the metallurgist
since it frees him from the limitations imposed by phase equilibrium; for instance it is
not easy to produce copper-lead bearing alloys by any other techniques. The addition
of non-metallic substances which would be insoluble in the liquid alloy and consequently
would not be incorporated into its structure, can also be achieved with the knowledge
that they will be evenly distributed throughout the material. Thus, graphite and copper
can be compacted for the manufacture of dynamo brushes, whilst small additions of
thorium oxide can be made to tungsten destined for the production of electric-lamp
filaments. The technique can even be extended to include the manufacture of alloys
which can also be produced by more orthodox methods. For example an alnico alloy
produced by powder metallurgy can be magnetically superior to one produced by
casting from the melt.
Closely associated with this technique of powder metallurgy is the production of
ceramics, which is the general name applied to a wide range of non-metallic compounds
such as silica, Si02 , and alumina, Al2 0 3 . Ceramics are usually hard, brittle, amorphous
or glassy solids which are produced by compacting and subsequent sintering. One of
their most important uses is as insulators, both thermal and electrical; ceramic di-
electrics, including glass, are generally stable at elevated temperatures and have
relatively high permittivities. Certain ceramic oxides are magnetic and, although they
are ferrimagnetic with generally lower saturation magnetization and relative permit-
tivity than metallic ferromagnetics, they have higher resistivities than metals or alloys
and hence have smaller energy losses due to Joule heating.
With the tremendous demands placed on materials recently by the technological
advances of supersonic flight and the exploration of space, the search for new materials
is being actively pursued and increasing use is being made of composite materials. The
principal attraction of composite materials is that they are lighter, stiffer and stronger
than more conventional materials. Considerable increase in strength can be achieved by
fibre reinforcement, i.e. embedding very strong fibres in a suitable matrix such as
polyester resin or a ductile metal, e.g. boron fibres embedded in aluminium. The matrix
itself is important because it must protect the fibre surface from damage due to
abrasion, it must separate the individual fibres so that cracks cannot run from one to
another, and finally it must be able to bond to the fibre surfaces so that the stress can
be transferred to the fibres. The strength of these composite materials tends to be
highly directional and usually they are less strong in compression or shear than in
tension.
Some everyday examples of composite materials are reinforced concrete and glass
fibre reinforced plastics which can be used for such diverse applications as kitchen
sinks, motor car bodies and motor tyres. The major attraction of glass fibre rein-
forcement is the ease with which we can obtain long strong glass fibres. These fibres
have immense strength when freshly drawn, comparable in fact with the strongest
steels, but the strength can only be sustained if the surface of the glass fibres is pro-
tected by some suitable matrix such as a plastic.
Although filaments of glass have proved to be strong as stiffeners, there are other
materials which are even stiffer, stronger and sometimes lighter. For example very
fine filaments have been drawn of such substances as tungsten, carbon, silicon carbide,
silica and boron, and the fibres of carbon and boron now in production are more than
twice as stiff as steel although less than a third as dense. Of all the components to
emerge in recent years the one which has attracted most public interest is the carbon
fibre reinforced plastic which has been used with success injet engines. The starting
point for the carbon fibres is usually a man-made fibre; acrylics such as poly acrylonitrile
and Courtelle which can be converted by pyrolysis at about 3000°C into pure poly-
crystalline carbon up to six times as stiff as glass fibres. These fibres can then be
bonded with a suitable resin, for example an epoxy or a polyamide.
However, the ultimate in strengthening materials may finally be achieved by rein-
forcing with single crystal whiskers which approach more closely the theoretical
strength than any other form of the material. Considerable attention has been paid to
the manufacture of whiskers of silicon carbide, boron carbide and aluminium oxide
and test specimens of composites reinforced with these whiskers reveal quite remark-
able strengths.
3.8 Amorphous semiconductors
Although the crystalline semiconductor device industry is very highly developed there
is reason to believe that amorphous devices will prove useful in the future. Currently,
considerable research effort is being directed towards the eventual commercial applica-
tion of amorphous semiconductors.
The term amorphous is sometimes used synonymously with glassy or vitreous states.
The latter are usually restricted to those materials obtained by supercooling a melt
while the term amorphous is reserved for fllms produced by vacuum evaporation,
sputtering, electrolytic deposition and related methods. Semiconducting glasses which
have received most attention are the chalcogenide glasses formed from compounds of
sulphur, selenium and tellurium with a variety of other elements such as phosphorus,
arsenic, antimony and bismuth. The transition metal oxide glasses are those in which
a major constituent is a transition metal oxide and of these the vanadium phosphates
012 0S-P2 Os) have been the most thoroughly investigated. In this system glasses with
up to 95 mol per cent of V2Os can be prepared by cooling from the melt. V2Os -Te02
and V20s-BaO have also been prepared. Ternary systems such as V20S-P20S-R20
(or RO) where R is an alkali or alkaline earth metal are also known. Many of the
chalcogenide glasses can be prepared by cooling from the melt although it may be
necessary to melt under vacuum or in an inert atmosphere and rapid cooling may be
required to inhibit crystallization.
For some glasses, for example AS 2Tea, conventional cooling from the melt is not
sufficiently rapid to prevent crystallization and they can only be prepared by evapora-
tion or similar techniques.
The glass-forming region for the ternary system Ge-Se-As is shown shaded in Fig.
3.18. Well inside this region the metal may be prepared by cooling the melt. Near the
boundary, splat cooling [11] may be used while outside it the amorphous phase can
be obtained by evaporation.
Splat cooling is used where conventional cooling from the melt is not sufficiently
rapid to prevent crystallization and with it cooling rates as high as 106 K S-l can be
achieved. In this technique a liquid droplet is driven at high velocity on to the spinning
surface of a cold metal such as copper. The droplet spreads out rapidly into a very thin
film about IJ,Lm thick in good thermal contact with the metal. An alternative is the
hammer and anvil method where two cold metal blocks are clapped together as the
liquid is dropped between them. Germanium and silicon can only be produced in the
amorphous state by deposition from the vapour. Amorphous Si and Ge fllms up to
0·2-0·3 J,Lm thick can readily be deposited by electron beam evaporation of the element
on to a cold substrate (less than about 670 K for Ge and 870 K for Si) [12]. They can
Ge
Se As
Fig. 3.18 Ternary system Ge-Se-As showing glass-forming region (shaded).
also be prepared by other vapour deposition techniques, for example sputtering in

argon, electrolytic deposition onto a copper cathode from an electrolyte of Ge Cl4 in
C3 H6 (OH)2 or decomposition of a volatile compound in a glow discharge.
3.9 Plastic materials
High polymers, i.e. plastic or elastic (rubbers) materials consist of molecules of large
molecular weight ("'10 3 _10 6 ) and a large number of different polymeric materials
can now be synthesized by chemical reactions in which these large molecules are
built up from relatively simple substances oflow molecular weight, i.e. the monomer.
The production of these high polymers from the simple monomers is termed poly-
merization. The simplest type of large molecule consists of a linear chain in which the
repeat units in the molecule are connected together by covalent bonds. However,
branched chains are by no means uncommon (Fig. 3.19), although they are some-
thing of a nuisance in practice because there is little or no control over the regularity
of the branching. The process of polymerization can occur in the solid, liquid or
S'- S - S - S- -S-S-S-S"
(a) Linear chain
5'- S - S - S - - S - T -S - ... -S-S"

I
S
I
(b) Branched chain S
Fig.3.19 Simple polymer configurations. (The repeat unit is represented by S and the end units
S' and SIt may not be identical but are usually different from S. The unit T may well arise from a
different monomer.)
gaseous states, although polymerization in the liquid state is by far the most common.
However, there are basically two different types of polymerizing reactions that can be
distinguished.
3.9.1 Polymerization
(a) Addition polymerization

This is a reaction which results in the bonding of additional monomer molecules to the
growing chain without the elimination of any by-product molecules. The classic
example of this type of reaction is the bonding of many ethylene molecules (C z H4 )
to form polyethylene (C Z H4 )n' as depicted schematically in Fig. 3.20. Obviously
H H H H H H H H H
I I I I I I I I I
c=c -c-c- - -_ .. -c-c-c-c-c-
I I I I I I I I I
H H H H H H H H H
(a) (b) (e)
Fig. 3.20 Formation of polyethylene. (a) Ethylene molecule with a double bond between the
carbon atoms. (b) Activated ethylene molecule. (c) Polyethylene.
there must be some agency, called an initiator, to initially break the carbon-carbon
double bond. Fortunately this is not as difficult as it may appear for the double bond
is in a highly strained state, since as we saw earlier, covalent bonds tend to separate
spatially from each other as much as possible. Typical initiators are free radicals or
charged ions which can be produced by thermal or photochemical decompOSition.
Once initiated the polymerization process advances rapidly, because each added mono-
mer produces yet another free radical, until the monomer molecules are gradually con-
sumed and then the probability of the chain terminating increases. This termination
may be caused by the joining of two chains or by the interaction between the end
free radical and another molecular species which does not produce another free radical
to continue the reaction.
Starting with a different monomer other types of polymer can be produced in which
the 'backbone' is still a linear array of carbon atoms but the side groups are not just
hydrogen as in the above example of polyethylene. Other common examples of addition
polymers include:
(i) Polypropylene
HHHHHH
I I I I I I
--C-C-C-C-C-C-
hCHI hCHI ACHI
3 3 3
(ii) Polytetrafluorethylene (PTFE)

F F F F F F
I I I I I I
-C-C-C-C-C-C-
I I I I I I
FFFFFF
(iii) Polystyrene
nnvY
-91-Y-I-Y-r-
HUHCJ H
Where 6 represents the benzene ring
H
I
H'C~'C/H
I 11
H.....c::::::C/C'H
I
H
The regularity and complexity of these side groups considerably affects the physical
properties of the resulting polymer, because, if the side groups are large as in the case
of polystyrene then neither molecular packing or relative molecular movement will
be very good (see subsection 3.9.2). Polymerization from a mixture of two monomers
is also possible and this leads to a class of polymers known as copolymers.
(b) Condensation polymerization (polycondensation)

Condensation reactions occur between molecules in such a way that a simple compound,
such as water, is eliminated. For example consider the reaction between ethylene
glycol and terephthalic acid represented by
HOCH 2CH 2OH + HOOCOCOOH ~ HOC H2 CH 2 OOCOCOOH + H2 O. (3.5)
As well as noting the elimination of H2 0 it is important to realize that there is

essentially no difference between the compound molecule and the two initial molecules
in that they all have reactive OH units at the ends. Thus this compound molecule
could subsequently condense with another molecule of acid or glycol or with another
compound molecule leading, in this example, to the polyester Terylene.
Thus, in general, condensation reactions are characterized by monomers reacting
with monomers to from dimers; dimers with dimers to form tetramers, etc. and
ultimately chains with chains. Unlike addition polymerization reactions which usually
result in linear polymers, condensation reactions often lead to branched polymer
chains with consequent differences in physical properties.
3.9.2 Structure o[polymers

Since the process of polymerization is such a random one there is little correlation
between the lengths of the individual chains. Thus, instead of associating a specific
molecular weight with a given polymer one can only talk in terms of an average
molecular weight or chain length.
So far it has been assumed that a linear polymer molecule consists of a straight
chain, or backbone of carbon atoms, with various possible side units attached. This
is, however, far from the case in practice because the tetrahedral nature of the
covalent bonds will cause the carbon backbone to zig-zig as shown diagrammatically
in Fig. 3.21 in two dimensions for polyethylene. Furthermore, in the absence of any
Fig. 3.21 Zig-zag nature of a linear polymer.
external forces which would keep the molecule extended in this way, the large free-
dom of rotation about the single bonds in the chain means that there is a high degree
of flexibility and so extensive bending and twisting of the chain results. Thus, the
general configuration of a linear polymer molecule tends to be that of an irregular
coil.
These long chain molecules are generally mixed together in a solid polymer in a
random manner just like a tangled bundle of coiled fibres. Whereas the molecules in
any individual chains are held together by strong covalent bonds, the bonds between
the various molecules are only weak secondary bonds commonly of the van der Waals
type. The basic structure, therefore, will be amorphous. Occasionally there will be
some regions in the material where the linear chains are aligned close enough to one
another so that the weak intermolecular forces are sufficient to keep them parallel.
Over these regions the material is said to be crystalline. These crystalline regions are
usually quite small and in fact one individual chain may form a crystalline region on
its own due to a regular arrangement of the folds. The random length of the individual
chains means that polymers are never completely crystalline and one individual molecule
may pass through several crystallites. These various polymer structures are illustrated
in Fig. 3.22. The crystallinity of a polymer has a considerable influence on its physical
(a) (b) (e)
Fig. 3.22 Polymer structures. (a) Amorphous. (b) Partly crystalline (different molecules). (c)
Partly crystalline due to the regular orientation of the coils of a single molecule.
properties. A polymer with a predominantly crystalline structure is appreciably stronger,

more rigid and less permeable to fluids than the corresponding amorphous polymer.
Usually the crystalline regions are orientated in a completely random manner but
application of an external force, as for example in the drawing of fibres, may orientate
the crystalline regions leading to anisotropy of the physical properties. Branched
chain molecules are less likely to form crystalline regions because the presence of the
branches prevents close enough approach of the separate molecules for the weak inter-
molecular forces to orientate them. This is also true for those linear molecules which
have excessively large side groups randomly arranged along the chain.
In addition to the polymer structures discussed above, separate linear or branched
chain molecules may be joined together at random points along the chains by primary
covalent bonds. This process is called cross-linking and results in a more rigid structure
as it tends to prevent slipping between the individual chains. A common example of
cross-linking occurs in the vulcanization of rubber in which the raw material is heated
in the presence of 1-2 per cent by weight of sulphur resulting in a random array of
sulphur cross linkages. If the percentage of sulphur is increased to about 30 per cent
of the rigid material, ebonite is produced. Cross-linking is one of the major effects
produced by irradiating polymers with high energy radiation such as'Y rays. In addition
it may be caused accidentally by oxygen or sulphur atoms catalysed by light, leading
to a decrease in the article's elastic properties.
3.9.3 Thermoplastic and thermosetting plastics

Although there are a vast number of plastic materials available with an associated wide
range of physical properties, most plastics can be usefully classified into one of two
groups; namely thermoplastic and thermosetting. The thermoplastic plastics are
essentially linear polymers which can be softened and resoftened indefinitely by the
application of heat. Examples are the polyethylenes (household containers) and poly-
methylmethacrylate (perspex). On the other hand thermosetting plastics undergo a
chemical change, such as extensive cross-linking, and after this their shape cannot be
changed by the application of heat or pressure. There are two convenient methods
whereby the cross-linking reaction can be initiated. In one case, e.g. phenolformaldehyde
resins (bakelite), cross-linking is accomplished by heating the resin in a suitable mould.
Alternatively resins such as epoxies, e.g. Araldite, are cured at low temperatures by the
addition of a suitable cross-linking agent, an amine (hardener), which opens the epoxy
ring to form a cross-linked structure. The establishment of the three-dimensional cross-
linked structure is termed curing.
References
1. Nielsen, S. Science J. December, 59-64 (1965).

2. Harrison, F. W. Research 12, 395 (1959).
3. Frank, F. C. Adv. Phys. 1,91 (1953).
4. Poplawski, R. P. and Thomas, J. E. Rev. Sci. Inst. 31, December, 1303-1308 (1960).
5. Laszlo, T. S. Image Furnace Techniques, Wiley (1965).
6. Pfann, W. G. Sci. Am. 217, December, 63-72 (1967).
7. Laudise, R. A. and Nielsen, S. Solid State Phys. 12,149 (1961).
8. Schafer, H. Chemical Transport Reactions, Academic Press (1964).
9. Henisch, H. K. Crystal Growth in Gels, Pennsylvania State University Press (1970).
10. 000, V. Y. and Ernest, E. O. SCPand Solid State Technology, October, 31-39 (1967).
11. Duwez, P. Trans. ASM 60, 607 (1967).
12. Hilsch, R. Non Crystalline Solids (edited by V. Frechette), ch. 15, Wiley (1960).
4 Practical Determination
of Structure
4.1 Introduction
Although optical microscopy was an invaluable tool in the early days of crystallography,
the information that it revealed was rather limited. Measurement of the angles between
the faces of well defmed naturally occurring mineral crystals enabled the overall sym-
metry of the crystal structure to be inferred. However, the large wavelength of visible
radiation meant that the resolution obtainable was much too poor to resolve detail on
an atomic scale, and no informaton as to the size of the unit cell and the actual positions
of the atoms could be deduced. Evaluation of this detailed structure had to await the
advent of X-rays during the first few years of this century. X-rays are electromagnetic
waves like visible light but with a much smaller wavelength. This wavelength is typically
10- 10 m and is of the same order of magnitude as the interatomic spacings in crystals,
and so the network of atoms in solids acts like a naturally occurring three-dimensional
diffraction grating. The techniques of X-ray crystallography have enabled the actual
atomic positions in a vast number of simple and complex structures to be determined
and, in addition, X-ray diffraction has provided valuable information on many other
aspects of structure including preferred orientation in polycrystalline sheets or wires,
and crystal imperfections such as grain boundaries and dislocations.
Initially there was no practical alternative to X-rays for investigating crystal struc-
tures, but following the de Broglie hypothesis of 1924 that moving particles possess
wave properties (eqn. (1.1)), both electrons and neutrons were shown to be diffracted
by crystals. Electron and neutron diffraction in no way replace the much more versatile
X-ray diffraction, but under certain circumstances they can provide complementary
information. All three techniques will be discussed in more detail in the subsequent
sections of this chapter.
4.2 Theoretical X-ray diffraction
Before discussing the experimental techniques used in X-ray crystallography the theo-
retical aspects of the diffraction of X-rays by crystals will be considered briefly. When
X-rays strike an electron the varying electric and magnetic fields associated with the
radiation force the electrons to vibrate at the same frequency as the incident X-rays
and the vibrating electrons in turn scatter secondary radiation of the same wavelength
in all directions. All the electrons in an atom contribute to the scattering of X-rays so
that the higher the atomic number of an atom the more effective it is as a scatterer
of X-rays.
Consider a collimated beam of monochromatic X-rays incident at an angle 9 to a

single horizontal planar array of atoms (Fig. 4.1). Each atom (or the electrons in it)
scatters secondary radiation of the same wavelength in all directions. However, only
in those directions which satisfy Huygens' construction for regular reflection from the
plane will all the scattered rays be in phase with each other and give a reasonably
intense scattered beam of X-rays. For this reason the plane of atoms acts like a plane
metallic mirror reflecting the incident beam, and the scattering of X-rays by the plane is
often referred to as reflection. In practice, of course, a crystal consists of a three-
dimensional array of atoms which may be thought of as a family of parallel planes
each similar to that of Fig. 4.1. Each of these will reflect as described.
Incident 'Reflected'
b..m~ ~b.. m
9~9 e
Fig. 4.1 Reflection by a single planar array of atoms.
Consider a simple three-dimensional lattice, as shown in Fig. 4.2, with the incident
parallel beam of X-rays of wavelength, A, making an angle 9 with a set of crystal planes
of interplanar spacing d. Assuming that the X-rays are not refracted on entering the
crystal (they are, in fact, refracted to a very slight extent but this only produces changes
of the order of 1 in 104 ) then each plane of atoms alone will tend to reflect a beam
Incident Diffracted
wave wave
tf,~t
e 9 e e e e
:
e
Fig. 4.2 Explanation of Bragg's law.
of X-rays in a direction making an angle 9 with these planes. However, these beams
may, due to their relative path differences, either interfere destructively or construc-
tively. The criterion for the existence of constructive interference and an intense
diffracted beam is that the reflected rays from the individual planes should be in phase
across the entire wavefront. For this to be so, the path difference between two succes-
sive rays must be equal to an integral number of wavelengths, i.e.
d sin 9 + d sin 9 = nA, where n is an integer
or
2d sin 9 =nA. (4.1)
This result is known as Bragg's law and forms the basis of modern X-ray crystallography.
Although it is common to find the Bragg law stated in this form, where n is the
order of reflection, or diffraction, it is not common usage in X-ray crystallography. If
diffraction occurs from the (100) planes of a lattice for example at an angle 9 1 , then
PRAcrICAL DETERMINATION OF STRUCTURE 67
when the path difference between the beams diffracted from adjacent planes is 2A,
instead of A, diffraction will occur at an angle 8 2 and the above equation will be
satisfied with n =2. These reflections are then called respectively the first and second
order reflections of (100). This terminology is a direct transfer from the science of
optical spectroscopy but it has little to recommend it in X-ray crystallography since
the second order reflection from (100) is equivalent to the first order reflection from
the (200) planes (Le. with d halved) and these planes are as uniquely defined as any
others (Chapter 2). Thus in practical X-ray crystallography the above law is of more
use in the form
2d(hkt) sin 8 =A, (4.2)
and each angle 8 is associated with a specific set of lattice planes (hkl). Thus, if A is
known (it can be measured directly using special ruled gratings) and the various values
of sin 8 can be measured, a set of values of d hk1 can be calculated. The interplanar
spacings d of any set of planes depends only on the type and size of the unit cell and the
Miller indices of the plane, for example:
h2 + k2 + [2
for a cubic crystal (4.3)
dlhkt) = a2
and
1 4(h 2 + hk + k 2 ) f
for a hexagonal crystal -2d = 32 +2", (4.4)
(hkt) a c
where a and c are respective lattice parameters. Combining eqns (4.2) and (4.3) it
follows that, in the case of a cubic crystal,
(4.5)
where A =A2 /40 2 =constant. For a cubic crystal the values of sin 2 8 will form a simple
series consisting of the constant A multiplied by a variable integer (h 2 + k 2 + f). The
Miller indices of each reflection, and the lattice constant can then be determined quite
easily. In the case of a hexagonal crystal the sin 2 9 values will follow a more complex
form, since two constants are involved, but it is not too difficult to manipulate these
figures to determine both the indices of the reflection and the unit cell parameters. The
same principle holds, of course, for all seven types of crystal system but as the sym-
metry of the unit cell decreases so the complexity of the problem increases.
The directions of the diffracted beams given by Bragg's law are governed entirely by
the geometry and size of the unit cell, and, therefore, these directions are not affected
by the arrangement of the atoms associated with each lattice point. However, the com-
plexity of the atomic structure within the unit cell does affect the intensities of the
diffracted beams. The diffracted beams are built up by a combination of the scattered
waves from the electrons of all the atoms in the unit cell and this involves two distinct
contributions:
(1) scattering from electrons in the same atom (the atomic scattering factor,{o), and
(2) the summation of this scattering from all the atoms in the unit cell (the structure
scattering factor, F).
If the atoms were merely points, their atomic scattering factors (the ratio of the ampli-
tude scattered by an atom to that scattered by an electron) would be equal to their
atomic numbers. However, atoms have a fmite size which is of the same order of
magnitude as the X-ray wavelengths and this causes phase differences between the waves
scattered from the various electrons. Therefore, the atomic scattering factor varies with
(sin ())/'A as illustrated in Fig. 4.3. Only at small values of (sin ())/'A does it approach the
atomic number.
fo
o~------------~----------~
(sin 8"!tA
Fig. 4.3 Variation of atomic scattering factor with (sin 8)/A.
Consider now the total intensity of a diffracted beam that results from the combina-
tion of the waves scattered by all the atoms in the unit cell; e.g. the (100) reflections from
a b.c.c. crystal. When the diffracted beams from successive (100) planes differ in path
length by one wavelength they will constructively interfere, but the atoms at the centres
of the unit cells will give rise to a scattered beam in the same direction which differs in
path length from these two by exactly X/2 and thus interferes destructively. In this
simple example assume that all the atoms are of the same type so that their atomic
scattering factors are equal, and furthermore, the concentrations of the atoms in the
respective planes are equal so that complete cancellation occurs and the (100)
reflections will not be observed.
In general to calculate quantitatively the total amplitude of a given reflection it is
necessary to sum the waves that arise from all the atoms in the unit cell and mathe-
matically this involves adding waves of the same wavelength but different amplitudes
and phases; the square of the resultant amplitude will be the required intensity. If the
positions of the atoms in the unit cell are denoted by x, y and z, where these coordinates
are expressed as fractions of the unit cell parameters, the resultant amplitude for a
given (hkl) reflection can be shown to be given by
n
Fhkl = '2./; exp {2nj(hx; + ky; + lz;) (4.6)
1
or
n n
Fhkl = '2./; cos 2n (hx; + ky; + lzi) +F'ili sin 2n(hx; + kYj+ lzj) (4.7)
1 1
and the intensity of the reflected beam is proportional to F~kl' For the b.c.c. crystal
considered above, having identical atoms at points (000) and (H!) in the unit cell,
eqn. (4.7) reduces to
I ex F~kl ex 12 [{I + cos n(h + k + l)}2 + sin2 n(h + k + 1)] . (4.8)
PRACTICAL DETERMINATION OF STRUCTURE 69
It can be seen from this equation that f = 0 for every reflection having (h + k + l) an
odd number. Thus the (100) reflection is not observed as was seen earlier. This condi-
tion holds for any body centred structure. A similar analysis in the case of a simple
f.c.c. crystal with atoms at positions (000), (BO), (4 O!)and (OB), reveals that the
intensity is zero for all reflections in which the integers (hkl) are partly even and
partly odd. Because of the systematic absence of particular reflections, the observed
series of (hkl) values obtained from the measured values of sin 2 0 enables the basic
structure to be deduced.
For more complex unit cells containing atoms of at least twO different types the
intensities may not completely vanish because of the difference in the atomic scattering
factors. For example in the CsCI structure where a caesium atom is at (000) and a
chlorine atom at (B!) quite a different result is obtained than that for the simple b.c.c.
structure discussed above. In this case eqn (4.7) becomes:
fa. {fcs+fcICOS1T(h+k+l)}2 + {fClsin1T(h+k+l)}2 (4.9)
which reduces to
f 0: (fcs+ fCl)2, when (h + k + l) is even
and
1.0: (fcs- fcD2, when (h + k + l) is odd.
In general the intensities of the various reflections are very susceptible to slight changes
in the coordinates of the atoms in the unit cell and a correlation between the measured
and calculated intensities enables the positions of the atoms in the unit cell to be deter-
mined precisely.
Thus, to determine completely the crystal structure of a material the various diffrac-
tion images must be recorded in such a way that both the angles of diffraction, 0, and
the intensities of the images can be measured. The most usual way of doing this is to
record the diffraction pattern photographically and measure the intensities either
visually or with some form of densitometer. However, for very large complex unit cells,
where there may be as many as 10 000 diffraction images, the information can only be
treated by recording the positions and intensities of the diffraction images automatically
using a scintillation counter or a proportional counter as detector.
4.3 Practical X-ray diffraction [1]
In order that Bragg's law can be satisfied and X-ray diffraction can occur the various
values of 0 and Amust be related. It is necessary in practice to vary either the angle
of inclination of the specimen to the beam or the wavelength of the radiation. The
three standard methods of X-ray crystallography allow for this in the following ways:
(a) in the Laue technique a stationary single crystal is irradiated by a range of
X-ray wavelengths;
(b) in the rotating crystal technique a single crystal specimen is rotated in a beam
of monochromatic X-rays; and
(c) in the powder technique a polycrystalline powder specimen is kept stationary
in a beam of monochromatic radiation.
Each of these three techniques will be discussed in more detail after a brief considera-
tion of the nature of the X-rays emitted from a standard high voltage X-ray tube. The
X-rays are not all of the same wavelength. The X-ray spectrum consists of two com-
ponents: (i) the continuous or white background radiation and (ii) the superimposed
high intensity peaks, as illustrated in Fig. 4.4. The most important peaks are usually
the Ka. and K(J peaks shown in Fig. 4.4. and, as can be seen, the Ka. peak is strictly a
close doublet of which the Ka.l is about twice as intense as the Ka.2 peak.
0.4 0.6 0.8 1.0

Wavelength (10-~)
Fig.4.4 Typical X-ray spectrum for a high voltage (-50000 V) tube.
For the Laue technique the whole range of wavelengths is used but for the other
two techniques a single wavelength is required. This can be satisfactorily achieved by
passing the X-ray beam through a suitable thin metallic filter which preferentially
absorbs the K(J radiation and some of the white background. For example, copper
radiation is commonly used in X-ray crystallography and a sheet of nickel 0·002 cm
thick will absorb about 99 per cent of the CuK(J but only 50 per cent of the CuKa.. If
it is essential to remove all the white radiation the X-ray beam must be reflected from
a given set of lattice planes of a large single crystal set at the correct angle for diffraction
of the Ka. radiation.
4.3.1 The Laue technique

A single crystal is mounted on a goniometer, which enables the crystal to be rotated
through known angles in two perpendicular planes, and maintained stationary in a beam
of X-rays ranging in wavelength from about 0·2 x 10- 10 to 2 X 10- 10 m. The crystal
selects out and diffracts those discrete values of X for which planes exist, of spacing d
and glancing angle (), satisfying the Bragg equation. A collimating arrangement is
employed to produce a narrow, parallel beam of X-rays and so there is no need for the
dimensions of the crystal to be greater than 1 mm. A flat photographic f11m is placed
to receive either the transmitted diffracted beams or the reflected diffracted beams
as illustrated in Fig. 4.5. As shown in the diagram the resulting pattern consists of a
series of spots. Sharp well defined spots on the film are good evidence of a perfect
crystal structure, whereas diffuse, broken or extended spots indicate lattice distortion,
defects or other departures from the perfect crystal lattice. Thus, it is a quick method of
detecting imperfections in single crystals.
The pattern reveals the symmetry of the crystal structure in the orientation used;
for example if a cubic crystal is orientated with a cube edge, i.e. a [100] axis, parallel
to the incident beam the Laue pattern will show the fourfold symmetry appropriate to
White'
X-ray
beam
~-G::=*:::::::>
/
Collimator SinglLcrystal
/
Screen for back-reflection
/
pattern Screen for transmission
pattern-showing
a typical pattern
Fig. 4.5 Schematic representation of the Laue technique.
this axis. This feature makes the Laue technique particularly convenient for checking
the orientation of crystals. However, the method has fundamental disadvantages for
crystal structure determination because the wide range of wavelengths employed leads
to overlapping of diffraction images from different planes of atoms, e.g. Al from (001)
and Al /2 from (002), and the unknown wavelengths producing the various reflections
makes indexing the reflections almost impossible. Furthermore the variation of intensity
with wavelength in the incident beam makes useful intensity measurements impossible.
4.3.2 The rotating crystal technique

A small single crystal, whose dimensions are typically 1 mm, is mounted on a gonio-
meter which, in turn, is rigidly fixed to a spindle so that the crystal can be rotated
about a fixed axis in a beam of monochromatic radiation. The specimen is usually
orientated with one of the crystallographic axes parallel to the axis of rotation. The
resulting variation in (J brings different lattice planes into position for reflection and
the diffracted images are recorded on a photographic film placed cylindrically, coaxial
with the rotating spindle (Fig. 4.6).
Photographic
film
Monochromatic Single
crystal
X-ray beam
- - t - Goniometer
~-tt::::=--- Rotating
spindle
Fig. 4.6 The rotating crystal technique.
The explanation of the observed diffraction pattern is somewhat complicated in

terms of the Bragg equation because the angle between the incident beam and the
lattice planes is constantly changing and the three-dimensional problem is difficult to
visualize. However, the general nature of the pattern can be explained quite simply
as follows. Consider a crystal mounted so that the c axis is parallel to the axis of
revolution, then diffraction cannot occur from the planes of atoms parallel to this
axis unless
c cos tPn = n"A, (4.10)
where n is an integer (Fig. 4.7a). The diffracted beams will therefore be along the
surfaces of a family of cones whose vertices are at the crystal, and whose semi-vertical
angles are given by the above equation (Fig. 4.7b).
(a) (b)
Fig. 4.7 Illustration of the formation of the diffraction pattern in the rotating crystal technique.
(a) Diffraction condition. (b) Cones of diffraction.
Of course, the diffracted beams will only occur along those specific directions lying
on the cones for which the correct phase relationship also holds for planes parallel to
the other two coordinate axes. When the ftlm is flattened out after development these
diffraction images will lie on a series of lines called layer lines, as illustrated in Fig. 4.8.
LaVe\'ine
•• . ., .. • \/ .. •• • •• l=2
•• •• •••
,• • • • • • •
\
,•, • • • • • •
I
--...-.--....--..--<>-----..... -...._-- l=O
•• •• •••
,
I
l: -1
I
~.~.~~.~.~~.~.__~.______~,__~.~.__~.~.__~.~. l=-2
Fig. 4.8 Typical rotation photograph.
All the images on the zero layer line come from planes parallel to the axis of rotation,
i.e. planes with 1=0 in this example, and the other layer lines arise from planes with
1= ± 1, ±2, ... , etc. Diffraction images from planes with the same values of h and k
but different values of 1, all lie on one of a series of curves known as row lines which
are transverse to the layer lines and in the particular case when the a and b axes are
perpendicular to c they intersect the zero layer line at right angles.
Measurement of the separation, Sn, of these layer lines provides a rapid, 1 per cent
accurate, measurement of the c parameter of the unit cell, since from the geometry
of the diffraction, if R is the radius of the camera (Fig. 4.7b),
Sn =R cot cf>n (4.11)
and elimination of cf>n between eqns (4.1 0) and (4.11) leads to
c = (nX/Sn)(R2 + S/)1I2. (4.12)
By subsequently orientating the crystal with the a and b axes parallel to the axis of
rotation, the other unit cell parameters may be qUickly determined.
The values of 8 for each of the reflections can be determined fairly easily from their
positions on the film and so theoretically indexing the reflections should be quite
straightforward. In practice, however, complications may arise because the large number
of possible reflections leads to considerable overlapping of images and this causes un-
certainties in both the indices and intensity of the reflections. Therefore, for a com-
plete structure determination this problem of overlapping reflections must be overcome
and in practice this is done in one of two ways; either
(a) the crystal is oscillated through a small angle of about 10° rather than rotated
through 2rr (however, this cuts down the information available on any single
photograph and so necessitates the taking of many exposures); or
(b) some form of moving film technique can be used, as for example in the
Weissenberg technique. In this method the cylindrical film is moved backwards
and forwards parallel to the axis of rotation in exact synchronism with the rota-
tion of the crystal. Furthermore there is a screen with a narrow aperture between
the crystal and the film so that only reflections from a single layer line are
recorded in anyone exposure and, because of the movement of the film, these
images are spread out over the whole of the film.
4.3.3 The powder technique

In many crystalline solids individual crystals large enough for the rotation crystal tech-
nique are not readily available. Such substances can, however, be examined by a
method devised independently by Debye and Scherrer in Germany, and Hull in
America. In this method a monochromatic X-ray beam is allowed to irradiate a small
specimen of the substance ground to a fine powder and contained in a thin-walled
glass capillary tube. Since the orientation of the minute crystal fragments is com-
pletely random, a certain number of them will lie with any given set of lattice planes
making exactly the correct angle with the incident beam for reflection to occur.
Furthermore these planes in the different crystallites are randomly distributed about the
axis of the incident beam so that the corresponding reflections from all the crystallites
in the specimen lie on a cone coaxial with the axis and with a semi-apex angle of twice
the Bragg angle, i.e. 28. The specimen is surrounded by a cylindrical film and two
small portions of each cone are recorded as lines on the film (Fig. 4.9). If the grain
size is fairly large (> 10-6 m) there is insufficient room within the irradiated volume
for enough crystallites to be in all possible orientations and the resultant powder
lines will be rather 'spotty'. This spottiness can be eliminated by rotating the specimen
during exposure as this increases conSiderably the number of crystallites which can
contribute to each powder line.
The Bragg angles 8 of the various reflections can be calculated by measuring the
separation of the pairs of lines since, from the geometry of Fig. 4.9b,
(21T - 48)/21T = OP/21TR (4.13)
and so the reflections can be indexed and the unit cell parameters evaluated. Since the
diffraction pattern is different for all elements and compounds, this powder technique
provides a fairly rapid method of analysis. In addition it is a useful metallurgical
technique and such things as phase changes can be studied by varying the specimen
temperature and noting the associated changes in the diffraction pattern.
Diffraction
. / cone
I
. COII'~ Beom
r:,c~~~nt. stop
Specimen
(a)
A P o 8 -Camera.
/1 I II ~
I
I I I I I radius R
Collimator hole
(c)
Monochromatic X-ray beam

(b)
Fig.4.9 Schematic illustration of the powder method. (a) Experimental arrangement. (b)
Diffraction geometry. (c) Developed f't1m.
Finally the interpretation of the data from a powder photograph is illustrated by

an example. The following values of 8 were measured on a powder photograph of an
unknown metallic specimen with CuKa radiation of wavelength 1·5405 x 10- 10 m;
19°4',22°11'; 32°33'; 39°13'; 41°4'; 49°28'; 56°3'; 58°16' and 68°44'. We saw in
section 4.2 that the fIrst thing to do is to look for some sequence in the values of
sin 2 8, and so the various values of sin 2 8 are tabulated in Table 4.1. It is fairly obvious
that in the example the values of sin 2 8 are simply related to each other by an expression
TABLE 4.1
(J sin(J sin 2 (J h 2 +k 2 +12 (hkl)
19°4' 0'327 0'107 3 (111)

22°11' 0'378 0'143 4 (200)
32°33' 0'538 0'289 8 (220)
39°13' 0'632 0'399 11 (311)
41°4' 0'657 0'431 12 (222)
49°28' 0'760 0'578 16 (400)
56°3' 0'830 0'689 19 (331)
58°16' 0'850 0'722 20 (420)
68°44' 0'932 0'869 24 (422)
of the form sin 2 8 = K(h 2 + k 2 + 12) and so the metal must have a cubic structure.
Furthermore the only indices that can be fitted to the data have h, k and I all even or
all odd, which fixes the crystal structures as f.c.c. Finally, since K = A2/40 2, a can be
calculated and in this case it equals 4.06 x 10- 10 m which suggests that the specimen is
aluminium.
4.4 Other applications of X-ray diffraction
In addition to its fundamental role in structure determination and analysis, X-ray

diffraction has several other important applications some of which will be discussed
briefly.
4.4.1 Pre/e"ed orientation in polycrystalline metals

In some polycrystalline metals, the constituent crystallites are arranged completely
at random and so an X-ray photograph would consist of a series of concentric rings,
caused by the powder technique cones, indicating the random orientation of the crystal-
lites. In others, there is a tendency for a particular axis or plane to become similarly
orientated and the crystallites are then said to exhibit preferred orientation (plate 4).
The orientation texture will vary with the crystal structure of the specimen and its
method of preparation. It is particularly common in metals subjected to rolling or
drawing to produce sheets or wires because the crystallites tend to align themselves
with a major axis parallel to the rolling or drawing direction. X-ray photographs will
clearly reveal this because instead of the continuous rings there will be certain regions
of enhanced intensity as the material now behaves more like a single crystal. It is
important to know whether or not a specimen is preferentially orientated because
preferential orientation can produce considerable anisotropy in the resulting physical
properties which may affect the subsequent fabrication of components. However, it is
not always disadvantageous, for example preferred orientation in transformer laminations
is preferable provided the sheets can be aligned with their easy direction of magnetiza-
tion parallel to the magnetic field.
4.4.2 X-ray topography [2]

Direct observation of crystalline imperfections, such as small angle grain boundaries
and dislocations is possible with X-rays using a technique known as X-ray topography.
The single crystal specimen is orientated with respect to a parallel monochromatic
X-ray beam so that a convenient set of lattice planes is inclined at the appropriate
Bragg angle, and the diffracted beam is recorded on a photographic plate placed as
close to the crystal surface as possible (Fig. 4.1 0). Local distortions of the lattice, associ-
ated with dislocations or chemical impurities for example, produce variations in the
diffraction conditions and cause a variation of intensity in the image. Thus a projection
of the defect structure near the crystal surface is produced and small angle grain
boundaries and other defects are clearly revealed.
Since there is no magnification inherent in the technique itself, the photographic
fIlm must have a very fine grain, so that the image can be considerably magnified
prior to examination. The theoretical resolution of this technique is limited by the
inherent width of the diffraction image of the defect being studied. For example, the
width of intensity variation from individual dislocations varies between 5 and 50 pm
and this limits X-ray topography for the study of individual dislocations to crystals
whose dislocation densities are less than 1010 m- 2 •
Photographic
plate
I
C::;::::====:::;:::J Diffracted
/ beam
Incident
beam
~
Slit
Diffracting
planes
Fig.4.10 Experimental arrangement for X-ray topography.
4.4.3 Study o/polymer materials

The application of X-ray diffraction methods to polymers is limited by the fact that
the majority of polymer specimens consist of both amorphous regions and
randomly orientated crystallites. Transmission photographs reveal a few discrete
rings due to the crystalline regions and, in addition, one or two diffuse haloes due to
the amorphous regions. Plate 5 shows these haloes for a sample of wholly amorphous
perspex.
The symmetry of the atomic arrangement in polymers is usually quite low and in
general the few discrete rings provide relatively little information on the detailed
atomic structure; although the position and relative intensities of the rings can be used
to study the effects of temperature and additives on the material. However, in the
case of polymers which have been orientated by drawing and then X-rayed with the
incident beam normal to the drawing axis the diffraction pattern is similar to that
obtained from a rotating single crystal, although the spots are considerably less sharp,
and so the dimensions of the unit cell and the configuration of the chains in the cry-
stalline regions can be determined. The diffuse 'amorphous' haloes are not very useful
other than enabling the relative proportions of amorphous to crystalline material to
be estimated. The diameter of the outer halo corresponds to a lattice spacing (from
the Bragg equation) of about 5 x 10- 10 m for all polymers and this distance is typical
of the separation of molecules in simple organic liquids. The inner halo, when present,
corresponds to a larger spacing and appears to be related to the side groups on the
polymer chains and may in fact correspond to the distance between polymer chains
separated by single side groups.
4.5 Neutron diffraction [3]
As was seen in section 4.1 the relationship between the wavelength and momentum
of a neutron is A= h/mu and if the neutrons are to be diffracted by the three-dimensional
gratings occurring in crystals this wavelength must be comparable to the interatomic
spacing, about 10-10 m. The only practical source of neutrons with a suffiCiently large
neutron flux to give measurable reflections is a nuclear reactor in which the neutron
flux is typically 10 18 m- 2 S-1 and even this figure is considerably lower than the photon
flux from a normal X-ray tube. For those neutrons which have suffered enough colli-
sions with a graphite moderator to come into thermal equilibrium with the carbon
atoms at a temperature T the most probable energy is given by
!mu 2 = (3/2)kT (4.14)
or
A2 = h2/3mkT, (4.15)
where k is Boltzmann's constant. This gives values of 1·55 x 10- 10 m and 1·33 x 10- 10 m
at oOe and lOOoe respectively, which are just the order of magnitude that is required.
However, not all the neutrons will have this velocity and so there will be a spread of
wavelengths which follows a Maxwellian distribution as shown in Fig. 4.11. A mono-
chromatic beam, which is essential for quantitative diffraction studies, can be ob-
tained by reflecting a collimated beam of neutrons from a given set oflattice planes
of a large single crystal specimen. It is arranged that the wavelength selected, A, is just
below the maximum and the intensity of the second order reflection (A/2) is then only
a few per cent of the first order reflection.
~
"iii
c:
....c:
G)
o
Wavelength xl 0- 10 m
Fig. 4.11 Wavelength distribution associated with thermal neutrons.
With this monochromatic beam, neutron diffraction experiments similar to the

rotating crystal and powder methods of X-ray crystallography can be performed.
However, the dimensions of the apparatus are much larger because the weakness of the
diffracted beams necessitates large cross sectional area beams. Neutrons do not affect
an ordinary photographic film so the diffracted neutrons are detected by a counter.
Usually this is a proportional counter filled with boron trifluoride gas enriched in the
boron isotope boron-IO which has a high capture cross section for thermal neutrons. For
powder specimens the counter rotates around a stationary specimen. In the case of a
single crystal the rotation of the specimen and counter is synchronized in such a way
that the counter rotates twice as fast as the specimen and the counter is always in the
correct position to receive the Bragg reflections. A typical experimental layout is
shown schematically in Fig. 4.12.
This brief discussion of the experimental apparatus required for neutron diffraction
is sufficient to show that it has many disadvantages compared to X-ray diffraction.
Collimator
Crystal -:1--+----.t.~
monochromator
Rotatable
specimen tablee---
To BF3 counter
Fig.4.12 Typical experimental arrangement for neutron diffraction.
However, it does have several important advantages which stem from the origin of the
scattering of the neutrons. In the case of X-ray scattering it is the electrons of the
atoms that are responsible but in the case of neutrons it is the nucleus of the atom
which causes the scattering. Since the nucleus acts as a point source the atomic
scattering factor,/o, does not vary with (sin 8)/'A and in addition/o does not vary in
any regular way with the atomic number of the specimen. This has two important
consequences:
(0 Ught atoms such as hydrogen and carbon are more effective as scatterers of
neutrons than heavy elements. Thus, in the case of light elements in the pre-
sence of heavy ones, as for example in hydrides or carbides of heavy elements,
neutron diffraction enables the positions of the light elements to be fIxed.
X-ray diffraction can only provide information on the arrangement of the
heavier element because the X-ray patterns are almost entirely caused by
scattering from these elements.
(li) Atoms whicll. are close to one another in the Periodic Table, such as iron and
cobalt, are virtually indistinguishable using X-rays, but have signifIcantly dif-
ferent atomic scattering factors for neutrons. Neutron diffraction is then a very
important tool in the investigation of certain alloys.
Furthermore, in the case of those atoms with a permanent magnetic dipole moment
there is an additional scattering contribution due to the interaction between this
magnetic moment with the small magnetic moment of the neutron. In paramagnetic
materials the scattering from the randomly orientated dipoles simply leads to a diffuse
background, but in ordered magnetic structures such as ferromagnetics, antiferro-
magnetics (see Chapter 9) co-operative diffraction occurs and additional information
on the magntiudes and directions of the magnetic dipoles can be obtained.
4.6 Electron diffraction [4,5]
Electrons, unlike neutrons, can be accelerated by electric fIelds so that their velocity
and hence effective wavelength can be altered at will. For the non-relativistic case,
where the electron velocity is much less than the velocity of light, we have
Ve = !mu 2 and "11.= h/mu
so that
h (150)112
"11.= (2 Vem) 112 ,..... V x 10- 10 m. (4.16)
Thus, if V= 150 V, A == 10- 10 m and if V= 50000 V, A ~ 0·05 X 10- 10 m. Although

the initial verification of electron diffraction by Davisson and Germer was performed
with accelerating voltages of only 50-250 V, the majority of subsequent electron
diffraction work has utilized much higher voltages (20 000-70 000 V) and therefore
wavelengths of the order of 0·05 x 10- 10 m. Electrons are mainly scattered by the
atomic electrons and so the atomic scattering factor varies with (sin 8)/"11. as it does for
X-rays. However, electrons are much more likely to be scattered than are X-ray photons
(in tpe approximate ratio 107 : 1) and so these high energy electron beams will only
penetrate very thin specimens of the order of 10-6 m or less.
Electron diffraction requires an evacuated chamber in which an electron beam from
an electron gun is accurately collimated by an arrangement of apertures and electron
lenses before it strikes the specimen. Because electrons are more readily scattered than
X-rays, the diffracted beam may be observed directly on a fluorescent screen. Alternatively
a photographic plate may be used. This is normally positioned much farther away from
the specimen than for X-ray diffraction because of the small Bragg angles associated with
the small wavelength electrons. A typical experimental arrangement is illustrated
schematically in Fig. 4.13.
Electron diffraction is widely used to investigate polycrystalline specimens and the
resulting pattern therefore consists of a series of concentric Debye rings. Usually the
transmitted diffracted beam is observed but reflection techniques can also be used for
thick specimens, although the small Bragg angles mean that back reflection cannot be
used and the electron beam has to be incident at very small grazing angles to the speci-
men. The crystal structure and any preferred orientation of thin polycrystalline films,
which are too thin to yield sufficient X-ray scattering, may be studied by electron
diffraction. In addition it is a vital technique for studying thin surface coatings, e.g.
oxides which are completely 'missed' by X-rays.
The fundamental difference between electrons and X-rays is that an electron beam
can be refracted by electrostatic or magnetic 'lenses'. It is then quite a simple matter
to convert the diffraction apparatus illustrated in Fig. 4.13 into an electron microscope
which has all the attributes of an ordinary projection optical microscope. The optical
microscope yields detail in the image due to variations in the absorption of light over
the specimen, but in the electron microscope the detail in the image is produced by
variations in the scattering of the incident electrons by the atoms in the specimen.
Regions of greater than average density, thickness or atomic number will produce more
scattering and appear darker on the screen. The great advantage of the electron
microscope is its much greater resolving power compared with its optical counterpart.
The resolving power of a microscope is approximately given by
R.P. ,..... 0·5A/N.A., (4.17)
where N.A. is the numerical aperture of the microscope. The wavelength of the electron
beam is some lOS times smaller than optical wavelengths but the resolving power is
not improved in the same ratio since inherent aberrations in the electron lenses restrict
the numerical aperture and limit the resolution to about 10-9 m. Therefore, individual
Electron gun
Anodes
150kV
To vacuum
pump
""
Magnetic lens
to improve
focussing
Thin
specimen
Viewing_
port
Fluorescent
screen
I:::===~ or photographic
::::.-- film
Fig.4.13 Electron Diffraction Apparatus.
atoms cannot be resolved but many otherwise 'invisible' features can be observed, for
example large molecules, minute particles, dislocations and other crystal defects, and
the electron microscope has proved of immense value in all branches of science and
especially to metallurgists and biologists.
4.7 Structure of amorphous materials [6]
Studies of the structure of glasses and amorphous materials have used X-ray, electron
and neutron diffraction techniques. The distinction drawn in section 3.8 between the
two types of material based on the method of preparation is not reflected in differences
in microscopic structure and from this point of view they can be considered to be
identical. However, the crystalline state is always the most stable and amorphous
materials exhibit a greater deviation from the stable equilibrium state than glasses
and generally contain a much higher proportion of defects. Both types will here be
called amorphous.
The essential difference between the amorphous and crystalline states is that in the
former the equilibrium positions of the atoms do not exhibit translational symmetry.
The spatial pattern is aperiodic. In a crystal, interatomic distances are fixed but in an
amorphous material there is short range order but no long range order. The interatomic
spacings of nearest neighbours (nn), next nearest neighbours (nnn) and so on now only
occur with a certain probability. Such a structure is described by a radial distribution
function F
F = 41Tr2 per),
where per) is the atomic or electronic density at a distance r from an arbitrary atom as
centre (r = 0). It is assumed that the density is uniform over a sphere of given radius in
order to analyse diffraction patterns but this assumption is not strictly justified. The
radial distribution function is used because diffraction techniques sample a volume of
material which is much greater than that in which local order exists and so give informa-
tion as a probability distribution.
T 1 I I I
f-- Radial distribution functions -

100 A Si film
f--(a)- - - - 4u 2 p (r): as deposited -
~(b) 47tr2 p (r): crystallized
-I-
I
•:
:
'J
I
;,
c::
o
,
II
-
'';::;
u
, ,
c::
::J
II
,
c::
o
'';::;
::J
:g....
.~
'0
,.
.
.!!!
.,
, ~!
'0
c: 1
I
II
I
I.
,
,
I I
I
II
'l J
~,
Ii
~b
"...
o 1.0 2.0 3.0 o 4.0 5.0
Radial distance r (A)
Fig.4.14 Radial distribution function of silicon. (a) Amorphous. (b) Crystalline.
The contrast between the crystalline and amorphous states is illustrated in Fig. 4.14
which shows the radial distribution function in each case for silicon.
The first peak is almost the same for both, indicating that the crystalline nearest
neighbour interatomic distance 2·35 A is maintained. The area under the peak, if it is
well separated from the rest, represents the number of nns (four) suggesting that the
local tetrahedral structure is virtually unchanged in the amorphous state. The second
peaks are also coincident at 3'86 A. A broadening of this amorphous peak is interpreted
as distortion of the bond angle by as much as ±20° from the tetrahedral value of
109°28'. The area under the second peak indicates the crystalline number of nnns
(twelve). The striking difference is the absence of an amorphous peak corresponding
to third nearest neighbours.
Various models have been proposed for amorphous structures. The most successful
one for the amorphous forms of germanium and silicon has been a random network
model [7] in which each atom is bonded to satisfy its normal valence without dangling
bonds but with some distortion of bond angles. Neighbouring tetrahedral units are
rotated relative to each other about a common bond. Enlarging this structure leads to
a random network containing five- and six-membered rings. The presence of the latter
tends to suppress the third neighbour peak because the occurrence of atomic separations
at the third neighbour distance is reduced.
Of the chalcogenide glasses, AS 2 S3 is a monoclinic crystal with a layer structure.
Each As atom has as nn three S atoms and each S atom has two As atoms as nn. In
the amorphous phase the nn and nnn coordinates are increased and it seems that the
layers become wavy and connected at some points. Fig. 4.15 (a) represents the crystal-
line arrangements of AS 2 S3 and (b) the amorphous structure on a random network
model.
(a)
(b)
Fig.4.15 Two-dimensional representation of (a) crystalline AS2S3. and (b) amorphous AS2S3
on a random network model.
TABLE 4.2
Classification of amorphous semiconductors by structure with comparison of number of nearest neighbours and nn distance for amorphous and crystalline states_
(a:xb] means that the average number ofnn of atom a of type b is x (from ref (8])_
Structure Type Exomples Numberofnn Numberofnn rl (amorphous) r 1 (crystalline)

(amorphous) (crystalline)
'"C
Tetrahedral Elements Ge, Si 4 4 (2-47-2_54)(2-37-2-41) 2-43,2·35 ::0
AIVB IV SiC 4 Si: 4C; C: 4Si >
()
o-j
AIIIB V GaSb 4 Ga: 4Sb: Sb: 4Ga 2-65 2-638
AIlIB VI InSe 4 In: 3Se; Se: 3In: In-Se: 2-60 In-Se: 2-50
n
>
In: lin In-In: 3-15 In-In: 3·16 t""
A~IIB¥I In: 3·46 Se; Se: 3·46 In (Ga, In): 4(Se, Te) 2·58 in In2Se3 t:I
(Ga, Inh(Se, Teh 2·57-2-60 in In2Se3 tT:I
In: 0·95 In Se, Te: 2-66(Ga, In) o-j
tT:I
In: (3-91-4·01 Se) ::0
Se: (2·59-2·67 In) is:
AIIBIVd' CdGe(P, Ash (P, As): 2Cd, 2Ge (P, As): 2Cd, 2Ge 2-50 in CdGeP 2 Cd-P: 2-55 in CdGeP 2 ~
Ge-P: 2·33 o-j
A1II B~V N 4 Si3 Si: 4N Si: 4N -1·7 1-7-1·8 0
Z
0
'Tl
Layer Elements C, As, Sb 3-2-3-4; 3; 3 (diamond 4, graphite -I-50, 2-40, 2·87 0·54,1"41),2-51, til
3)3,3 2·87 o-j
A2 VB¥I ::0
(As, Sb, Bi)liS, Scv (As, Sb, Bi) : (2-9-3·6)(S, Se, Te) (As, Sb, Bi) : 3(S, Se, Te) - c:
Teh + (A I, BI CVIl) (S, Se, Te): (2-0-2-4)(As, Sb, Bi) (S, Se, Te): 2(As, Sb, ()
o-j
Bi) c:
::0
tT:I
Chains and Elements Se, Te 2, - 2,2 2-31-2-34, - 2·32, -
rings
Icosahedra Elements B 6 -6 -1·8

00
w
Selenium and tellurium form a third group, trigonal in the crystalline state with a
structure based on helical chains. Selenium also occurs in a structure based on eight-
membered rings. The radial distribution function obtained for amorphous elenium
depends on the method of preparation but explanations have been given in terms of
both six- and eight-ring models.
Table 4.2 classifies amorphous semiconductors giving the number and separation
of nn in both crystalline and amorphous states.
4.8 Other techniques
In addition to these three fundamental diffraction techniques for studying the struc-
ture of materials there are many other techniques that can be employed and a few of
them are discussed briefly.
4.8.1 Field-ion microscopy

Field-ion microscopy is unique in that, unlike all other techniques, it is able to resolve
the individual atoms composing the surface of a solid. In principle it is a very simple
technique and is a point projection device rather than a true microscope. The speci-
men to be examined is electropolished to produce a very fine point and then mounted
in a vacuum chamber opposite a fluorescent screen. An imaging gas, which is usually
helium, at a pressure of about 4 x 10-3 torr is then admitted to the chamber. The
specimen is maintained at a positive potential of 10-20 kV and the small radius of
curvature of the tip of the specimen produces field strengths which are great enough to
ionize the helium atoms as they approach the specimen surface. The field is not
uniform over the entire surface but increases locally in the vicinity of atomic sites and
so the ionization probability is greater close to these atomic sites. The resulting positive
ions are then repelled from the surface and follow a radial path until they produce on
the fluorescent screen an image of the atomic configuration in the specimen surface
magnified about a million times. The complete three-dimensional structure of the
specimen can be examined by successively evaporating off the surface layer repeating
the imaging process.
This technique is increasing in its range of application and has been successfully
applied to such topics as the basic study of lattice defects, radiation damage, adsorbed
surface layers and alloy structures.
4.8.2 Infra-red spectroscopy [9,10]

Infra-red spectroscopy has proved to be a very valuable experimental technique for
studying the chemical and structural properties of polymers. In general, emission or
absorption spectra occur when atoms or molecules undergo transitions between dif-
ferent quantum states and in the infra-red region of the electromagnetic spectrum
(X"" 10- 6 -5 X 10- 5 m) these energy changes are associated with molecular vibrations and
rotations. In the case of polymers containing a vast number of simple repeat units the
molecular rotations and vibrations are characteristic of the small groups of atoms
making up these units. Although the infra-red band spectra of polymers can be very
complex, they will reveal features which are characteristic of the basic repeat units.
In practice absorption spectra are examined, because emission spectra are too weak
for practical use, and the experimental principle is the same as that used for optical
spectroscopy although the individual spectrometer components are, 'of course, different.
A typical source is an electrically heated Nernst filament which consists of a mixture
of rare earth oxides. The radiation can be monochromatized by either a grating, or a
prism of NaCl or KBr which is transparent to infra-red radiation. The transmitted
radiation is detected by some form of sensitive black body heat detector such as a
multi-junction thermocouple.
Since the spectra are characteristic of the polymer repeat units, infra-red spectro-
scopy is a very useful method of analysis of polymers. In addition, however, the details
of the band spectra may be different for amorphous and crystalline specimens of
the same material. Some bands are associated with only one or other of the two
regions, and the degree of crystallinity can be estimated from the relative band
intensities. Furthermore, the absorption of plane polarized infra-red radiation is sensi-
tive to the orientation of the polymer molecules and so infra-red spectroscopy can
provide evidence on the structure of polymer materials.
Another important technique in the study of molecular vibrations and rotations
which is closely associated with infra-red spectroscopy is that of Raman spectroscopy.
If an intense beam of monochromatic light is incident on a transparent medium, the
scattered radiation contains very faint components whose frequencies differ from that
of the incident light in a regular way. This Raman effect can be explained as follows:
if a photon of light is scattered by a molecule and the quantum state of the molecule
is changed in the collision then the frequency of the scattered radiation will be
changed. If, for example, the incident photon has a frequency v and the energy of the
molecule is increased by an amount M, the frequency of the scattered radiation VI is
given by
hv = hv I + I::.E. (4.18)
This difference in energy corresponds to a change in the rotational or vibrational
energy of the molecule and so a study of Raman spectra can give the same sort of
information about molecular structure as absorption infra-red spectroscopy.
4.8.3 Observation of dislocations

In addition to the direct observation of dislocations using X-ray topography and
electron microscopy which has already been discussed, the presence of dislocations may
also be detected by two other techniques, chemical etching and dislocation decoration.
During the last fifteen years or so, chemical etching of single crystals has yielded
abundant information on dislocation densities, dislocation arrays and the movement
of dislocations. Since a dislocation line has an excess stress associated with it and
dissolved impurities tend to segregate along dislocations because of their misfit in the
lattice, an emergent dislocation may be more readily attacked by certain solutions
than the remainder of the surface. This leads to the production of well defined dis-
location etch pits. Suitable etching solutions have not been found for all single crystals
but in many cases reliable etchants are known and the one-to-one correspondence
between dislocations and etch pits has been verified experimentally. Unfortunately,
however, this etch pit technique is unable to reveal dislocations in the interior of the
crystals.
Dislocation loops within a crystal may be observed using the decoration technique
which also relies on the tendency for solute atoms to segregate to dislocation lines. If
into silicon, for example, a little copper is diffused at 900°C, on cooling to room
temperature the copper atoms segregate to the dislocation lines. These atoms can then
be made visible by illumination with infra-red radiation which is transmitted by the
silicon but not by the copper solute atoms. Similarly the dislocations in transparent
AgBr crystals can be decorated by causing print-out of the silver. However, in general,
this technique is rather limited in its range of application.
References
1. Cohen, J. B. Diffraction Methods in Materials Science, Macmillan (1966).

2. Newkirk, J. B. and Wernick, J. H. (Editors). Direct Observation of Imperfections in Crystals,
Interscience (1962).
3. Bacon, G. E. Neutron Diffraction, Oxford University Press (1962).
4. Thomas, G. Transmission Electron Microscopy, Wiley (1962).
5. Andrews, K. W., Dyson, D. J. and Keown, S. R. Interpretation of Electron Diffraction Patterns,
Adam Hilger (1967).
6. Turnbull, D. and Polk, D. E. J. Non·Cryst. Solids 8-10,19-35 (1972).
7. Zachariasen, W. H. J. Am. Chem. Soc. 54,3841 (1932).
8. Grigorovici, R. J. Non-Cryst. Solids 1, 302-325 (1969).
9. Sawyer, R. A. Experimental Spectroscopy, Dover (1963).
10. Wolfe, W. L. (Editor). Handbook of Military Infra-Red Technology, Office of Naval Research,
Dept of Navy, Washington (1965).
Questions
1. Calculate the Bragg angles for Mo-Ka radiation (X = 71·2 X 10- 12 m) diffracted
from the (110) and (200) planes of tungsten, given that tungsten is b.c.c. with a lattice
parameter of 316 x 10- 12 m. Would you expect a diffracted beam from the (100) or
(111) planes?
2. A powder photograph of a certain metal, taken with radiation of wavelength
154 x 10- 12 m, exhibits diffraction lines corresponding to the following Bragg angles:
20°14',29°23',36°50',43°58',50°45',58°44', 66°35', 78°34'. Assuming that the
metal is cubic, determine whether the lattice is f.c.c. or b.c.c. and calculate the unit cell
parameter. By comparing this value with tabulated values for metals try to identify the
metal used.
3. A specimen of powdered aluminium at a temperature of 293 K gave a diffracted
X-ray beam at an angle of 138° to the direction of the incident beam. When the tem-
perature of the specimen was raised to 593 K the angle between the diffracted beam
(from the same set of planes) and the incident beam changed by 2°10'. Calculate the
mean coefficient of expansion of aluminium between 293 and 593 K.
4. Calculate the Bragg angle at which electrons accelerated from rest through a .
potential difference of 80 V will be diffracted from the (111) planes of an Lc.c.
crystal of lattice parameter 350 x 10- 12 m.
S. A beam of thermal neutrons emitted from the opening in a reactor is diffracted by
the (111) planes of a nickel crystal at an angle of 28° 30'. Calculate the effective tem-
perature of the neutrons given that nickel is Lc.c. with a lattice parameter of
352 x 10- 12 m.
6. A transmission Laue photograph is taken of a b.c.c. crystal of lattice parameter
286 x 10- 12 m. Calculate the minimum distance from the centre of the pattern to the
diffraction images if the specimen is 60 mm from the mm and the X-ray tube voltage
is 35 kV.
5 Mechanical Properties
of Materials
5.1 Introduction
The mechanical properties of materials, their strength, rigidity and ductility, are of
vital importance in determining their fabrication and possible practical applications.
Materials exhibit a wide range of mechanical properties ranging, for example, from the
hardness of diamond to the ductility of pure copper and the amazing elastic behaviour
of rubber. Furthermore many materials behave quite differently when stressed in
different ways; for example cast iron, cement and masonry are much stronger in com-
pression than in tension, a fact that was not lost on early architects who avoided using
materials in tension whenever possible, whereas wood is several times stronger in
tension than it is in compression because the cell walls in the wood structure tend to
buckle in compression. In the subsequent sections of this chapter the various mech-
anical properties of materials are discussed and an attempt is made to explain the
behaviour of materials under stress. Initially, however, a brief review is given of some
of the experimental techniques that are used to investigate these mechanical properties.
5.2 Mechanical testing
The most common mechanical test is the tensile test in which a specimen is stretched
by an increasing load and the resulting stress-strain graph produced. The results of
such a tensile test can be used to introduce most of the terminology to be met later
on. Fig. 5.1 shows a typical nominal (or engineering) stress-strain curve for a metal
such as copper. The nominal stress is defined as the load divided by the original cross
section area and the nominal strain as the extension divided by the original length.
Initially as the stress is increased the strain increases uniformly (over the region
OX) and the deformation produced is completely reversible. Over this elastic
region the strain is extremely small and Hooke's law is obeyed, i.e. the stress
is proportional to the strain. Beyond a limiting stress X, called the yield stress, the
strain increases much more rapidly with increasing stress and the deformation is no
longer reversible; this is called the plastic region. In some materials, such as low carbon
steels the yield point is more clearly defined than as shown in Fig. 5.1 and typified
by a sudden drop in the stress, but because the yield point is not always clearly
defined engineers often use the 0·2 per cent proof stress as the safe working stress,
i.e. the stress required to produce 0'2 per cent plastic strain. This proof stress is marked
by the point Y in Fig. 5.1 and is exaggerated for clarity. At N necking occurs and the
stress at this point is called the ultimate tensile stress or tensile strength and is in fact
the maximum nominal stress. Beyond N the nominal stress automatically decreases
but the specimen continues to elongate until fracture occurs at F. However, because
F
'"1/1
~1/1
coc:
'E
o
z
o \0.2% 10 20 30
Nominal strain (per cent)

Fig. 5.1 Typical nominal stress-strain curve for mild steel or copper.
of the appreciable change in cross sectional area that occurs during plastic deforma-
tion it is often desirable to talk about true stress and true strain where the true stress
is defined as the ratio of the load to the minimum cross sectional area and the true
strain is defined as the integral of the ratio of an incremental change in length to the
instantaneous length of the sample, i.e.
true stress = 10adjAminimum
and IF
true strain = J z' dl
10
A true stress-strain curve is shown in Fig. 5.2 and it can be seen that the true stress is
not a maximum at the initiation of necking but increases continually until fracture
occurs.
----
_.... .... ....
True
1/1
1/1
...~
(/)
Strain
Fig. 5.2 Comparison between nominal and true stress-strain curves.
MECHANICAL PROPERTIES OF MATERIALS 89
A material whose tensile behaviour is typical of that shown in Fig. 5.1 or 5.2 is
termed a ductile material. However, many materials fracture following little or no
plastic deformation and these are termed brittle materials.
Although the tensile test is the most common there are several other mechanical
tests that are commonly employed. Compression testing is quite common for brittle
materials which are usually much stronger in compression than in tension. Necking
does not occur in compression testing and the resulting curves are much closer to the
true stress-strain curve illustrated above. Ductile materials are rarely tested in com-
pression because of the frictional constraint of the apparatus on the ends of the
specimen which gives rise to a complicated stress distribution at the surfaces. Hard-
ness testing measures the resistance of a material to an indentor of a predetermined
shape and an empirical hardness number may be assigned from measurements of the
applied load and the dimension of the indentation. Finally the static tensile properties
of a material are generally better than the dynamic properties which result from the
repeated application of a load. The fatigue test determines the stress which a specimen
can withstand for a given number of cycles of the applied stress. Specimens are
usually tested to failure for different stresses and the number of cycles prior to
failure is noted.
5.3 Elastic behaviour
Elastic deformation is reversible and the stress and resulting strain are proportional to
one another and obey Hooke's law; the constant of proportionality between stress and
strain is called a modulus of elasticity. Elastic behaviour is not restricted to tensile
stresses and three elastic moduli are commonly defined:
(i) Young's modulus, E, relates tensile stress 0t to tensile strain e: E =ot/e;
(ii) the shear modulus, G, relates shear stress r to shear strain r: G = r/r; and
(iii) the bulk modulus, K, relates bulk stress 0 to bulk strain ..1V/V(relative change
in volume): K = o/(..1V/V)
In addition, as a specimen elongates in the elastic region its cross sectional area
decreases and another elastic constant, Poisson's ratio J.l., can be defined as the ratio
of the transverse to the axial strain. These elastic moduli are usually anisotropic in the
case of single crystals but, since the mechanical engineer usually works with poly-
crystalline materials in which the individual crystallites are arranged completely
randomly, it can generally be assumed that the mechanical properties of materials
are isotropic. Then quite simple relationships exist between these four elastic
constants:
E= 3K(1- 2J.l.)
and
(5.1)
On the atomic scale a tensile force, for example, will tend to elongate the specimen
and increase the interatomic spacings of the atoms. Thus Young's modulus will be
proportional to aF/ar and, for the small atomic displacements encountered in the
elastic region (---1 per cent), aF/ar, which is the tangent at r = ro of the interatomic
force-interatomic separation graph of Fig. 2.1, will be approximately constant, as
expected theoretically. In addition the modulus of elasticity will be the same for both
tension and compression. The magnitude of aF/ar depends quite markedly on the
magnitude of the interatomic forces as shown in Fig. 5.3 and so the values 0 f the
elastic constants are directly related to the fundamental interatomic forces. The cor-
relation between the magnitude of Young's modulus and the type of bonding is
evident from the data in Table 5.1, although it should be noted that the value of
Young's modulus is temperature dependent. The somewhat anomalous elastic prop-
erties of elastomers will be left to section 5.8 when the mechanical properties of
polymer materials will be discussed collectively.
F F
\
\
\
/'0
r r
\
aF'
-
ar ", ,
,
\-aF
\ -
ar
(a) (b)
Fig. 5.3 Variation of aF/ar with interatomic bonding. (a) Strong bonding. (b) Weak bonding.
TABLE 5.1
Material Bonding Young's modulus

(Nm-2 )
MgO ionic 30 X 10 10
Copper metallic 13 X 10 10
Diamond covalent 54 X 10 10
S.4 Plastic behaviour
Plastic deformation is characterized by a permanent deformation of the specimen and

in a tensile test, for example, a permanent extension of the specimen is produced.
Plastic deformation can best be understood by considering the behaviour of a single
crystal specimen. One way in which a permanent extension can occur is illustrated in
Fig. 5.4 where it can be seen that the elongation has occurred by a shearing of the
specimen on a few crystal planes. This process is referred to as slip and the slip steps
are observable on the surface of the specimen. In a tensile test, since the ends of the
specimen are not free to move laterally, lattice bending and rotation occur as illus-
trated in Fig. 5.4c.
Slip does not occur on all sets of lattice planes but is restricted to certain planes
which are characteristic of the crystal structure. The slip planes and slip directions
which are together referred to as a slip system, are given in Table 5.2 for a few com-
mon metal crystal structures. In general the slip direction is parallel to the direction
along which the atomic packing is densest and the slip planes are those which have the
largest interplanar spacings.
TABLE 5.2
Structures Slip planes Slip directions
b.c.c. {IOI} <Ill>

Lc.c. {111 } (110)
h.c.p. {000l} <1120)
F F
Lattice bending
and rotation
Slip
directions
(a) (b) (c)

Fig.5.4 Plastic deformation caused by slip.
However, these slip systems will only be operative if the applied shear stress exceeds
a critical value. Let us consider a cylindrical specimen of cross sectional area,
A, in which the normal to the slip planes makes an angle () and the slip direction an
angle rp with the stress axis as illustrated in Fig. 5.5. The resolved force in the slip
Slip
plane
Fig. 5.5 Critical resolved shear stress.

direction is F cos cp and since the area of the slip plane is A/cos (), the shear stress, T,
is given by
T = (F/A) cos () cos cp = a cos () cos cpo (5.2)
This expression has a maximum value when both () and cp are 45° which explains why
there is a tendency for specimens under tension to fracture along planes at 45° to the
tension axis. Experimentally slip is observed when T reaches a critical value of the
order of 10 5 to 106 Nm- 2 •
Now consider the atomic processes that must be occurring during slip so that a
theoretical estimate can be made of the critical shear stress required to make two
atomic planes slide over one another. For the two atomic planes in their equilibrium
configuration shown schematically in Fig. 5.6a, assume that under the application of
+I
(SCDCDO
d I I
I
I
I
Shear I
stress I
I
T I
Displacement
x of atoms in
upper layer
(b)
Fig. 5.6 Theoretical mechanism of slip.
an applied shear stress the upper layer moves as a whole over the lower plane by a
distance x. When x = al2 the atoms in the upper layer will be directly over those in
the lower plane and be in a position of unstable equilibrium and so the stress will be
zero whenever x =0, a12, etc. If it is assumed that the stress is periodic in nature, as
illustrated in Fig. 5.6
T =Tc sin (21Tx/a), (5.3)
where Tc is the critical or maximum stress. For small strains (x < a) the usual theory
of elasticity should apply so that T = G(xld) and, since sin () ~ () as ()~ 0
T = Tc sin (21Txla) = G(xld) (5.4)
or
Tc = GaI21Td. (5.5)
For most crystals a "" d and T c "" G/21T. The shear modulus of most materials is of the
order of 1010 Nm- 2 and so this theoretical value for the critical shear stress is several
orders of magnitude greater than that observed experimentally. Furthermore, this
theoretical analysis requires an elastic strain of 25 per cent before any permanent dis-
tortion could occur whereas elastic strains of only 0·5 per cent are typical. Although
the above calculation is by no means rigorous it is obvious that slip does not occur by
one crystal plane simply sliding over another.
This discrepancy between theory and experiment led to the postulation of dis-
locations in the 1930s although at that time there was no direct evidence for their
existence. The movement of both edge and screw dislocations in their slip planes
requires much less stress than calculated above even though the atoms immediately
ahead of either resist the movement to some extent. This is because the dislocation
forces the atoms out of their stable positions. The atoms immediately behind push the
dislocation forward since they can then fall back into their equilibrium positions. The
Burgers vector of an edge dislocation and the dislocation line itself define the slip
plane and edge dislocations normally move in this plane. In the case of a pure screw
dislocation the Burgers vector and dislocation line are parallel and do not define a
unique plane so that this type of dislocation is free to move in any plane containing
the Burgers vector. In both cases the movement of the dislocation produces a per-
manent deformation and a slip step at the surface as illustrated in Fig. 5.7.
Edge dislocation
" ,
line
h-<::~~~~
_ _T
-~
T _..........- \
Screw
dislocation
Slip line
plane
(a) (b)
Fig. 5.7 Formation of a slip step by the movement of dislocations. (a) Edge dislocation. (b)
Screw dislocation.
In practice, of course, dislocation loops are made up of a combination of edge and

screw dislocations. However, they can be resolved into their separate components and
the slip produced by the gliding of a general dislocation loop is similar to the simple
examples described above. Very thin whiskers or fIlaments can be grown from the
vapour phase with few, if any, dislocations. These exhibit critical shear stresses which
agree quite closely with the theoretical values and provide evidence that the weakness
of metal crystals is a consequence of the presence of dislocations.
So far emphasis has been placed on the behaviour of metallic elements in which all
the atoms are identical. Two or more different atoms of different size must be con-
sidered for compounds and the process of slip on some of the possible slip planes may
result in a highly unstable situation; for example slip in an ionic crystal could disturb
the regular anion-cation arrangement demanded by electrostatic consideration. For this
reason the critical shear stress for slip on the theoretically expected planes may be so high
that slip is impossible before the specimen fractures. The effective number of slip systems in
compounds is therefore reduced and compounds tend to be more brittle than elements.
Slip is not the only mechanism that can produce plastic deformation and a shear
stress may cause mechanical twinning (see section 2.12) with a resulting permanent
shear strain. Unlike slip, twinning produces an abrupt reorientation of the lattice and
it can only occur in those directions and on those planes which produce mirror images
of the lattice. Furthermore, because of this mirror image restriction, the shear strain
produced is limited to specific values whereas the shear strain produced by slip can
increase continuously from zero until the specimen fractures. The critical shear stress
for twinning is higher than that for slip and the former does not generally occur unless
slip is restricted in some way. Twinning occurs most commonly at low temperatures
when the critical shear stress for twinning is less temperature dependent than that for
slip, or as a result of high strain rates. It may also occur in h.c.p. metals when the
resolved shear stress on the basal plane is low since this is normally the expected slip
plane. The actual mechanism of mechanical twinning is not fully understood although
it is again believed to be some form of dislocation mechanism.
5.4.1 Dislocation multiplication

The lattice spacings for most crystals, and hence the Burgers vector for dislocation
lines is of the order of 3 x 10- 10 m. Slip lines, however, are often visible with a micro-
scope and this implies steps of the order of 3 x 10- 7 m or more, and the movement of
about 1000 dislocation lines across a given slip plane. Often the slip steps in 'pure'
single crystals are very large indeed and visible with the naked eye. This must imply
that there is a mechanism for generating dislocations inside the crystal since in the
process of slip each line moves to the edge of the crystal and then vanishes.
One possible mechanism of dislocation multiplication is that due to Frank and
Read [1]. Consider a line dislocation, ab, which is fixed at its ends by impurities for
example, with an applied stress normal to the line of the dislocation. Due to this
applied stress the dislocation line will bow out and be successively deformed to the
stages 1,2, 3, 4 and 5 (see Fig. 5.8). Between stages 4 and 5 the two points P and Q
will meet and the curved structure of stage 4 breaks up into the ring dislocation 5 and
a new line source abo This sequence can be repeated indefinitely and one unit of slip
Fig. 5.8 Frank-Read source.

is produced by each loop that is generated. The stress applied to operate the Frank-
Read source must be sufficient to overcome the restoring force on the dislocation line
since the excess lattice energy associated with a dislocation means that it has an
effective line tension which tends to resist deformation of the initial straight line. The
critical stress required to operate such a source is approximately given by
Tc =Gb/I Nm- 2 , (5.6)
where b is the Burgers vector of the dislocation and I the length of the dislocation line.
5.4.2 Additional dislocation motion and dislocation interactions

The motion of dislocations is not entirely limited to gliding in their slip planes and
additional dislocation movements can occur which have important consequences for
the mechanical behaviour of materials. Under favourable conditions a dislocation can
move from one slip plane to another, which enables slip to continue even if slip on
the original plane is impeded in some way. Edge dislocations can climb from one plane
to another by the diffusion of additional atoms (or vacancies) to the dislocation line.
It is not necessary for the entire dislocation line to climb up or down and the extra
half plane of atoms may be increased or decreased over only a portion of the original
dislocation line; the discontinuity in the dislocation line is called a jog (Fig. 5.9a).
(a) (b)
Fig.5.9 (a) Oimb and (b) Cross slip.
Because climb relies on the process of diffusion it is more likely to occur at elevated
temperatures. Cross slip is the movement of a screw dislocation from one slip plane to
another. Because its Burgers vector is parallel to the dislocation line, a screw disloca-
tion can cross slip quite easily on to any plane which contains the Burgers vector (Fig.
5.9b). Cross slip does not involve the diffusion of atoms and so it is not a thermally
activated process.
The discussion, so far, has been restricted to the behaviour of isolated dislocations
ignoring the fact that most crystals contain fairly high dislocation densities. There-
fore, the effect of these other dislocations that are present is considered briefly.
Because of the stress field associated with each dislocation line there will be an inter-
action force between different dislocations and in the simple case of parallel disloca-
tions several conclusions can be deduced quite readily. Parallel screw dislocations of
the same sign will always repel one another whereas parallel screw dislocations of
opposite sign will attract one another and if unimpeded they may ultimately annihilate
one another and leave a perfect lattice. The nature of the force between two parallel
edge dislocations is more complex since it varies with both the sign of the dislocations
and their separation. However, in general, parallel edge dislocations of the same sign on
the same or nearby slip planes repel each other, but if they are on more widely spaced
slip planes they tend to attract each other and align themselves above one another in
a plane normal to the slip plane to form a low-angle boundary (section 2.12). Parallel
edge dislocations of opposite sign on the same or adjacent slip planes attract one
another and may annihilate each other to leave a perfect lattice or a row of vacancies.
Of course not all dislocations are parallel to each other and if a pair of non-parallel
dislocations of either type are forced to intersect as they glide under the application of
an applied shear stress, jogs are created in one or both of the dislocation lines as
illustrated in Fig. 5.1 0 for the case of two edge dislocations. The presence 0 f these jogs
in the dislocation lines makes them less mobile and so a greater applied stress is required
to move them. This has important consequences in the strain hardening of metals
(subsection 5.6.1).
Fig.5.10 Formation of jogs by the intersection of two edge dislocations.
5.4.3 Behaviour of polycrystalline materials

Although the discussion has centred on the mechanisms of plastic deformation with
respect to single crystals, the same general considerations regarding dislocation motion
and multiplication apply equally well to polycrystalline materials. The grain boundaries
prevent the gliding of dislocations and make polycrystalline specimens stronger than
single crystals. On the other hand at high temperatures the grain boundaries may
weaken a metal rather than strengthen it by producing creep (section 5.7). Further-
more, grain boundaries will provide an additional constraint on the deformation of the
specimen since each single crystal 'grain' cannot necessarily deform as if it were isolated
but must comply with the deformation of its immediate neighbours.
5.S Fracture
Fracture is the separation of a specimen into two or more parts by an applied stress
and can be classified as either brittle or ductile. Brittle fracture occurs after little or
no plastic deformation, whereas ductile fracture occurs after extensive plastic defor-
mation.
5.5.1 Brittle fracture [2]

Brittle fracture usually occurs by the rapid propagation of a crack under applied
stresses which are several orders of magnitude lower than the theoretical stress re-
quired to break the interatomic bonds in the solid. Amorphous materials such as
glass are completely brittle but crystalline solids usually exhibit some plastic defor-
mation before fracture. The explanation of the fracture of materials like glass was
rust proposed by Griffith who assumed that in a brittle material there are many fine
cracks, which concentrate the applied stress at their tips. For an elliptical crack as
shown in Fig. 5.11 the maximum stress at its tip is given by
am =2a(c/p)1/2, (5.7)
~m
1"----'1
I I
r---2c~
a
Fig. 5.11 Griffith crack model.
where c is half the length of an internal crack or the length of a surface crack and p is
the radius of curvature at the tip, which may approach atomic dimensions in a brittle
material. With such stress concentrations the cohesive strength can be exceeded at the
tip of a crack under a fairly low applied tensile stress. If the crack is to propagate
through the material the release of stored elastic energy must be sufficient to provide
the energy associated with the two surfaces produced. Consider a surface crack of
depth c and unit width, then the strain energy released by this crack can be found by
integrating the strain field (a 2 /2£) per unit volume from infinity to the surface of
the crack and is given by
UE = a2 rrc 2 /2E. (5.8)
The energy consumed in forming the two crack surfaces will be
Us = 2'Yc, (5.9)
where'Y is the surface energy per unit area. Such a crack can only grow spontaneously
if its growth does not increase the overall lattice energy, i.e. if dU/de ~ 0, where
U= -UE + Us, i.e.
-d (rrc
2 2
-- ( ) d
=-(2'Y c) (5.10)
de 2E dc
or
( £)1/2
a = 2'Y-
rrc
(5.11)
This result shows that the stress necessary to cause brittle fracture varies universally
as the square root of the crack length and so the tensile strength of a completely
brittle material will depend on the length of the largest crack existing in the material.
Although this derivation strictly applies to a thin plate under tensile stress, similar
results can be deduced for other specimen geometries.
Direct evidence that inherent cracks are the cause of brittle fracture has been
observed in investigations with glass, since freshly prepared glass fibres with high sur-
face perfection exhibit very high tensile strengths. This strength is drastically reduced
by handling which causes minute surface cracks, which need be only a few microns
deep, and glass is usually extremely brittle. Sheet glass can be strengthened for such
applications as car windscreens by heat treatments that produce compressive stresses
in the surface which effectively hold the cracks together.
In the case of crystalline materials the Griffith theory has to be modified somewhat
to take account of the small amount of plastic deformation that occurs. Basically,
however, the fracture mechanism is the same although the critical crack depth is
somewhat larger. In single crystals fracture occurs along specific lattice planes which
are called cleavage planes. In polycrystalline materials brittle fracture can either take
place along the cleavage planes or along grain boundaries due to the weakening effect
of impurities which have segregated to the boundaries, leading to a characteristic
granular appearance of the fracture surfaces.
5.5.2 Ductile fracture

Ductile fracture is not influenced to any great extent by minute surface blemishes
because plastic flow at the tip of a crack will blunt it and thus lower the stress con-
centration. In the case of most ductile materials in tension three distinct stages in the
fracture process can be distinguished: (a) the specimen begins necking and minute
cavities form in the necked region; (b) the cavities coalesce and form a minute crack
in the centre of the specimen; and (c) the crack spreads outwards to the surface of the
specimen in a direction at 45 0 to the tensile axis resulting in recognizable cup and
cone fracture surfaces. The initial cavities are often observed to form at foreign
inclusions where the gliding dislocations can 'pile up' and produce sufficient stress to
form a void or microcrack.
The engineer requires both strength and ductility for his structural materials because
ductility avoids unpredictable brittle fractures and tends to increase the strength of the
material by work hardening. However, a ductile material may exhibit brittle fracture,
for example:
(a) The work hardening not only increases the strength of the material but also
lowers the ductility and so a material which initially adapts to applied stress
may subsequently lack sufficient ductility to cope with further applied stress in
the vicinity of structural flaws.
(b) A decrease in temperature may lead to a transition to brittle fracture in some
materials, notably b.c.c. metals, because the yield stress usually increases with
decreasing temperature whereas the fracture stress remains apprOximately
constant. In the case of many steels the transition temperature is often quite
close to normal atmospheric temperatures and several steel structures have
suffered catastrophic brittle fracture. For example, in 1963 the thick steel shell
of one of the boilers for a British nuclear power station fractured while on test.
Nuclear engineering imposes a further hazard in this respect because neutron
irradiation tends to raise the transition temperature.
5.5.3 Fatigue failure
Ductile materials may also fracture when subjected to cyclic stresses which are con-
siderably lower than the static fracture stress and this process is referred to as fatigue.
The number of stress cycles prior to fracture is a function of the applied stress and,
fortunately, many materials have a maximum level of stress, referred to as the endur-
ance limit, below which they are not subject to fatigue failure. Fatigue fracture results
from the presence of fatigue cracks which are usually initiated by the cyclic stress at
surface imperfections such as machine markings and slip steps. Although the initial
stress concentrations associated with these cracks 'are too low to cause brittle fracture
they may be sufficient to cause slow growth of the cracks into the interior. Eventu-
ally the cracks may become sufficiently deep that the stress concentration exceeds the
fracture strength and sudden failure occurs.
5.6 Strengthening of materials
The engineer is vitally interested in all strengthening mechanisms because of the

technological advantages of stronger materials, but increased strength usually means
a decrease in ductility which may cause fabrication problems and so he is always
faced with some form of compromise.
The inherent strength of a material is limited by plastic deformation and fracture.
Since plastic deformation involves the motion of dislocations, materials could obviously
be strengthened by simply using dislocation-free specimens. Unfortunately this is not
possible (apart from single crystal whiskers which may eventually be used in reinforced
structures) and so one must try to prevent the inherent dislocations from moving so
readily. This philosophy forms the basis of strain hardening, solution hardening and
precipitation hardening. The problems posed by the brittle fracture of otherwise
inherently strong materials are generally lessened by using them in some form of com-
posite or reinforced structure such as prestressed concrete and fibre glass, as described
in section 3.7 and this concept may ultimately lead to a vast new field of strong
materials [3, 4, 5].
5.6.1 Strain (or work) hardening

To understand the basis of strain hardening we must return to the stress-strain diagram
of Fig. 5.1 and consider the plastic region in a little more detail. If a specimen is
stressed to a point W, below the ultimate tensile stress (see Fig. 5.12) and then the
stress is removed the specimen relaxes along WW' as shown, and is left with a permanent
elongation. If the stress is now reapplied a new, higher, yield stress Y' is observed. Thus,
under the influence of applied stress the yield stress gets successively larger (in the case
of pure copper single crystals the increase may be as much as a factor of 10 2 ) and it
becomes progressively more difficult to deform the specimen. This is the basic effect
of cold working a metal, but in addition to the increase in yield strength, hardness and
tensile strength, the ductility and general ability to deform obviously decreases.
Furthermore, other physical properties are affected and there is a slight decrease in
electrical conductivity and density as well as a tendency for the corrosion resistance
to be considerably reduced.
The theories of strain hardening depend on the assumption that as a result of strain
hardening there is an enormous increase in the dislocation density and a corresponding
decrease in the ease with which these dislocations can glide. After a deformation of
only a few per c~nt the dislocation densities increase from an initial value of about
W'
Strain
Fig.5.12 Increase of yield strength by plastic deformation.
lOll m- 2 to as many as 10 14 or 10 16 m- 2 • As these dislocations move they become

piled up at grain boundaries and other lattice imperfections or, because the dislocations
act on many different slip planes they intersect each other producing numerous jogs
and generally become 'tangled'. In either case it is then much more difficult for other
dislocations to glide through the material. Metals with an h.c.p. crystal structure which
can only slip in the basal plane show a low rate of work hardening, whereas cubic
metals, which have several slip systems, tend to exhibit high rates of work hardening.
When a metal is cold worked during its fabrication by any of the many industrial
processes, such as hammering, forging, stamping or drawing, the yield stress increases
as described above and the metal becomes harder and more difficult to work. While
the increase in strength is usually important, excessive cold working may decrease the
ductility to such an extent that brittle fracture might occur in subsequent fabrication
processes. Hence it may be necessary to increase the ductility again, before further
shaping operations can be performed, by annealing the specimen. Annealing is funda-
mentally the opposite process to work hardening and usually consists of maintaining
the deformed metal for a certain period of time at a temperature of about half its melt-
ing point in degrees K. Annealing, or the removal of strain hardening, can be distin-
guished by three temperature regions namely (a) recovery, (b) recrystallization and
(c) grain growth. Recovery consists of a rearrangement of the dense dislocation net-
works formed by cold working into simpler, more ordered, arrangements which reduce
the lattice energy. The most important recovery processes are the annihilation of dis-
locations of opposite sign and polygonization whereby dislocations of the same sign
tend to align themselves to form small angle boundaries. Both of these processes will
require climb and cross slip of the dislocations and so will be assisted by elevated tem-
peratures. During recovery no change occurs in the grain structure and the yield point
may not be decreased appreciably but the overall lattice stress is reduced and there is a
noticeable increase in electrical conductivity.
At a somewhat higher temperature than that required for recovery, the cold worked
structure is replaced by the growth of new strain-free grains in the deformed matrix.
The new grains have large angle boundaries separating them from the strained matrix
and their orientations differ considerably from that of the grains they consume. This
process is referred to as recrystallization and after recrystallization the strength and
hardness of the metal is reduced and the ductility increased. Although dependent on
such factors as grain size as well as temperature, a recrystallization temperature can be
defined as that temperature at which a highly worked specimen completely recrystal-
lizes in about an hour. Typically the recrystallization temperature is about 0-4··0·5 of
the melting point in degrees K and a few specimen values are shown in Table 5.3. They
reveal several interesting facts. Pure copper, for example, cannot be strengthened by
cold working if it is later to be used for steam pipes as it would automatically anneal
or soften, and so copper alloys are preferable. Furthermore it is obviously pointless to
strain harden lead if it is to be used above O°c.
TABLE 5.3
Material Recrystallization temperature CO C)
Copper (pure) 120

Copper (5% AI) 360
Low carbon steel 580
Lead -5
Further increase of temperature above the recrystallization range leads to a further

reduction of the internal energy by shrinkage of the smaller grains and growth of the
larger ones, thus decreasing the stress associated with the original grain boundaries.
A major disadvantage of work hardening as a method of increasing the strength of
a metal or alloy is that the strengthening effect is lost when the specimen is annealed
or used at high temperatures.
5.6.2 Solution hardening

A second and most important method of strengthening a metal is the addition of an
alloying element that goes into solid solution. These solute atoms, if different in size
and electronic structure from the host atoms, will distort the lattice and produce internal
strains. These strain fields act as obstacles to dislocation motion and hence raise the
strength of the material. The distribution of the solute atoms is an important factor in
the hardening produced and short range ordering produces more hardening than a
completely random arrangement. Furthermore, the solute atoms may collect and form
a solute atom 'atmosphere' around the dislocations present in the material as, for
example in low carbon steel where the carbon atoms tend to segregate along dislocation
lines. It was observed in subsection 2.11.1 that a dislocation line is a region of higher
energy than the rest of the lattice (see Fig. 2.16). The solute atoms can reduce the
strain energy if large substitutional atoms settle in the tension region and small ones
in the compression region. The effects of this solute atmosphere is to pin the disloca-
tions so that a higher stress is required to free them from this atmosphere than is
needed for their subsequent motion and so the yield point is characterized by a sudden
drop in the stress (section 5.2).
5.6.3 Precipitation and dispersion hardening

A third method of strengthening metals is that of producing a fine distribution of hard
particles, which can then impede the motion of dislocations within the matrix. In certain
alloy systems this method of strengthening can be more effective than either of the
two previous techniques, and it can be achieved in one of two ways.
Precipitation (or age) hardening can be employed for a variety of alloys which
exhibit a solid sobubility which decreases with decreasing temperature. The process
requires an initial solution treatment to dissolve the solute atoms and then a quench
to room temperature to produce a supersaturated solid solution. The precipitation is
then initiated by reheating to a temperature below the solid solubility limit and held
for a predetermined 'ageing' period. Close control of this temperature and time is
maintained to produce an optimum distribution of the precipitate. The amount of
ageing is quite critical. Under-ageing causes relatively few particles to precipitate and
over-ageing increases the size of the particles and hence decreases their number so that,
in both cases, the degree of hardening is less than optimum. An example of age harden-
ing is found in the AI-Cu system from which the 'Duralumin' series has been developed.
Dispersion hardening is the technique of achieving a fine distribution of hard particles
by allowing certain gases to diffuse into the solid. A reaction between the gas and the
alloy matrix produces the hard particles. For example steel which is to be nitrided to
increase wear resistance usually contains aluminium in solid solution and it is heated in
an ammonia atmosphere so that nitrogen diffuses into the steel and a fine dispersion of
aluminium nitride is formed.
5.7 Creep
So far it has been assumed that stress and strain occur simultaneously but in the case
of many materials this is not entirely true and under the influence of a constant applied
stress the material may continue to deform indefinitely. This process is called creep
and is readily observable in the sloping lead-covered roofs of old churches where, over
the years, the lead has deformed under its own weight to produce a sheet considerably
thicker at its lower edge.
Since materials tend to work harden during the process of deformation, continued
deformation under constant stress means that there must be some recovery taking
place. The rate of recovery increases with increasing temperature and so the creep rate
is strongly dependent on temperature and creep is an important consideration in high
temperature applications. A characteristic creep curve is illustrated in Fig. 5.13. There
Fracture
Primary Secondary
Time
Fig.5.13 Creep behaviour under constant applied stress.
are four main areas of interest: (i) an initial instantaneous strain which can be partly
elastic and partly plastic; (ii) a primary region of creep of decelerating creep rate; (iii) a
secondary period of constant minimum flow rate; and (iv) a tertiary creep region of
accelerating strain rate, which ultimately ends in fracture.
In the primary region the creep rate decreases due to the competing effects of work
hardening and recovery until the rates of work hardening and recovery are equal and
the creep rate is then a minimum (secondary region). At low temperatures the creep
rate decreases to virtually zero so that the dimensions of the specimen stabilize and the
applied stress can be safely supported indefinitely. At higher temperatures tertiary creep
can occur due to necking of the specimen or grain boundary sliding and this continues
until the specimen fractures. Precipitation hardened alloys are generally used in high
temperature creep resistant applications because, in addition to acting as barriers to slip
and grain boundary sliding, the fine dispersion of particles apparently restricts the rate
of recovery.
5.8 Mechanical properties of plastics
The mechanical behaviour of plastic materials varies considerably from the brittle
behaviour of perspex to the amazing elastic behaviour of rubber. Unlike the majority
of materials, which can only sustain elastic strains of about 1 per cent, rubber is an
example of a class of materials called elastomers, which can be strained elastically by
several hundred per cent. The tensile properties of an elastomer can be explained
qualitatively from the model of the structure of polymer materials as a tangled bundle
of fibres described in subsection 3.9.2. In rubber the individual molecules are coiled
I
I
E I
~ I
> Glass I
I
1_--------1
------; Crystal I
I I
: I
I
Temperature
Fig. 5.14 Variation of volume with temperature for an amorphous material illustrating the
melting point T m and the glass transition temperature T g.
up on themselves and joined to one another by a few sulphur cross linkages which
prevent plastic or viscous flow (see below). Thus an applied tensile stress can be trans-
mitted from molecule to molecule via the cross linkages and straighten out the molecules
producing an immense increase in length. On removal of the applied stress the molecules
revert to their more stable coiled state. This behaviour is not typical of most polymers
because either the configuration of the side groups or the influence of weak inter-
molecular forces tends to prohibit self coiling of the molecules. In general the mechanical
behaviour of polymers varies markedly with temperature.
In the liqUid state a polymer consists of a random collection of wriggling long chain
molecules and as the temperature is reduced the thermal agitation decreases until, at
the melting point Tm, crystallization may occur with a corresponding change in volume.
However, as already observed crystallization of polymer material is rather difficult and
amorphous polymers show no change in volume at Tm' but remain supercooled liquids
until a lower temperature is reached, where molecular rearrangement ceases and the
liquid vitrifies into an amorphous solid (Fig. 5.14). At this lower temperature there is
a change in the rate of decrease of volume and hence in the thermal expansion
coefficient. This behaviour is not restricted to polymers and is typical of all amorphous
materials, such as glass, and the temperature at which the supercooled liquid finally
vitrifies is called the glass transition temperature, Tg • The resulting mechanical
behaviour at room temperature is governed by the magnitudes of Tm and Tg relative
to room temperature. If Tm and Tg are both below room temperature the polymer is
a liquid, whereas if T m and Tg are both above room temperature the amorphous regions
behave very much like glass. A completely amorphous polymer such as perspex with Tg
about 60°C, tends to be very rigid and brittle at room temperature. If room tempera-
ture lies between Tm and Tg the situation is rather more complicated because the
polymer is either a completely supercooled liquid or a combination of crystalline and
supercooled liquid regions. The presence of the amorphous liquid regions in a partially
crystalline polymer has a marked effect on the mechanical behaviour of the material
since they give a certain amount of flexibility to the material as in the case of poly-
ethylene. The response of the supercooled liquid regions to an applied stress is rather
complicated because, in addition to an instantaneous strain in the individual molecules,
the stress causes the individual molecules to slide past one another as in a viscoelastic
process. A viscous material is of limited technological application but fortunately the
viscous flow can be decreased by increasing the degree of crystallinity, as in high density
polyethylene. This is much more rigid than the normal material and is widely used for
liquid containers. Alternatively a certain amount of cross linking may be introduced to
restrict the relative motion of the molecules. Both T m and Tg are governed by the
strength of the intermolecular forces and can be adjusted to a certain extent by
varying the chemical composition of the polymer side groups. By a suitable choice
of T m' Tg , the degree of crystallinity and cross linking, a polymer material can be
designed for a specific technological application.
In thermosetting polymers the process of curing creates a rigid amorphous solid.
The cross linking prevents relative motion between the molecules and the resulting
material is fairly brittle.
References
1. Frank, F. C. and Read, W. T. Phys. Rev. 79,722 (1950).

2. Field, J. E. Brittle fracture: its study and applications, Contemp. Phys. 12 (1), 1-31 (1971).
3. Kelly, A., Smith, G. C., Forsyth, P. J. E. and Kennedy, A. J. Composite Materials, Iliffe (1966).
4. Kelly, A. Strong Solids, Oxford University Press (1966).
5. Gordon, J. E. New Science of Strong Materials, Penguin (1968).
Questions
1. A steel wire of length 1 m and cross sectional area O· 5 mm2 is stretched horizontally
between two pillars. A mass of 0·1 kg is suspended from the mid-point of the wire.
Calculate the depression of the mid point. [Young's modulus of steel = 2 x lOll Nm -2.]
2. (a) Deduce an expression for the bulk modulus in terms of Young's modulus and
the shear modulus.
(b) Show from theoretical considerations that for an isotropic material Poisson's ratio
cannot be greater than 0·5. Check for as many materials as possible that this
theoretical value is not exceeded.
3. Show that, for a homogeneous isotropic material
Ele = 2(11 + 1).
A gold wire, 0·32 mm diameter, elongates by 1 mm when stretched by a force of
103·3 N and twists through 1 rad when equal and opposite torques of 14·5 x 10- 6 Nm
are applied at its ends. Calculate Poisson's ratio for gold.
4. Aluminium is an f.c.c. metal and deforms by slip on {Ill} planes and in (110)
directions. A single crystal is stressed in tension along its [11 0] direction until slip
starts.
(a) On which {Ill} planes and in which <}10) directions will slip occur?
(b) If the critical shear stress for slip is 106 Nm -2 what is the applied tensile stress?
5. A glass plate has a sharp crack of length 1·5 11m in its surface. Calculate what stress
is necessary for the crack to propagate if Young's modulus for glass is 7 x 10 10 Nm- 2 and
the energy of the fracture surface is 0·5 J m- 2 •
6. The relation between the changes in electrical resistance and strain for a strain gauge
is given by the gauge factor (8RIR)j(0/1l). Show that, if the resistivity is assumed to be
independent of strain the gauge factor is given by 1 + 211. Check the validity of this
assumption by finding the gauge factor for several strain gauges and comparing with
this theoretical value.
7. Cleavage occurs on {100} planes of MgO. If a stress of 40 x 106 Nm- 2 is applied
parallel to the [111] axis will cleavage occur, and if so, on which cleavage planes?
Critical fracture stress for cleavage is 12 x 106 Nm- 2 •
6 Thermal Properties
6.1 Introduction
In this chapter the thermal properties of solid materials are considered from an atomic
point of view. It will be important to understand the fundamental thermal concepts
of temperature and heat capacity from such a viewpoint and to integrate these con-
cepts with others that have been met already. Then it is possible to proceed to an
explanation in atomic terms of familiar macroscopic thermal properties such as thermal
conductivity and thermoelectricity. Thermodynamics shows that it is not possible to
talk precisely about the intrinsic heat content of a body but only about its internal
energy, the total kinetic and potential energy of its constituent parts. This internal
energy may be increased or decreased by the transfer of energy to or from the system
in the form of 'heat' or 'work'. The latter mechanism, which invariably involves a force
moving through a distance, will not be of direct concern here.
The internal energy resides in atomic, molecular and electronic motions and these in
turn can be characterized by the occupation of certain quantized states of the system,
the energy levels. Temperature, the characteristic of thermal equilibrium, can then be
described in statistical terms through the occupancy of these energy levels. At tem-
perature T, the occupancy of each level depends exponentially on the energy of the
level measured in units of kT. It is convenient to consider a crystalline solid as a
regular array of bound atoms, molecules or ions with which there mayor may not be
associated large numbers of 'free' electrons. The lattice and any associated free electrons
can be treated separately although this step is not always justified. The discussion will
centre on the thermal properties of the lattice and of the free electrons. The general
ideas of statistics applicable to both will first be considered.
6.2 Thermal statistics
The understanding of temperature and internal energy derives from the classical work
of Maxwell and Boltzmann and it is instructive to begin with a resume of their results.
Assume that in a gas of free particles at temperature T K the only motions of interest
are the translational movements of the particles associated with their velocities. These
motions can be resolved into three mutually perpendicular directions and each particle
is said to have a 'degree of freedom' for the motion in each of the three directions.
Maxwell showed that ~kT of energy can be associated per particle with each degree of
freedom. k is Boltzmann's constant, the ratio of the molar gas constant R to Avogadro's
number. It has the value 1·38 x 10- 23 J K- 1 • Clearly k measures the thermal energy of
a molecule per degree of 'temperature' above absolute zero. Alternatively it can be
THERMAL PROPERTIES 107
considered as the specific heat of the molecule, the amount of energy required to
produce unit temperature rise.
The total energy per particle is then (3/2) kT. For bound particles, however, there is
the potential energy of the binding forces as well as kinetic energy. Maxwell further
showed that the average potential energy is equal to the average kinetic energy. Accord-
ingly at room temperature each bound atom in a solid will possess an average total
energy of 3 kT (0'075 eV). Where this energy, though small, is comparable with energy
level separations, it can playa significant role; in semiconductors for example, by
ionizing the very shallow impurity levels.
The concept of a mean energy implies that some particles have less and some more.
Fig. 6.1 illustrates the distribution of kinetic energies of vibration, E, deduced by
Maxwell for a collection of particles at temperature T. The ordinate rp(E ) represents
the fraction of particles having energy E per unit energy interval, i.e. the actual fraction
1
2kT
li:J
'--I I
9- - I
4kT
Mean:
energy I
1
o kT 2kT Eo 3kT
E
Fig. 6.1 The Maxwell distribution of kinetic energies.
in the interval D.E will be given by r/>(Eo)D.E (Fig. 6.1). This is a statistical distribution
which is somewhat different when the particles whilst still in thermal equilibrium are
being acted on by an external force, as are bound electrons in a magnetic or electric
field. In such a case the thermal contribution to the total energy will result in an
increase in the potential energy. The distribution of this potential energy among the
particles was shown by Boltzmann to follow an exponential law. If No particles have
a given potential energy then the number with amount U in excess of this will be
No exp (-U/kT). This distribution is illustrated in Fig. 6.2.
An alternative statement of the Boltzmann relation is that the probability that a
given particle has potential energy U is proportional to exp( -U/kT). If U is much
greater than kT the probability is very small and vice versa. An example is the distri-
bution of the molecules with height in the atmosphere where the force acting is gravity.
The potential energy of a molecule is mgh where h is the height above the earth's sur-
face. The concentration at height h is therefore proportional to exp(-mgh/kT) as is
the atmospheric pressure at that height.
Again, in the calculation of the relative population of electronic energy states in
atoms, the potential field is an electric one. Not every atom will be in its ground state.
The receipt of thermal energy by way of the atomic vibrations of the lattice can cause
the potential energy to be raised sufficiently to attain the first excited state. Using the
3kT
U
Fig. 6.2 The Boltzmann distribution (number of particles N with excess potential energy U as a
function of U).
above statistics, usually called Maxwell-Boltzmann (M.B.) when both kinetic and
potential energies are involved, the relative occupation of the ground state (0) (Fig.
6.3) and first excited state (1), in thermal equilibrium will be given by:
number in state I exp(-EdkT)
(6.1)
number in state 0 exp(-Eo/kT)'
henceN1 =No exp{-(El - Eo)/kT}.
, st excited state
.
>
Cl
41
c:
w
Ground state
--------------------------0
Fig. 6.3
If there were N atoms altogether (N = No + N 1 ), then the proportion in the excited

state E 1 at T K would be
(6.2)
Equation (6.2) shows that there are always more atoms in the state of lowest potential
energy. Had (El - Eo) been 1 eV at 300 K then only about 10- 15 per cent would have
been in the excited state, whereas had (El - Eo) been 0·02 eV, about 32 per cent
would have been.
The statistical prediction of the effect of thermal energy upon the relative popula-
tion of energy states is of immense importance in all electronic and magnetic properties
of solids and their variation with temperature. For a given set of energy levels it is the
temperature which governs the distribution providing us with a statistical interpretation
of the meaning of temperature.
6.3 Heat capacity
The heat capacity of a body is that thermal energy necessary to raise the temperature
by one degree Kelvin and it is usually expressed as a molar quantity. At constant
volume no mechanical work is performed, all the thermal energy is converted into
internal energy U. Hence the heat capacity is given by
(6.3)
In practice measurements of C are made at constant pressure, Cp ' but the two values
can be related.t
At zero temperature the internal energy is a minimum and the heat capacity is zero.
This is a consequence of the third law of thermodynamics. As the temperature is raised
the heat capacity variations indicate the various mechanisms by which energy is taken
up in the solid. A typical measurement is shown in Fig. 6.4 for germanium, whose heat
25 -
I
0
E 20
Cl
~
I 15
~
-
;:;>
0 10
)(
C. 5
V
0 100 200 300

Temperature T (K)
Fig. 6.4 Heat capacity of germanium.
capacity exhibits a rise from zero to a plateau followed by a very gradual increase
thereafter. Many materials show this kind of behaviour but differ in the rapidity of the
rise. For example, the plateau in lead is reached by 90 K but in silicon not until 600 K.
A direct application of M.B. statistics would attach an average total energy of 3kT
to each atom and hence of 3NkT to each mole of solid. The heat capacity, from eqn
(6.3), is the derivative of this, namely 3Nk (25 x 103 J K -1 kg mol- 1 ) and indeed the
plateau value is close to this. The explanation of the fall off of Cv at low tempera-
tures was given first by Einstein and then in more detail by Debye in his theory of
specific heats. The ideas behind these theories are directly related to the statistical
ideas discussed above.
Without worrying about the details think of a solid as a set of oscillators vibrating
with a characteristic frequency. These will be the entities which take up thermal energy
during heating or emit energy during cooling. Each oscillator will have a spectrum of
possible energy states because theory shows that for a simple harmonic oscillator the
energy E is related to the frequency v of vibration by
E =(n + !)hv, (6.4)
where n is an integer (Fig. 6.5).
The temperature of the collection of oscillators will decide the statistical distribution
of energy states in which these oscillators find themselves. Suppose the temperature is
such that the great majority of oscillators are in the lowest state. If the temperature is
lowered beyond that point the oscillators are incapable of parting with any more energy
so the specific heat suddenly becomes zero. In practice there is always a statistical
t Cp - Cv =90<2 KVT where 0< is the linear expansion coefficient, V is the molar volume and K
is the bulk modulus.
spread in the occupation of levels so there is a tailing off in the specific heat rather
than a sudden drop at low temperatures. Similar arguments apply during warming up.
A typical frequency of vibration for an atom in a solid is 1013 Hz and the energy ofits
lowest state is thv (0·02 eV). The temperature appropriate to this energy is given by
the classical expression kT leading to a value of T = 232 K. This is the temperature in
this rough calculation at which the oscillator would be in its ground state. Below this
temperature it would not be contributing to the specific heat. Einstein carried out a
statistical calculation assuming that all the oscillators vibrated independently with the
same frequency. His result was that the average total energy E of the system of N
oscillators of frequency Vo is given by
E = 3Nhvo/ {exp(hv/kT) - 1}. (6.5)
Equation (6.5) gives E ~ 3NkT at high temperatures corresponding to a specific heat
of 3R but at low temperatures gives values which follow the curve of Fig. 6.4 fairly
7
"2hv
>-
...
Cl
GI
c:
w 5
"2hv
3
"2hv
1
- - - - - - - - - - - "2 hv
Fig. 6.5 Energy levels of a simple harmonic oscillator of frequency II.
well. In a real solid the atoms cannot be considered to vibrate independently because
of the bonding between them. The motion of one atom must affect its neighbours and
vice versa. The frequencies of vibration are really a property of the solid as a whole.
In a one-dimensional line of atoms various vibrations are possible of different wave-
lengths and therefore different frequencies (Fig. 6.6). Thus, there is really a spectrum
of frequencies for the atomic oscillators and Debye attempted to take this into account
by modifying the Einstein theory and by considering the vibrations to be those of an
elastic medium. The velocity of the waves is the velocity of sound in the solid, since
the waves are sound waves. Debye's statistics were a little more complicated but his
result was in better agreement with experiment than Einstein's. Suppose the maximum
oscillator frequency is vo, then if T~ hVo/k, the theory predicts that the energy distri-
bution for oscillators is Maxwell-Boltzmann like and the specific heat is 3R. But if
T ~ hVo/k the specific heat decreases with temperature as described above, being pro-
portional to T3 in fact. Thus the temperature dependence of specific heat is determined
by the maximum oscillator frequency and this in turn depends on the strength and
type of binding of the atoms, or in Debye's terms on the elastic properties of the
solid. The temperature hVo/k for a solid is known as the 'Debye characteristic tem-
perature e'.
The ideas of Debye lead on to a very important concept in the theory of solids
namely the phonon. The oscillators of Fig. 6.6 each have an energy which is quantized
Evibration = h x frequency . (6.6)
• • • • • • • • • • • • •
• • • • • • • • •
• • • •
• • • • •
• • •
• •
• • •
• • • • • •
• • • •
• • •
• • • •
• • • • •
• • • •
Fig. 6.6 Atomic vibrational modes of a one-dimensional solid.
By analogy with the photon it is convenient to treat this vibration as a 'particle'. As

this identification is a loose one, it is sometimes called a 'quasi-particle' which has
energy and momentum and is named a phonon. The heat content of a solid appropriate
to the lattice can be thought of then, either as the energy of standing waves of varying
wavelengths of the lattice as a whole, or, equally validly as the energy of a collection
of phonons. Each phonon is a standing wave of definite wavelength, frequency and
energy. But there is also the possibility of energy and momentum exchange leading to
the creation or annihilation of these standing waves or phonons.
Debye's phonon theory explains the temperature dependence of the thermal capacity
of a solid very well and yet only the lattice has been considered. The contribution of
free electrons has not been included and so it is clear that this must be small. Accord-
ing to classical M.B. statistics the contribution to heat capacity is (3/2) kT per free
electron but the observed contribution is much less than this. The reason can be under-
stood from the Sommerfeld model of a metal (Appendix I). The only electrons able
to receive thermal energy and hence contribute to the heat capacity of the solid are
those within a few kT of vacant energy states.
These electrons are relatively few at ordinary temperatures so that the electronic
heat capacity depends only on the fraction which contribute (Fig. 6.7). The number
increases linearly with absolute temperature.
...... --
,~\
~O'cPo' -Density of
,pfPJ~ g~ states
/ ~ g Probability of
., •• 0 occupancy at
/ .g T=O
/ 10.. kT
/ o.
Probability of
occupancy at
o g~ temperature T
• 0 •
o •
•
EF Energy
Fig. 6.7 Electron occupancy of the density of states in a metal.
The internal energy of free electrons =number x mean thermal energy

ex T x (3/2)kT
ex T2
therefore heat capacity contribution =dU/dT ex T.

This linear dependence is observed both at low temperatures when the lattice con-
tribution is negligible (ex T 3 ) and at high temperatures when this contribution has a
maximum value of 3R.
At low temperatures then
molar specific heat (Cv ) =aT 3 + bT,
lattice electrons (6.7)
where a and b are constants.
6.4 Specific heat anomalies
Occasionally, quite sudden changes in the specific heat of a substance are observed over
a narrow range of temperature. One situation for which this can happen is when there
is an electronic energy state of the atoms of a solid not far removed in energy from the
ground state by say, e eV (Fig. 6.8).
The excitation of electrons from the ground state will occur with a probability pro-
portional to exp( -e/kT). When T < e/k most atoms will be in the lowest state and
when T ~ e/k the atoms will be equally divided between the lowest and the excited
state. For a range of temperature intermediate between these extremes there will be a
sharp increase in the number of atoms excited and a corresponding change in the
internal energy. A dramatic increase in specific heat will be observed over a small
range of temperature where kT is near e which may typically be 0·1 eV. The behaviour
of the specific heat as the temperature changes is shown in Fig. 6.9.
THERMAL PROPER TIES 113
Excited state
>-
~
CD
C
W
>< )( )( )( )( )( )( ><
Ground state
Fig. 6.8 Ground state conf'Jguration of atoms giving rise to electronic specific heat anomaly for
€~kT.
Cex 1.0
!
+"
0.8
'"
/
I I\. \
I
!
i
"~ ~
«I
CD 0.6
.c
i
11
t.l
t--
;;::
I
.g 0.4
c.
en
~
---r--r--
0.2 J
j
o 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
kl/,t
Fig.6.9 Typical specific heat anomaly Cex due to electronic excitation.
8" r
600
I
Cl
.>I.
:J.
....«I
CD 400
.r.
t.l
~
t.l
CD
C.
en
200
800
Temperature (K)
Fig. 6.10 Specific heat of nickel (showing a magnetic order-disorder phenomenon).
A specific heat anomaly also occurs when some kind of rearrangement of atoms or
molecules of a crystal takes place, for example when a phase change occurs in an alloy.
But there are other cases where anomalies appear during a change of order not directly
related to atomic or crystal structure. Examples which will be met in other chapters
are the alignment of electric dipoles in ferroelectric materials, or of magnetic dipoles
in ordered magnetic materials. A more subtle kind of ordering occurs in superconduct-
ing materials where a change in the 'ordering' of electron momenta leads to a specific
heat anomaly. Fig. 6.10 shows a typical specific heat anomaly in a ferromagnet occur-
ring at the Curie temperature where the ferromagnetism (ordered array of magnetic
dipoles) changes to paramagnetism (disordered array) as the temperature increases.
6.S Thermal expansion
A considerable part of the thermal energy of a solid is in the form of atomic vibrations;
the higher the temperature the more energetic the vibration and consequently, the
greater the amplitude. As a result of the varying amplitude the measured lattice spacing
between atoms is a mean figure and it is necessary to know how it depends upon the
temperature.
Interatomic distance r
'0
>-
Cl
CD
C
III
m
0';:::;
c
....o
III
a..
Fig.6.11 Interatomic potential energy diagram.
The lattice constant for a particular solid arises from the balance in forces between
the repulsion of neighbouring ion-cores due to their electron shells overlapping and the
attraction of the particular bonding type (ionic, covalent, metallic). The eqUilibrium
lattice constant is shown in Fig. 6.11 corresponding to the minimum in the depend-
ence of the potential energy upon interatomic distance. The addition of vibrational
energy to an atom can be represented in Fig. 6.11 by the horizontal line A 1 A 2 , the
height above 0 being the maximum kinetic energy of vibration. The extremes A 1 and
A2 correspond to the separations at which the kinetic energy has been transferred
into potential energy and represent the limits of the vibration. For this motion the
mean interatomic distance is midway between A 1 andA 1 , at Ao and for small energies
lies above O.
For higher temperatures and consequently higher vibrational energies (e.g. A ~ A;) the
mean interatomic distance increases since although A ~ is little different to A 1 due to
the strength of the repulsive ion-core interaction, A ~ can differ considerably from A 2 ,
the attractive force being weaker in general. This resulting expansion of the lattice
structure, due to the injection of thermal energy occurs because the potential VCr) is
not symmetrical. Had it been symmetric the mean position of the atom would always
be above 0 and no expansion could occur on the increase of vibrational energy.
Thermal expansion is defmed as the fractional change in either length or volume
per unit temperature rise, e.g. for the linear coefficient
<lL = (1/1) d//dT. (6.8)
The expansion coefficient is largest for those materials with the shallowest potential
curves. These are the relatively weakly bonded materials such as the alkali metals.
Strongly bound insulators, however, such as ionically bound glass, and quartz, or the
covalently bonded materials such as silicon, would be expected to have a low expansion
coefficient. This dependence is shown in Table 6.1 where the coefficients are for linear
expansion.
TABLE 6.1
Linear expansion coeffiCients (K-l)
Potassium K 83 x 10-6
Aluminium Al 23 x 10- 6
Iron Fe 12 xl0- 6
Silicon Si 2·3 x 10- 6
Germanium Ge 5·5 x 10-6
Quartz (fused) Si02 0·5 x 10-6
Crown glass 9 x 10- 6
Polyethylene 180 x 10-6
Natural rubber 670 x 10-6
Bakelite 40 x 10-6
Molecular solids, such as polymers, have very weak attractive forces and consequently
exhibit large thermal expansion, e.g. rubber and polyethylene. It is interesting to note
that rubber contracts when heated but this is due to the temperature dependence of its
elastic modulus. The strength of the bonding in these materials can be increased by
inducing cross-linking between monomers (Section 3.9.2) and this severely reduces the
expansion, e.g. bakelite (Table 6.1).
6.6 Thermal conductivity
It has been seen that at a given temperature a material will contain a 'gas' of energetic
free electrons if the material is metallic or semiconducting, plus a concentration of
lattice phonons. In equilibrium these electrons and phonons are moving in random
directions and hence transporting energy, with no net flow in any particular direction.
This energy is eventually lost by interactions either between electrons and phonons,
electrons and electrons, or phonons and phonons. In all the interactions energy is
merely being transferred, and so an equilibrium is a dynamic situation with energetic
electrons being continually excited and de-excited and phonons being continually
created and destroyed.
Should a material be subjected to a gradient in temperature, the hot and cold regions
will be characterized by different phonon concentrations and energies and different
mean electron energies. As a result there will be a natural diffusion of the more
energetic electrons to the region where their mean energy is lower, and of phonons
from the higher to the lower concentration. In both cases this corresponds to a net
energy transfer from a high to a low temperature region. The mechanism of transfer will
not be one of direct flow from high to low temperature of appropriate electrons and
phonons but will be a dynamic one in which the process is gradual, energy being lost
and gained often en route. Phonons can be regarded as travelling down the sample with
the velocity of sound in the material and with a characteristic mean free path. Unlike
electrons the total number of phonons is not conserved, but phonons can be created
at the hot end to carry more heat and destroyed at the cold end. The energy transfer
increases the mean electron kinetic energy and the total phonon energy of the low
temperature region, i.e. it raises its temperature, and this will continue until the whole
solid achieves a stable equilibrium temperature. Should the temperature gradient be
continuously impressed upon the material, then the energy transported must be trans-
ferred to the coolant at the low temperature end. Heat is then being continuously con-
ducted along the sample.
The ability of a material to conduct heat is given by its thermal conductivity K
which is defined as the quantity of heat flow Q, per unit area A, per unit-time t, per unit
temperature gradient dT/dx, Le.
dQ/dt = -KA(dT/dx) (6.9)
The negative sign indicates that the heat flow is in the direction of decreasing tempera-
ture. Table 6.2 gives some values of K for a range of materials. By simple kinetic theory,
TABLE 6.2
Thermal conductivities (Wm-1 K-l)
Ai, 420
AI 210
Fe 63
(Nichrome) Ni-cr (70-30) 14
Ge 59
NaO 7
Glass O·g
Diamond 630
Polystyrene 0·1
Expanded polystyrene 0·03
Rubber 0·2
Wood 0·2
Concrete 0·9
thermal conductivity K is related to the mean free path A of the carrier by the relation
K=\CVA,
where C is the specific heat and v the velocity. Assuming the formula applies to phonons,
their velocity and mean free path are therefore important. The velocity of a phonon,
regarded as an elastic wave is determined by the elastic constants of the medium
V =(d/p) 1/2 , (6.10)
where d is an elastic constant and p is the density; d will be Young's modulus for a
longitudinal wave and the shear modulus for a transverse wave. Phonons have mean
free paths which may be one-tenth of those of electrons. In a metal an electron may have
a mean free path of 100 lattice spacings. In disordered alloys, electron mean free paths
are much reduced.
The best thermal conductors are metals in which the free electrons are dominant and
very mobile. Non-metallic materials conduct primarily by phonons and in general K is
much smaller for these materials than for metals because of the reduced mean free path
and velocity. However in both semiconductors and metals the electron contribution is
restricted to that proportion near the Fermi level. This is not the case for phonons which
do not obey the Pauli Exclusion Principle. Note also the influence of density on velocity
(eqn (6.10)); light elements tend to have high thermal conductivities.
Some non-metallic materials have a value for K in excess of that for the metal silver.
They are substances which can be manufactured almost to crystalline perfection. The
lack of defects assures large phonon mean free paths and hence a large K. Typical materials
in this class are diamond and sapphire. In contrast, in amorphous materials the random
structure interferes with the movement of phonons so that K is lower than in the
crystalline counterpart.
It has been seen that for most materials the properties of thermal conduction are
determined by the electronic and crystalline state. Some solids, however, are not perfect
lattices, but are porous containing voids (e.g. concrete) or have been deliberately ex-
panded into a very low density form containing voids (e.g. polystyrene). The voids
represent regions of very poor thermal conduction since air is a poor conductor and
so the material as a whole will be characterized by a low value of K. Such materials
represent a most important group of commercial thermally insulating materials.
6.7 Thermoelectricity [1]
6. 7.1 Thermoelectric power

Since current carriers in materials are electrically charged and can transport heat energy,
it is not surprising to find that these two properties interact. The effects due to the
interaction are called thermoelectric. If a temperature gradient is maintained across a
metal or semiconductor, energetic carriers at the hot end tend to move to the cold end
preferentially. As a result of this electron (or hole) flow the ends become electrically
charged.
For example in Fig. 6.12 where the carriers are supposed to be electrons, the
energetic electrons leave the hot end and travel to the cold end making that end
negative. Immediately however the electric field produced by the separation of
charges gives rise to an electric current opposing the one induced by the temperature
gradient. An equilibrium is soon established in which these currents balance. The
potential difference which is created in these circumstances is known as the thermo-
electric e.m.f. characterized by the thermoelectric power S which is defined as the
potential drop per degree temperature difference:
S=dV/dT. (6.11)
+~------~--~--~~------~~~~
+
Hot + Cold
+
"Heat" current of electrons

Fig. 6.12. Origin of the thermoelectric power in a uniform bar subjected to a temperature
gradient.
For materials in which the dominant carrier is the electron, S is negative (e.g. N-type or
intrinsic silicon); where the dominant carrier is the hole, S is positive e.g. P-type silicon).
The manner in which electrons and holes lead to opposite polarity effects is shown in
Fig. 6.13.
T+ dT V- dV T+dT V+dV
Net Net
+0 -0
-" l
."CCD
EOUl
:unf
.&; 11).-
I-Cij"a
-.- j
EII)Ul
~_:::J
G)O:::
.&;.&; . -
I- "a
Net Net
T -0 V T +0 V
S =~ = negative dV =POSITIve
S =liT
(a) (b)
Fig. 6.13 Thermoelectric power. (a) Metal or N-type semiconductor. (b) P-type semiconductor.
Referring to eqn (6.11) and interpreting d Vas energy per unit charge (dV - kT/e),
S - k/e which is a specific heat per unit charge or the amount of 'heat' carried by
each electron. In a metal only electrons near the Fermi level contribute and that
fraction of the whole is kT/E F for a metal at temperature T in which the Fermi level
isEF • S must then be ofthe order (kT/E F) k/e which is typically 10 JlV/degree. In a
semiconductor, because ofthe band gap, most carriers can have energies above the
Fermi level. For a band gap EG the specific heat of excited carriers is -EG/T, i.e.
S - (EG/kT) k/e which is about 103 JlV/degree, much bigger than for metals. Some
values of S are shown in Table 6.3 where this difference is apparent.
TABLE 6.3
Element Thermoelectric power S (~V K-l)

(at room temperature)
AI - 0·47
Fe - 51·3
Si -408
Ge + 303
6. 7.2 Seebeck effect
S is an absolute property of a material, but it can never be determined directly since
in order to measure the thermoelectric potential, a voltmeter and suitable leads are
required. These leads will have the same temperature drop across them as the material
to be measured, and so the measured potential will be that characteristic of the material
reduced by that characteristic of the leads. Thus, it is only possible to measure differ-
ences in thermoelectric power, e.g. for materials 1 and 2 in Fig. 6.14:
(6.12)
Absolute values of S can be obtained indirectly by use of one material of known S, e.g.
S =0 for superconductors.
Material 2
T+I1T
T+3T
Material 1
T+3T
Material 2
T
Fig.6.14 Seebeck effect.
If the two materials of Fig. 6.14 are identical, then of course there will be no
thermoelectric potential. Should they be dissimilar, however, there will be a potential,
the production of which is known as the Seebeck effect. This is utilized in the common
thermocouple and Table 6.4 shows some values of S 12 for various thermocouple
combinations at room temperature
TABLE 6.4
S12 (pV K .... ) for some common thermo-
couples
Copper-constantan 43
Orromel-alumel 41
Pt-Pt 10% Rh 6·4
Iron-constantan 54
6.7.3 Thomson effect

The thermoelectric effects so far discussed have involved a simple interchange between
energy gained thermally and energy gained from an electric field. The equilibrium has
corresponded to no net flow of carriers. Consider now the effect of producing a net
flow of carriers and at the same time imposing a temperature gradient upon a material.
A new phenomenon known as the Thomson effect appears which depends upon the
direction of current flow.
A net current can be made to flow by applying a potential difference across a

specimen, using an external e.mJ. The passage of this current will of course give rise
to a Joule heating effect but this will be ignored here for there is a further heating or
a cooling effect, thermoelectric in origin. Suppose the applied voltage causes a net
flow of carriers to move from the hot to the cold end of the specimen. In order for
these electrons to remain in thermal equilibrium with the lattice, which they will do
by collision, energy will be given by these 'too hot' electrons to the lattice and sub-
sequently evolved, i.e. a heating effect. However, should the carriers be moving cold
to hot, they will require extra energy from the surroundings in order to be in equili-
brium at the hot end, i.e. a strong cooling effect is produced. These Thomson effects,
which are properties of a given material, not of a combination of materials, are sum-
marized by the following equation, where Qrepresents the rate of emission of heat,
and J is the conventional current density:
Q=-p-rJ dT/dx (6.13)
where the constant PT is the Thomson coefficient.
If electrons are the majority carriers, PT is negative, and if holes are, it is positive. It
can be shown that
PT =TdS/dT. (6.14)
A typical value of PT is lpV K- 1 •
6. 7. 4 Peltier effect
This effect occurs at a junction of two materials when a current flows through it.
Depending on the circumstances, the current flow produces either a heating or cooling
at the junction and this is known as the Peltier effect. The Peltier coefficient n'(B for
a junction AB is dermed as the rate of heat absorption per unit current flow. There
is a simple relation between Sand n, namely S = nIT. When a molecule moves from
the liquid phase into the vapour phase a latent heat is involved. Similarly an electron
in a material A at a junction, in moving to material B can be thought of as being in a
different phase, a latent heat of transfer from A to B being required. By analogy with
the liquid-vapour transition, if there is a 'vaporization' of the electron (electron goes
A -+ B say) heat will be extracted from the junction to provide the corresponding
transfer energy and the junction will cool (Fig. 6.15). If there is a condensation
latent heat given to

electron, junction cools
--+....:......~e
Material A MaterialS
e---+-o--
latent heat given up by
electron, junction heats
Fig. 6.15 Origin of Peltier heating and cooling at a junction.
(electron travelling B -+ A) the corresponding 'latent heat' will be given up at the

junction and it will heat up. Clearly in a double junction ABA the thermal effect at
AD will be opposite to that at BA.
These ideas are particularly important from a practical viewpoint when applied to a
semiconducting P-N junction. At such a junction (see Bibliography, Sproull, for
example) there is a potential barrier developed in equilibrium (Fig. 6.16) even though
no electric field is applied.
If the junction is reverse biased (Fig. 6.16c) electrons will flow from P- to N-type,
but in doing so they will flow down the potential barrier before reaching thermal
equilibrium on the N-type side. As a result the energy gained by the electrons from
the potential field must be given up to the lattice by collision in the thermalization
process and so a heating effect is produced at this junction. For forward bias (b),
Major~y
..Minority
Majority.
..Minority
Majority
..
iii
:;::; •
c .Minority
Ql
>
0
...ClQl
.....
Q.
J
C C
0 CD
u
Ql N N P
iii
+ +
• Distance
(a) (b) (c)
Fig.6.16 Peltier effect in a P-N junction by electron transport. (a) Zero bias-thermal eqUilibrium.
(b) Forward bias-cooling. (c) Reverse bias-heating.
however, the potential energy of the electrons crossing is increased at the expense of
their thermal kinetic energy. Only the most energetic are capable of crossing and so
the effect on the N side is that the mean energy and hence the electron temperature is
lowered. To restore the thermal equilibrium, heat must be absorbed from the lattice
and a cooling effect is produced.
Similar arguments apply to holes in semiconductor junctions and also to electrons
in metal-semiconductor junctions. The largest effect occurs in the combination which
gives the largest energy difference between the conduction states on the two sides of
the junction.
The Peltier effect can be used as shown in Fig. 6.17 where the electron current flow
from left to right is in effect transporting the amount of energy f:lE per electron from
metal 1 to metal 2, cooling metall and heating metal 2. Such an arrangement is the
basis of compact, robust and simple thermoelectric heaters or coolers.
Thermoelectric applications [2] involve the use of the Seebeck effect to generate a
voltage from a temperature difference, the 'thermoelectric generator'; and the Peltier
effect to cool, the 'thermoelectric refrigerator'. Materials for these applications are
assessed through a figure of merit Z =S2 ojK, ojK being the ratio of electrical to thermal
conductivities. Hence it is important for a high Z to maximize S2 0 and, since 0 = nep.,
the ratio of mobility to thermal conductivity p.jK. Fig. 6.18 shows the general depend-
ence of S, 0 and K on the charge carrier concentration.
>-
Cl
"-
CD
c:
CD
....iiic: 1:1£
~
CD
oa. Fermi level
c: ~ - - - ...ferm·
e %COnduc:~~
--
- - 'jel/e/
~~
t)
CD Fermi level
W
~conduc~i~l
Metal 1
cooled
Semiconductor
-~ Metal 2
heated
Fig. 6.17 Use of the Peltier effect for heat transport.
s
"-
CD
~
a.
u
.;:
....u
CD
Qj
I
o
E
Q;
~
I-
log n
I Kelectron
I
I
-----~---------------~---
I I
I I K phonon
I
I
log n
Insulators Semiconductors Metals
Fig.6.l8 Factors influencing the thermoelectric figure of merit, Z, as a function of log (carrier
concentration, n) showing maximum occurring in the semiconductor region.
The maximum of S2 a occurs in the semiconductor region with K slowly varying. In
practice the most effective materials for thermoelectric applications are bismuth
telluride Bi2 Te3 and antimony telluride Sb 2Te3 or an appropriate alloy of both.
Values of S are typically 300 p.V/degree and z,.., 2·5 X 1O- 3/degree. A very compact
thermoelectric refrigerator, perhaps measuring 1 cm x 1 cm x 0·5 cm can pump 5-10 W
of heat with a current of 2 A and as a generator might produce 500 mWat an e.mJ. of
2 V for a temperature difference across the faces of 120°C.
References
1. Ure, R. W. Thermoelectricity, lnterscience (1961).

2. Goldsmid, H. J. Applications of Thermoelectricity, Methuen (1960).
Questions
I. Molecules of an ideal gas are distributed above a plane (z =0) in a force field F
given by F= (-3 - 2z) x 10- 21 where z is the distance above the plane. Calculate the
ratio of molecules per unit volume at a height of 6 m to that at 3 m at 300 K.
2. Show that for the Einstein model of a solid (eqn (6.5» the molar specific heat at
constant volume Cy is given by
(eE) 2 efdE/T
C y = 3R T (eeE/T _1)2 '
where eE = hVo/k.
3. Estimate the relative contributions of electrons and lattice to the specific heat (at
constant volume) of sodium at 20 K. The Fermi temperature of sodium is 3·6 x 104 K
and its Debye temperature is 150 K.
4. Obtain the relevant data and calculate the thermoelectric figure of merit for the
following materials: (a) cO'pper, (b) germanium, (c) silicon, (d) indium antimonide,
(e) bismuth telluride, and (f) antimony telluride.
7 Electrical Properties
7.1 Introduction
The most important property characterizing the electrical properties of a solid is the
electrical resistance R, which is more conveniently discussed in terms of a geometry
independent quantity the resistivity p. For a solid of length I and cross section area A
R = pi/A. The units of R are ohms and those of p ohm metre. Electrical conductivity
a = lip is also widely used and the units of a are reciprocal ohm metre, i.e. (ohm
metrer l often written mho metre- l . Ohm's law may then be stated as a relation
between current density J and electric field 8..
J=a&. (7.1)
The conductivity of solids is remarkable because it spans so wide a range of values,
about twenty-three orders of magnitude. The best metallic conductors such as copper
and silver have values of a about 108 n- l m- l and a good electrical insulator, for
example polystyrene, has a conductivity of la-IS n- I m- I . No other quantity varies
to such an extent and it seems a formidable task to explain such a variation.
The ideas of Drude at the beginning of this century on electric conduction in metals
are fundamental and provide a simple view of the behaviour of electrons in all materials.
Drude's work was based on the idea of a metal as a lattice of positive ions through which
electrons moved freely according to the laws of kinetic theory. The electrons move at
random at thermal speeds but under the influence of an applied field gain an additional
drift velocity. Collisions with the lattice are the source of electrical resistance.
In such a collision an individual electron has its drift velocity reduced to zero, and
immediately afterwards its motion is random. In this situation the current density J
from n electrons per unit volume of charge e and drift velocity v is
J=nev. (7.2)
If the average time between collisions is 2T, then during this time the electron is acted
on by a force F = -e8. where 8. is the applied electric field.
dv
m-=-e8. m = mass of electron
dt
e8.
dv=- -dt
m
&t
v = -e - + constant.
m
But at t = 0, v =0 (immediately after each collision) and the integration constant is zero.
ELECTRICAL PROPERTIES 125
... .. e&2r
Hence the velocity Immediately before a collIsIOn = - - -
m
therefore
mean dn·ft veIoClty
· =- -
e&r, (7.3)
m
r is called the rekzxation time and is the time interval in which there is unit probability
of a collision.
From eqn (7.2)
ne 2 &r
J=-- (7.4)
m
so that the conductivity
a =-!..- = ne 2 r =ne (er) (7.5)

& m m
By eqn (7.3)
er
v=- &.
m
The velocity in unit electric field v/& defines the mobility J..! of the electron.
Hence J..! = er/m. The units of mobility are m 2 V-I S-I. Note that Ohm's law
follows immediately from eqn (7.4).
It follows from the definition of mobility and eqns (7.1) and (7.2) that
J= neJ..!&
and
a=neJ..!. (7.6)
Eqn (7.6) is of fundamental importance. The electrical conductivity depends on two
factors, the number n of carriers per unit volume and their mobility J..!. The way in
which these two quantities vary particularly with temperature provides the key to the
understanding of electrical properties of materials. For example, in a metal n is constant
and J..! varies relatively slowly with T. In semiconductors the exponential dependence
of n on temperature is of primary importance while in some insulators it is the ex-
ponential dependence of J..! on temperature that is significant while n is constant. An
understanding of the relative contributions of n and J..! to a enables the whole spectrum
of values of a to be explained.
7.2 Metals [1]
When pure, metals have a low resistivity ranging from 1·5 x 10-8 Urn to 150 x 10-8 Urn
at room temperature. The variation of resistivity with temperature of a typical metal
eu is shown in Fig. 7.1. It will be observed that the resistivity increases linearly with
temperature over a wide range of temperature.
The essential feature which distinguishes metallic behaviour is that the d.c. electrical
conductivity tends to a constant value as absolute temperature T ~ O. That is, there are
no temperature induced effects necessary for metallic conduction.
About 80 per cent of all known elements are metals and there is some variation in
resistivity with position in the Periodic Table. Table 7.1 gives some typical values.
10
E
a
GO
I
o
.-
~
~
'>
:;; 5
'iii
CD
II:
0
Temperature (K)
Fig. 7.1 Resistivity of copper as a function of temperature.
TABLE 7.1
Electrical resistivities of metals
Metal Group of Periodic Table Resistivity at 300 K

(1 ()tI.nm)
Na IA 4'75
K IA 7'19
Ag IB 1'61
Au IB 2-20
Mg IIA 4'30
Ca IIA 3'6
Ba IIA 3"9
Zn lIB 5'92
Cd lIB 7'27
A1 IIIB 2'74
In I1IB 8'75
Sn IVB 11'0
Ph IVB 21'0
As VB 29'0
Sb VB 41'3
Cr transition metal 12'9
Fe transition metal 9'8
Co transition metal 5-8
Ni transition metal 7'0
Mn transition metal 14'4
La rare earth metal 79'0
Ce rare earth metal 81'0
Eu rare earth metal 89'0
Gel rare earth metal 134'0
Ho rare earth metal 77'7
The lowest resistivities (at room temperature) are generally found in Group I and
the highest among the rare earth metals. The main experimental facts relating to the
resistivities of metals which have to be explained are:
For pure metals
(1) The range and variation, particularly the high values for transition metals and
the agreement with Ohm's law.
(2) The temperature dependence. Over a wide range of temperature near room
temperature P ex T but at low temperature P ex Tn where n '" 3 to 5 and there-
fore P -+ 0 as T-+ O.
(3) The pressure dependence. Resistivity decreases as pressure increases and for
the alkali metals eventually passes through a minimum.
(4) The Wiedemann-Franz law, which states that the ratio of thermal conductivity
K to electrical conductivity a is constant, and the modification of Lorenz that
K/aT is constant (Lorenz number).
(5) For impure metals or dilute alloys, Matthiessen's rule, that the resistivity change
due to a small amount of impurity in solid solution is independent of tempera-
ture. This rule is more generally interpeted by the equation
Ptotai = Ppure + Pimpurity
where Ppure is temperature dependent and Pimpurity is not.
Theories of metals have developed from the early work of Drude and later the
Sommerfeld model to the more recent applications of wave mechanics.
The Wiedemann-Franz law may be deduced from an extension of the Drude theory
of section 7.1 using kinetic theory.
For a particle of thermal velocity u and mean free path I
2T = llu.
Note that the kinetic velocity u is not the same as the drift velocity v. The former
arises from the thermal energy per molecule (or electron) whereas the latter is an
average velocity imposed by an electric field and is superimposed vectorially on u.
A typical value of u at room temperature is 4 x 105 m s -1 whereas v is 0 f the
order of 10- 3 m S-1 in a metal in unit electric field. The relaxation time T is typically
10- 14 s.
The thermal conductivity K of a free electron gas is [2]
K = !nklu, where k is Boltzmann's constant
and from eqn (7.5)
a = ne 2 l/2mu.
Since
(7.7)
i.e.
mu = 3kTIu
ne 2 /u
a=--
6kT'
K nklu6kT k2 T
-= =3-
a 2ne 1u
2 e2 •
The constant of proportionality 3(k/e)2 is known as the Lorenz number and has
the value 2·23 x to- 8wn deg- 2 • It is a good estimate for experimental values of K/oT
for many metals at room temperature.
Equation (7.7) also predicts the temperature dependence of a for, substituting in
eqn (7.5),
a ex: 7 ex: l/u ex: I/VT; P ex:VT.
This prediction is incorrect since experiment shows that P ex: T. The error lies in the
assumption that the temperature dependence of P arises from the temperature depend-
ence of the electron velocities. A wave mechanical treatment shows that the mean
velocity of electrons in a metal is independent of temperature. The temperature
dependence of the resistivity arises from the scattering effect of the thermal vibrations
of the atoms on the electrons (as waves). The mean free path [is then inversely pro-
portional to the mean square of the amplitude of atomic vibrationsA o.
[ex: I/A 0 2
since
A 0 2 ex: mean potential energy ex: kT; P ex: [-I ex: T.
In the Sommerfeld model (Appendix I) a free electron has a velocity appropriate
to the Fermi level, much greater than kT at room temperature. This leads to a much
greater estimate of the mean free path which can now be several hundred interatomic
distances. The more recent developments of band theory have led to more precise but
complicated estimates of the relaxation time. It is necessary not only to take into
account the details of particular band structures but also the effect of lattice vibrations
on the electron scattering. This type of scattering leads to a well established r5 law
for p at low temperatures.
The variation of band structure explains why p varies with position in the Periodic
Table but the transition metals pose a particularly difficult problem because of the
presence of unfIlled inner d shells. The influence of these d bands on the scattering of
s electrons is thOUght to be the cause of the increased resistivity observed for these
metals.
7.2.1 Impurities
The presence of impurity atoms, for example in dilute alloys, introduces additional
scattering effects which are not easy to quantify. If scattering were of the Rutherford
nuclear type then the effect would be proportional to the square of the excess charge
of the impurity atom. The influence of impurities may be separated from normal
scattering by assigning two different relaxation times, 70 for impurity scattering and 7
for normal scattering.
Since
p=--ml
ne 2 7
p=~(l+~)
ne 70 7 2
P = Po + Ppure (Matthiessen's rule).

A measurement of electrical resistance at low temperatures is therefore a good
guide to the purity of a metallic specimen since Po is independent of temperature
while Ppure ex: T. For an alloy consisting of a dilute solution of metal B in metal A,
giving a complete range of solid solution for small concentrations, the resistance
follows Nordheim's rule:
p a:x(l -x),
where x is the concentration of A atoms and (1 - x) is the concentration of B
atoms.
This rule arises from the disturbance of the periodicity of the lattice by the pres-
ence of the foreign atoms and the usual effect of scattering by thermal vibrations is
superimposed. Figs 7.2 and 7.3 illustrate Matthiessen's rule and Nordheim's rule for
copper.
Impurity concentrations
given in atomic per cent
E
c:
GO
I
o
~
.~ 4
>
'';::;
III
'iii
Q)
II:
Temperature IK)
Fig. 7.2 Resistivity of copper alloys as a function of temperature illustrating Matthiessen's
rule [3,4).
4
Atomic per cent
Fig. 7.3 Resistivity of binary alloys of copper as a function of concentrations of the second
component, illustrating Nordheim's rule [3, 4 J.
When alloys are no longer dilute,disorder, or defects or both can cause complicated
behaviour. For transition metal alloys too the simple rules no longer apply. Table 7.2
gives the resistivities of typical alloys.
TABLE 7.2
Electrical resistivities of alloys (s.&,nm)
Alloy Composition 295 K 4K
Manganin Cu84 Mn12 Ni4 48 x 10'-2 43 x 10-2

Constantan Cu60Ni40 52·5 x 10'-2 44 x 10-2
German silver Cu47 Zn41 Ni9 Pb2 30·5 x 1(,2 26·5 x 1()2
Stainless steel 73·5 x 10'-2 51 x 1()2
Cupro-Nickel Cu80 Ni20 26 x 10'-2 23 x 1()2
Brass (as drawn) Cu70 Zn30 7·2 x 10-2 4·3 x 1()2
Brass(annealed) Cu90 Znl0 3·8 x 1()2 1·9 x 1()2
7.2.2 Pressure
At room temperature the general behaviour of p is to decrease initially with increasing
pressure and it may pass through a minimum for example for Na and K. The initial
decrease is due to the effect of pressure in reducing the amplitude of lattice vibrations
(p ex: mean square amplit~de of vibration, section 7.2). The subsequent increase is
probably due to modification of the electron band structure which leads to increased
phonon scattering.
7.3 Semiconductors [5]
The electrical properties of semiconductors are determined by

(a) the existence of a gap in the energy states, and
(b) the presence of impurities.
The existence of an energy gap between the highest filled band and the next highest
band empty at T = 0 is a feature determined by the Brillouin zone structure of the
material (Appendix I). The highest mled band is called the valence band and the next
highest band empty at T =0 is the conduction band (Fig. 7.4).
Such a semiconductor is pure and is supposed to contain no impurity either ac-
Cidentally or deliberately introduced. It is an intrinsic semiconductor and at absolute
zero is an electrical insulator. At fmite temperatures electrons may be thermally
excited across the gap between valence and conduction bands provided the gap is not
too big. Two kinds of carriers of electricity are then created, electrons in the conduc-
tion band and holes in the valence band. It is the possibility that these two current
carriers, one negatively charged, the other positively charged, can exist simultaneously
in a crystal and behave almost independently that gives rise to the interesting properties
of semiconductors. It follows that it is possible to modulate the bulk conductivity of
semiconductors by changing the concentrations of electrons or holes while still
maintaining charge neutrality.
When a voltage is applied to such an intrinsic semiconductor a current flows which
is due to the motion of holes and electrons. The drift velocities of the two types of
carrier in the electric field are different because of their differing effective masses
(Appendix I).
The current density J in electric field & may be written
J = nelle& + pellh&,
Conduction
band (empty)
1
Electron
energy
Valence
band (full)
~ '" Filled bands

occupied by
/ more tightly
?zzzzzzzzzzz, bound
electrons
Fig. 7.4 Band structure of a Semiconductor at T = 0 K.
where nand p are the electron and hole densities (number per unit volume) fJe and
fJh their respective mobilities, that is velocity in unit electric field; and e the electronic
charge. In an intrinsic semiconductor the concentration of holes is equal to the con-
centration of electrons since each electron excited into the conduction band creates a
hole in the valence band. The number n depends on the temperature, the energy gap,
the density of states and the position of the Fermi level. In an intrinsic semiconductor
the Fermi level lies half way between the top of the valence band and the bottom of
the conduction band. The formula for the electron density is [5]
_ (2rrm*kT)3/2 (~) (7.8)

n- 2 h2 exp - 2kT '
where m* is the electron effective mass and Eg is the energy gap width.
Clearly the presence of the energy gap requires carriers to be thermally activated
across it as expressed by the exponential term in eqn (7.8). Thus the number of carriers
and hence the conductivity increases rapidly with temperature in contrast to metallic
behaviour. Just as for metals, lattice scattering has an important effect on the motion
of carriers and for this reason the mobility is found to be dependent on temperature
according to the relation
fJ = CT-(3/2) (C = constant). (7.9)
Impurities are introduced by substituting them for atoms of the host intrinsic semi-
conductor. This may be done either by diffusing in foreign atoms, or by introducing
them during crystal growth. If, as is usual, the valency of an impurity differs from the
host, then it may have one more or one less electron to participate in bonding. If one
more, the excess electron is relatively weakly bound to the parent atom, because
polarization effects screen it from the normal binding force of its parent. This effect is
represented by the relative permittivity of the medium. The binding energy of the carrier
is reduced by the factor 1/(€r€o)2 (see Chapter 8).
The ionization energy thus becomes extremely small; a typical value of €r is 12 for
germanium and the ionization energy for an impurity atom of arsenic is 0·01 eV. This
atom is therefore ionized at quite low temperatures and at room temperature most
arsenic atoms present as impurities would be ionized.
The band picture of such an extrinsic semiconductor looks as if extra energy levels
have been created very near the bottom of the conduction band.
Figure 7.sa illustrates the band structure at T = 0 when the arsenic atoms provide
extra energy levels which are occupied by electrons, the complete entity (the arsenic
atom) being neutral. At room temperature electrons are ionized into the conduction
band, one from each atom, leaving behind a single positively charged arsenic ion in each
case. The electrons in the conduction band are now free to take part in electrical con-
ductivity when a field is applied.
Electronl
Energy
Conduction
band (empty)
-0.01 ------
ev '....Impurity levels
(neutral)
~ Valence band
(a)
Electronl Conduction
energy e- e- e- e- e- e- band
1111!ol
Positively charged
impurity levels
""~>"'7"':7"'7"'l7"'7"'l'7"7"7"?""7 Valence
~band
(b)
Fig.7.S Band structure of impure (N·type) semiconductor. (a) At T= 0 K. (b) At room
temperature.
If the impurity atom bond is deficient in one electron similar arguments show that
an extra level is provided in the band gap, near the top of the valence band. Such levels
ionize by capturing electrons from the valence band creating holes in that band. These
holes can then contribute to electrical conductivity. Semiconductors which have more
electrons than holes are called N-type and those having more holes than electrons are
called P-type. The balance can be adjusted by control of the impurity content of the
host semiconductor. The impurities of Fig. 7.5 are called donors and those of Fig. 7.6
acceptors.
There is a simple rule which describes the statistical balance between electrons and
holes in extrinsic semiconductors at any given temperature:
If ni =electron or hole concentration in an intrinsic semiconductor at a given
temperature,
n =electron concentration in an extrinsic semiconductor and
p =hole concentration in an extrinsic semiconductor
np = ni 2 • (7.10)
The position of the Fermi level is modified by the presence of impurities. Fig. 7.7
illustrates this for both N- and P-type.
The temperature dependence of electrical conductivity of an extrinsic semi-
conductor will be determined primarily by the variation in the number of holes and
Conduction Conduction
band band
_________ Neutral impurity e- e- e- e- e- e- Negatively

-:levels (P type)
~"
"7'?"7'?"7'?--r-_ _
~;, /0valence Valence ••d levels

Impurity
~%2/i~//;band (full) band
(a) (b) Holes
Fig.7.6 Band structure of P·type semiconductor. (a) At T =0 K. (b) At room temperature.
Fermi Fermi
level level
Bottom of C.B.
Nimpurity
r----___
levels
N-type impurity
Intrinsic Intrinsic
level level
P-type impurity P-type impurity
- - - - - - - - - - -Pimpurity
Top 0 f V.B. levels
o o
Impurity density Impurity density
(a) (b)
Fig. 7.7 Fermi level as a function of impurity density for (a) low temperature and (b) high
temperature.
electrons and to a small extent by a mobility factor. At low temperatures carriers from
impurities only will contribute, but at higher temperatures when all the impurities are
ionized, intrinsic carriers will increase rapidly in number. As well as the temperature
dependence of the mobility caused by lattice scattering, the scattering effect of im·
purities leads to a characteristic ]'3/2 dependence. Thus lattice scattering predominates
at low temperatures and impurity scattering at high temperatures. Table 7.3 lists im·
purities which may be used in germanium and silicon to create extrinsic semiconductors.
The classic semiconductors germanium and silicon occur in Group IV of the Periodic
TABLE 7.3
Donor and acceptor impurities in Ge and Si
and their ionization energies
Impurity Type Ge (eV) Si (eV)
P N 0'12 0'045
As N 0'0127 0'05
Sb N 0'010 0'039
B P 0'0104 0'045
AI P 0'0102 0'06
Ga P 0'0108 0'07
In P 0'0112 0'16
Table. They are covalently bonded materials with energy gaps of 0·78 and 1·2 eV respec-
tively. Carbon which precedes silicon in the table, is a large gap semiconductor when
in the form of diamond, while tin which follows germanium is metallic in one phase
and semiconducting in another.
Consider indium antimonide, InSb. Indium and antimony are in the same row of
the Periodic Table as germanium. Indium is in Group III and antimony in Group V and
so have the same electronic core of inner shells. Indium has three outer electrons and
antimony five. The structure of indium antimonide is an f.c.c. lattice with A atoms at
the corners, and B atoms one quarter way along a diagonal, belonging to an inter-
penetrating f.c.c. lattice. Indium occupies all A sites and antimony all B sites. The
structure is essentially the same as diamond or germanium but there is some ionic
character to it. There are some residual charges on the Sb not quite neutralized by the
average of four electrons round it and there is a corresponding residual negative charge
on the indium. As a result, the charge clouds shrink giving the effect pictured in
Fig. 7.8.
~Sb~
I
~
~
Fig. 7.8 Polarization of electron charge cloud in InSb.
This structure is known as zinc blende (ZnS) or sphalerite. A related structure is that
of wurtzite (ZnS) which can be obtained by rotating alternate (111) layers of zinc
blende through 180 0 to give a structure with hexagonal symmetry. Both zinc bIen de and
wurtzite structures are closely related to the more densely packed sodium chloride
structure.
Various combinations of elements from Group III and Group V form important
semiconducting compounds. Similarly combinations of Group II and Group VI elements
may be formed and these have increased ionic character. In ZnS for example the sulphur
ion core S6+ exerts a strong electrostatic attraction on neighbouring electrons. Other
examples are combinations of Group N and Group VI elements and silicon carbide
is a Group IV-N compound.
All these possibilities provide a wealth of semiconducting compounds with widely
varying properties each capable of being doped with impurities to extend even further
the diversity of the range. Some examples of these materials will now be considered.
Z3.1 II-VI compounds [6]

These materials include oxides, sulphides, selenides and tellurides of Be, Mg, Zn, Cd
and'Hg and are given the general name of chaicogenides. The energy gaps are generally
large and the preseace of impurities leads to interesting and important luminescent
and photoconductive effects.
ELECI'RICAL PROPBRTIES 135
The crystal structures of several II-VI compounds are the same as those of III-V
compounds. Examples are given in Table 7.4 which illustrates the change from the
ionic binding of the NaCI structure to the more covalent binding of (b) and (c).
TABLE 7.4
//- VI compounds having (a) sodium chloride, (b) wurtzite
and (c) zinc blende structures
mement o S Se Te
Mg (a) (a) (a) (b)

Cd (a) (c) (c) (c)
Zn (b) (c) (c) (c)
Be (b) (c) (c) (c)
Because of the interesting optical properties of these compounds their electrical

properties have received comparatively little attention. Most have energy gaps
between 2 and 4 eV but mercury telluride, HgTe, and mercury selenide, HgSe,
are exceptions. They are semimetals having a small overlap of about 0'1 eV of valence
and conduction bands, and show a small electron effective mass and hence a high
mobility. The mobility of HgTe has been measured as 12 m2 V-I S-1 and that of
HgSe as 8 m2 V-I S-I at 77 K.
In II-VI compounds there are two particularly important scattering mechanisms
for electrons. The first is known as optical mode scattering. This effect may be regarded
as a polarization of the lattice by an electron or as an effect caused by high frequency
lattice vibrations in which the two types of ion move out of phase. An electric polariza-
tion is thus produced and the polarization field influences the motion of an electron
leading to a mobility varying with temperature in a complicated manner depending on
the strength of the electron-lattice interaction.
The second type of scattering is known as piezoelectric scattering and arises because
compounds such as CdS, CdSe and ZnO are piezoelectric. In this case, the low fre-
quency lattice vibrations, which are analogous to sound waves in the crystal and arise
from in-phase motion of the ions, produce the mechanical stress which induces
polarization fields through the piezoelectric effect. This leads to a T-1!2 dependence
of the mobility.
7.3.2 III-V compounds [7, 8]

Typical structures for these compounds are given in Table 7.5. Many of these com-
pounds have rather high electron mobilities and the band gaps have a considerable
spread as indicated in Table 7.6.
TABLE 7.5
1//- V compounds having (a) boron nitride, (b)
wurtzite and (c) zinc blende structures
Element N P As Sb
B (a) (c) (c) (c)

Al (b) (c) (c) (c)
Ga (b) (c) (c) (c)
In (b) (c) (c) (c)
TABLE 7.6
Properties 0[[[/- V compounds
Compounds Energy Hall mobility (m2 V-I s-I) Melting

gap (eV) Electrons Holes point ("C)
AISb l'6 0'02 0'02 1050

GaP 2-4 0'0017 1350
GaAs 1'53 0'34 0'02 1238
GaSb 0'80 0'4 0'07 705
InP 1'34 0'34 0'005 1070
InAs 0'45 2'3 0'024 940
InSb 0'25 6'5 0'1 525
Table 7.7 gives some effective masses of electrons and holes which have been mea-
sured but all these figures are subject to variation with the conditions of measurement
and should be regarded as approximate.
TABLE 7.7
Ratio of effective masses of electrons me
and holes mh to free electron mass for
lll- V compounds
me/mo mh/mO
InSb 0'034 0'2

InAs 0'02 0'41
GaP 0'2 0'4
GaAs 0'06 0'5
AISb 1'8 ± 0'8 0'4
InP 0'07 0'4
Two particularly interesting applications of these compounds will now be considered.

The first effect is the amplification of acoustic waves and is manifested notably by CdS,
ZnO and to a lesser extent GaAs and InSb. The effect, known as acousto-electric
amplification relies on the piezoelectric property of these materials [9]. The second
application is the Gunn diode (subsection 7.3.3).
By means of an externally applied transducer, a piezoelectric crystal may be set
into vibration, the vibrations being analogous to the thermally induced lattice vibrations
or to those of an elastic (sound) wave. When such an acoustic wave travels along a
crystal of CdS, for example, it not only deforms the lattice but the piezoelectric property
of the crystal produces additional electric fields. If the mean free path of an electron in
the crystal is very much greater than the wavelength of the sound wave it hardly
notices the piezoelectric field. On the other hand if the mean free path is very much
less than the sound wavelength, the electron is constantly sampling the piezoelectric
field and so electrons tend to collect in regions of high electric potential, while regions
of low potential are denuded of carriers. Thus a piling up of electrons occurs associ-
ated with the sound wave. This leads to the creation of electronic space charge which can
have the effect of screening the piezoelectric field. This is minimized if the distance
over which the screening occurs is almost the same as the sound wavelength. If the drift
velocity of the electron is greater than that of the sound wave the electrons try to give
Plate 1 A molten zone between a single crystal seed and a sintered rod of nickel oxide
(T - 2300 K).
Plate 2 Epitaxial growth surface of nickel oxide showing <100> cleavage cracks (x 95).
NiO---
-Interface
MgO---
- Cleavage crack
in MgO
Plate 3 Cross section of 100 I'm epitaxial layer ef NiO on MgO showing slip lines in the MgO
near the in terface (x68).
Plate 4 An X-ray back reflection photograph (using monochromatic radiation) of rolled nickel
sheet showing preferred orientation.
Plate 5 An X-ray transmission photograph of amorphous perspex using monochromatic

radiation.
'"<:I
::c
-<
V>
n
;I>
t""'
01 '"<:I
:;0
o
[100]
1 ;:g
:;0
::l
t"!1
V>
o'Tl
;I>
==
>-l
t"!1
~
;I>
t""'
V>
Plate 6 Uniform regions of antiferromagnetic domains in nickel oxide separated by irregular boundaries (x 155).
(a) 294 oK (b) 403 oK
(e) 456 oK (d) 480 oK
(e) 500 OK (f) 518 OK
Plate 7 Topographs illustrating the variation with temperature of the misorientation associated
with domain walls in nickel oxide (x35).
Plate 8 Magnetic domain patterns including magnetic 'bubbles' in a 7 J.Lm layer of

Y2 -18 YbO-3Gdo -S2Fe3-9Gal-1 012 grown epitaxially on a substrate of gadolinium
gallium garnet.
up some of their excess momentum to the wave (phonons are emitted) to try to restore
equilibrium with the lattice and as a result the acoustic wave is amplified. The method
used to achieve this effect is shown in Fig. 7.9.
Light
ttt
----
R.F. in ----
R.F. out
~Quartz
transducers
Pulsed electric
field
Fig. 7.9 Experimental arrangement for the observation of acoustic amplification.
Acoustic waves are developed in the sample by exciting a quartz transducer with radio
frequency waves and are observed after passage through the sample through their effect
on a second transducer. The sample is illuminated to provide plenty of carriers by
excitation and a pulsed drift field is also applied to the sample.
Figure 7.10 shows typical results in which acoustic gain is observed for drift fields
greater than about 7 x 104 V m- I . This effect offers interesting possibilities for future
developments which may include acousto-optical devices, oscillators and amplifiers.
+
N 25
J:
::i!:
It) 20
.... 15
~
..c 10
'0
CI>
> 5 -
co
;:
'0
0
C
:::J
0
-5 --
Ul
'0 -10
c
0-15
:;:;
co
~ -20
!
-< 16
Fig. 7.10 Attenuation of acoustic waves in CdS(15 MHz) [10].
7.3.3 The Gunn diode [11, 12, 13]

This interesting device is usually based on a thin crystal of GaAs but the effect is also
observed in indium phosphide InP and cadmium telluride CdTe.
The effect observed is a rapid repetitive fluctuation of the current in the sample at
very high frequencies -109 Hz. This frequency is in the microwave or radar region of
the spectrum and so if the specimen is suitably housed, microwave e.m. radiation is
produced, the startling feature being that the only power supply required to achieve
this effect is a 6 V battery. The effect arises because in GaAs the band structure is such
that electrons can have two widely different mobilities. If carriers change from one
mobility to another in moving along the crystal a negative slope appears in the current
voltage characteristic. Ohm's law is no longer obeyed for certain applied electric fields
(Fig. 7.11).
-
c:
......
CD
::I
U
I
I
I
I ~B
Electric field
Fig.7.11 Current density versus electric field for GaAs showing the influence of variation of
electron mobility with electric field.
Suppose this is the case for the electric field region 8.A to ~. Because the sample
has a negative resistance, the situation becomes unstable as far as the electrons in that
region are concerned. Some have high mobilities and some travel slowly. The result
is that the impurities in part of the specimen become uncompensated, the electrons
having moved on too quickly and a dipole region is formed (Fig. 7.12).
eee+++ - e
eee+++ - e
eee+++ - e
eee+++ - e
Slow Fast
electrons electrons
Ga As crystal
Residual
uncom pen sated
positive charge
from impurities
CD
~ Or-~~--~--~--------
IV
.s::.
U
Distance
Fig. 7.12 Formation of a dipole domain in GaAs.
This dipole 'domain' which is a region of relatively high resistance travels down the
specimen towards the anode. Once there it collapses and a new one is formed at the
cathode. During the period of travel of a domain, the specimen current is low, when
the domain has collapsed it is high. So the repeated motion of a domain along the
specimen causes current oscillations. The specimen is very thin about 30 Jim and the
velocity of a domain about 10 5 ms- I giving rise to a signal frequency of 10 9 Hz. The
device is thus a compact microwave source with a particularly economical power supply.
7.3.4 Other semiconducting compounds

Two other groups of semiconducting compounds deserve a brief mention. There is a
group ofIV-VI semiconductors based mainly on lead [14]. Some properties are sum-
marized in Table 7.8. Their importance stems from their optical properties and use as
detectors of infra-red radiation.
TABLE 7.8
Properties of IV- VI semiconductors
Compound Energy gap Electron Hole Relative permittivity

Eg (eV) mobility mobility
l'e(m2 V-I 8- 1) I'h(m 2 V-I 8- 1) 300K
High 77 K Low
frequency frequency €rco €rs
€rco €rs
PbS 0·41 0·06 0·07 18-4 184 17·2 172

PbSe 0·27 0·12 0·1 25·2 227 22·9 206
PbTe 0·31 0·18 0·09 36·5 428 32-8 380
7.3.5 V- VI compounds
These are the sulphides, selenides and tellurides of antimony, bismuth and arsenic
(Table 7.9). Interest in these compounds has been stimulated by the properties of
Bh Te3 as a material for thermoelectric generators and refrigerators.
TABLE 7.9
Properties of V- VI compounds
Eg(eV) l'e(m 2 y-l 8""1)
Sb2S3 1·7 546

Bi2S3 1·3 850
AS2Se3 1·6
Sb2Se3 1·2 -0·0015 -0·0045 612
Bi2Se3 0·35 0·06 706
A82Te3 -1 0·008 360
Sb2Te3 0·3 0·027 620
7.4 Transition metal compounds [15,16]

These materials, particularly the oxides, are of considerable interest because in
spite of superficially similar electronic structures they show widely different electrical
properties. The oxides of nickel, cobalt and manganese for example are very good
insulators whilst titanium monoxide, TiO, and chromium dioxide, Cr02, are metallic
and some oxides of vanadium, V0 2 , V203 and nickel sulphide, NiS, are believed to
show a metal-insulator transition.
Nickel oxide is a classic example of a material which according to simple band theory
should be a metal since it would have a partially filled 3d band (Fig. 7.13).
However, pure NiO has a conductivity of about 10- 10 n -1 m -1 at room tempera-
ture varying exponentially with temperature as in a semiconductor. It seems likely that
the band structure of the 3d levels of nickel oxide and similar compounds is not
determined by crystal structure, as in ordinary semiconductors, but by what is known
as correlation. An electron wishing to leave a Nj2+ site must form Ni3+ and move to
another Ni2+ converting it to Ni+. The Coulomb repulsion between the 'mobile' electron
and the two electrons already attached to the Ni 2 + site render this process very unlikely.
There is a reluctance for such electrons to move because of an effective gap in energy
between the two states equivalent to the energy of formation of Ni+ and Ni3+ sites from
two Ni 2+ sites. Moreover, the mobility of the carriers is so low that they have time to
polarize the lattice ions around them. This further inhibits their mobility which may be as
EnergYI 45 band empty
JIZZ zz Z2 zz Z2 Z2 Z2 2 fal~iaIlY} ~ndt~aongyS~~i!

?IZ27ZZZZZZZZZZ FUUII electr~c. field
of 0 2 Ions
~2pbandfull
~(from oxygen)
Fig.7.13 Simplified band structure for NiO.
low as 0·5 x 10-4 m 2 V-I s-I.Carriers can be created more easily by doping with lithium
which is readily ionized forming a Li+ ion and a Ni 3 + ion. One lithium atom thus
effectively creates a 'hole' on a Ni3+ which can now move about by accepting an electron
from another Ni 2 +. The ease with which transition elements can be induced to change
their valency has led to the name mixed valence compounds, and the presence of
carriers is often due to non-stoichiometry of the pure compounds, the presence of
nickel vacancies in NiO for example.
Figure 7.14 shows conductivity-temperature curves for nickel oxide, some com-
pounds of vanadium and nickel sulphide.
7.5 Polarons
The idea that an electron can polarize the lattice around it is an important one in dis-
cussing the mechanisms of electrical conductivity of low mobility materials and so this
concept will be considered briefly.
If a slow electron polarizes the ions around it, another electron distance r from it
has a potential energy due to electrostatic interaction given by
VI = -(e 2 /47r€o€sr),
where €s is the 'static' or low frequency relative permittivity of the material. If, however,
Fig.7.14 (a) Electrical conductivity of NiO as a function of I/Temperature. (b) Electrical con-
ductivity of NiS as a function of I/Temperature [17]. (c) Electrical resistivity of V0 2 as a function
of Temperature [18]. (d) Electrical conductivity OfV 2 0 3 as a function of I/Temperature [19].
10
1Ii' -
E
c:: 10- 2
1 0- 8 '-::---='-=---='"-:----=-"=---='"=:-----='"=- ~ __ l_ I I
3.5 2.5 2.3 21 19 17 1.5 1.3
la)
(Temperature)-1Ixl0-3 K-l)
Polycrystalline NiS Thin film V02

108
1- E
E 106 c:: 10- 3
c:: ~
.~ 104 :~
...u
.~
<II
·iii
G>
10-4
cr:
'"
"C
c:
0
(J 103 10-5
10- 6
30
Ib) Ic) Temperature 1°C)
108
(d) I 104
E
-c::.~ 10 2
V2~
.~
u
-6c 10- 2
0
(J 10-4
10-80 1 4 8
(Temperature)-l (x1 0- 3 K-l)
the ions had not been induced to move, the potential energy would be given by
V 2 = -(e 2 /41r€o€oor),
where Eoo is the high frequency relative permittivity. In this case the ions have been
effectively prevented from moving, for example when an applied electric field
oscillates at too fast a rate for the ions to be able to follow.
The difference in these terms represents the effect of motion of the ions and gives
a potential
(7.11)
where 1/ET = 1/Eoo - liEs, which traps the electron in the potential well it has created
for itself. The shape of the polarization well is shown in Fig. 7.15 where the curve
essentially represents eqn (7.11). Over a range rw within the well the equation does
not apply and V T is assumed constant.
ttl
:;::;
c:
....o
Q)
r
0.
Cl
c:
'0.
0.
.::
ttl
Fig. 7.15 Potential well for a polaron.
The electron can occupy one of a number of quantized states in the well. This
entity (electron + lattice polarization) is known as a polaron. Another way oflooking
at it is to consider the polarization as a particular set oflattice vibrations (optical
modes) induced by the presence of the electron. Thus the trapped electron may be
thought of as being surrounded by a cloud of phonons, a rather more picturesque
description. The behaviour of a polaron depends on a number of factors. One is the size
of the well compared to the interatomic spacing. If the polarization is very localized the
polaron is called small and usually moves by thermal activation. That is, if thermal vibra-
tions produce by chance a fluctuation in the lattice nearly similar to the distortion the
electron is already in, it can tunnel wave mechanically to the new position. But an
activation of the form e- WjkT has been necessary. Conduction occurring by this
process through random diffusion of the electron is called thermally activated hopping.
It is characterized by an increase of mobility with temperature. It has also been shown
that a polaron can move in a band of levels without activation when the radius of the
polarization well is large compared to an atomic spacing, and sometimes when it is not.
However, the motion of polarons is always characterized by a large effective mass and
low mobility. The electrical properties of a number of transition metal oxide insulators
has been interpreted in terms of the motion of polarons [20] .
7.6 Magnetic semiconductors [21,22]
The transition metal oxides which are semiconductors, may also be grouped in a wider
context with other compounds containing magnetic ions of the transition or rare earth
series as magnetic semiconductors. The magnetic moments of the individual magnetic
ions are arranged in a regular way on the crystal lattice to give ferro, ferri or antiferro-
magnetic arrangements (see Chapter 9). NiO, MnO and CoO, below a particular tempera-
ture, are examples of antiferromagnets, the ferrites (ferrimagnetic spinels, Mlt-OFe~+03)
and garnets (Y 3FeS012 yttrium iron garnet) are ferrirnagnetic, and the chromium
spinel cadmium chromium selenide CdCr2Se4 and europium chalcogenides (EuO, EuS,
EuSe) are ferromagnetic. An interesting group of compounds is the rare earth pnictides,
i.e. compounds of a rare earth (3+ ion) with N, P, As, Sb or Bi. These are III-V com-
pounds with an NaCI structure. Electrically they range from metallic to insulating
materials and their behaviour is not yet explained. Another group of ferromagnetic
compounds possesses a structure based on the mineral perovskite, CaTi0 3 and are
called perovskites, and have the general formula AB0 3 . They are mixed valence
compounds and typical ones are rare earth mixed oxides such as lanthanum manganate,
lanthanum chromate and the alkaline earth mixed oxides calcium, barium and strontium
manganates and titanates. The actual structures are often distorted forms of the cubic
perovskite structure. Those, having the formula AFe03, are called orthoferrites. If these
E
.,a
...
I
o
8=0
.!5.
x=O
~
'>'';::
UI
8=0
·~1.4
a:
8=1.3 Wbm- 2 1.2
x=0.01 PRT=18x10- 2
200 300
Temperature (K) Temperature (K)
Fig.7.16 Temperature dependence of the resistivity of poly crystalline EUI_XGdxSe for various
Gd concentrations x and magnetic flux densities B [23).
compounds are not stoichiometric perhaps by having an oxygen deficiency, or foreign

ions present, as in LaxSrl_xMn03,the electrical conductivity can be increased but
generally the materials are high resistivity semiconductors with low mobility carriers.
The rare earth chalcogenides are exceptional in showing a strong influence of an applied
magnetic field on the electrical properties. One example shown in Fig. 7.16 is the
effect of a magnetic field on the resistivity of Eu 1_xGdxSe.
The detailed behaviour of these complex compounds is not well understood but in
general because the mobile carriers have spin magnetic moments, they are strongly
influenced in their motion by the direction of spins on neighbouring sites. Just as, in
the formation of a polaron the lattice is polarized, so neighbouring spins may be
polarized by a moving spin, forming a magnetic polaron. In the neighbourhood of a
Curie temperature (Chapter 9) when thermal vibrations are disordering spins, the
motion of a carrier may be strongly influenced by scattering produced by the disordered
spins. The dose relationship between electrical and magnetic properties in these com-
pounds offers the prospect of new ways of controlling electrical phenomena by
magnetic means in future devices. The magnetism of typical compounds is summarized
in Table 7.1 O.
TABLE 7.10
Compound Type of magnetism below Curie temperature
NiO antiferromagnetic
Fe203 antiferromagnetic
MOF~03 ferrimagnetic
CdCr2Se4 ferromagnetic
EuO ferromagnetic
EuSe ferromagnetic
LaMn03 ferromagnetic (in distorted form at low temperatures)
SrMn03 antiferromagnetic (at low temperatures)
MnCr2S4 ferrimagnetic
(Note: M =Fe, Zn, Ba, Mg, Ni)
7.6.1 The metal-insulator transition

There is a close link between the magnetic state of some magnetic compounds and their
electrical properties and this has been demonstrated very clearly for chromium doped
V203' It is also possible for a material to change from the electrically conducting
(metallic) state to the insulating state under suitable circumstances. This change is
termed a metal-insulator transition. A transition of this kind may be observed in
chromium doped V 203' By varying temperature and pressure a phase diagram has
been constructed for this compound. The results are shown in Fig. 7.17. Above the
critical point P no metal-insulator transition is observable.
Critical
point P
300
g
...::::JCD Metal
...to
~
Q)
0.
E
~ 100
o
Pressure (kbar)
Fig.7.17 Phase diagram of (V l_xCrxh03 for x = 0.0375 [24].
The possibility of a sudden metal-insulator transition with variation in atomic

spacing was first pointed out by Mott and so it came to be known as the Mott transition.
The arguments he put forward may be summarized as follows:
In a lattice of atoms where there is one electron per atom localized at each atomic
site, the movement of one electron from Site A to Site B (Fig. 7 .18a) is made difficult
by the Coulomb repulsion of the electron already on Site B (Fig. 7 .18b). Moreover, the
electron in moving from Site A leaves behind a positive charge which tends to attract
it back. The combination of single positive charge and excited electron bound to the
charge cannot carry a current. Such a material is clearly an electrical insulator. But
suppose there were already many electrons present. Then the-attractive power of the
positive charge would be screened because the electrons would tend to be attracted to
it and neutralize its charge. Thus the excited electron sees a modified potential of the
form
_(e 2 /41f€o€sr) exp {-(rll)}, (7.12)
where r is its distance from the positive charge, I is the screening length, and €s the
static relative permittivity. Beyond a distance I the attraction is negligible. I may be
shown to be given by
2 = me 2 n l/3 (~) 113

z2 h 2 €o€s1f 1f '
where n is the density of electrons.
t t t t t
(a)
t A t t t t
(b)
Fig.7.18 Motion of a localized electron in an array of atoms with one electron per atom. (a)
Ground state. (b) Excited state.
Now the lowest bound state of the hydrogen atom has a radius
(7.13)
Using this formula here
(7.14)
But if 1< aH there will be no bound state for the electron while if I > aH it can be pre-
vented from leaving the parent atom. Thus a transition from the state when all the
electrons are bound to the state when they are all free will occur when
l=aH.
Substituting in eqn (7.14) the condition for the transition is n- 1I3 ~ 4aH, i.e.
n 1l3 aH ~ 0'25. (7.15)
It is predicted by this simple argument that if the atomic spacing is greater than
4 Bohr units of radius, then the preferred state will be insulating. If the atomic spacing
could be varied a transition would be observed from insulator to metal at a value of
4aH . This prediction was made long before any such behaviour was observed. The first
experimental results which suggested that the transition might take place were ob-
tained with heavily doped germanium at low temperatures. More recent results on the
transition metal compounds have led to further development of the subject of metal-
non-metal transitions [25,26]
7.7 Amorphous materials [27,28]
Much interest is at present being shown in the electrical properties of amorphous

materials. Crystalline order has been a dominating feature of most of the materials
discussed so far. Amorphous materials are characterized by long range structural dis-
order with a substantial degree of short range order. The arrangement of atoms is
random and so is the crystalline potential in which the electrons move. Yet the simple
......
... -... _______Nc_rv_stalline
......
-E
I
\
8 \
\
2 P
a \
Fig. 7.19 Temperature dependence of the electrical conductivity of InSb. (1) doped 1 per cent
Te (N-type). (2) doped 1 per cent Zn (P-type) in crystalline and amorphous states (29).
fact that such a well known amorphous material as glass is optically transparent sug-
gests the existence of an energy gap in the available states. Band theory suggests that
energy gaps arise from the regularity of crystal atomic planes. How then c~ such a gap
exist in the energy states of an amorphous material? This contradi~tion is a point of
great theoretical interest and it has been demonstrated that a 'disordered' potential is
capable of having a band structure which is rather different from the one that has been
used so far.
The main features of the electrical properties of amorphous materials have been
found by examining the properties of thin amorphous layers of simple materials
such as selenium, germanium and silicon. In this form these materials behave as
semiconductors with a conductivity of the form
U = Uo exp (-f:lE/kT). (7.16)
There were significant differences in some cases between the behaviour of amorphous
and crystalline materials. Fig. 7_19 shows the electrical conductivity for InSb doped
N and P in both states.
The differences in the two types of the same material are obvious. In the amorphous
state the conductivity is much lower and there is very little difference between the
behaviour of Nand P material. The activation energy AE (eqn (7.16)) is 0·55 eV for
the straight line part abo This would correspond to an energy gap about 0·4 eV greater
than that of the crystalline material. This energy gap can be modified by thermal
treatment of the sample. The behaviour of thermoelectric power emphasizes the
difference. The extrinsic nature of the N- or P-type conductivity completely disappears
in the amorphous state (Fig. 7.20) and it seems then that the effect of impurities is
0.2
2
-----
I
:..::
> 0.1 Crystalline
.s
Gi o-
~
o
~ -0.1
';:
1:)
CD -0.2
Qi
o
E
... -0.3
CD
.r::
~
-0.4
-0.5 '--2:':----!4:------:!:6----:!:S:------
(Temperature)-1( xl 0- 3 K- 1)
Fig.7.20 Thermoelectric poweroflnSb (1) N· and (2)P-type in crystalline and amorphous states
(29).
suppressed. In some materials direct measurements of drift mobility have been made and
found to be as low as 10- 7 m2 V-I S-I for electrons and 10- 5 m 2 V-I S-I for holes. Attempts
to explain the differences in the two states have led to a model which, although incomplete,
is successful in explaining some of the main features of the experimental results. It is
interesting because of the number of new ideas it contains. The basic consideration is
the effect of disorder on the normal band structure of a crystalline material. This
can be investigated theoretically by seeking solutions of the Schr6dinger equation
when the potential is disordered. A simplified approach is to consider the motion of
an electron through a series of square potential wells of random depth. The results
show that bands of energy states exist just as for crystalline materials and that these
bands are separated by energy gaps. At the edges of these bands, however, localized
states are present which spread into the forbidden gap. The extent of this spread
depends on the type of material. Where compositional disorder is present as well
as structural disorder, the spread may be so great that overlap with localized states
from an adjacent band edge may occur. Then the crystalline energy gap is either severely
blurred or non existent (Fig. 7.21a and b).
The density of states within a simple band of a crystalline material is modified as
shown in Fig. 7.22. Tails oflocalized states extend the spread in energy beyond the
crystalline band width E B - EA'
Some explanation is necessary for the distinction between the states in the band and
the localized states, as both have rather special meanings here. A localized state is an
Conduction
band
:-::-=-=:-=-::-:-::-=-::-=-:-::~:-:-::-:~
Valence
-~------------~~~
Valence ~----------~-----~ states
band band
(a) (b)
Fig. 7.21 Localized states in band structure of amorphous materials. (a) Blurring of band edge.
(b) Overlap of localized states in band gap.
UI
Q)
+'
IU
+'
UI
....o
>-
+'
"iii
c
Q)
o
Energy E
Fig. 7.22 Density of states as function of energy in a band (amorphous states).
electron trap from which an electron can only escape with the help of phonons. This
implies a mobility of the form /J. = /J.o exp (-E/kT) where E is an activation energy and
the motion is called hopping. The band states in this problem are also rather special
because an electron moves in a diffusive manner in them leading to a mobility which
is not activated. If the band gap is blurred by the presence of localized states, how can
a definite activation energy be observed in experimental measurement of electrical con-
ductivity? This difficulty is overcome by assuming a very sharp drop in carrier mobility
at the band edge of extended states, where the transition occurs to motion in localized
states in which the mobility is very small. Fig. 7.23 shows the expected variation in
mobility.
This sudden drop in mobility is said to derive from the existence of a mobility gap,
and it is the activation in mobility across the mobility gap which gives the form a =
ao exp (-AE/kT) because /J. = /J.o exp (-AE/kT) where AE is the mobility gap.
The mobility varies in the following way near the band edges EBand Ee. Within
the band of states well below EB the mean free path will be low compared to the
crystalline case because of disorder, and /J. is typically 10- 2 m2 y-1 S-l. The mobility may
also be modified by trapping. In the region aboveEB' that is in the localized states, the
mobility is very low, about 10- 5 m 2 y-1 S-l . But immediately below EB in the region
t - - - - Mobility gap-
Band Band
Localized
states
EnergyE
Fig. 7.23 Mobility of electrons as a function of energy showing mobility gap (amorphous state).
EaEB, the motion is diffusive and the mobility is an order of magnitude higher than
in localized states in the tail of the band. This region is a kind of transition region from
extended states to localized states and the motion here is a Brownian movement. These
ideas on mobility result from the mathematical treatment of motion in random
potentials [30] and are rather speculative at present.
The insensitivity of some properties of disordered materials to impurities is due
to the fact that local valency requirements can always be satisfied. For example an
arsenic atom in crystalline germanium disturbs the bonding to fit into the lattice, but
in amorphous germanium it can always be expected to fmd attachments for its five
bonds because the situation is so much more flexible (Fig. 7.24).
___ r Ge
Ge
~ Ge Ge
Ge
(a) (b)
Fig.7.24 Bonding to an impurity atom in (a) crystalline and (b) amorphous germanium.
7.8 Switching [31,32]
Certain glassy semiconductors have shown interesting electrical effects involving sudden
changes of resistance. These are generally classed as switching properties and typical
materials which show them are the chalcogenide glasses, which are glasses containing
elements of Groups III, IV, V and VI of the Periodic Table. For example Ge, As, S
and Te are combined to form Teo.sAso·2 SiO'l GeO·2 or ASo.4TeO.SGeo.l' When two
electrical contacts are made to a thin fIlm of such materials, a two terminal device is
formed which may show either of the following current-voltage characteristics
(Fig. 7.25).
\
\
....c ....c \
,,
...... ...l!!
,
CD
::J \
::J
U U
Voltage Voltage
(a) (b)
Fig. 7.25 Current-voltage characteristic of (a) threshold switch and (b) memory switch.
A device having a characteristic similar to Fig. 7.25a is known as a threshold switch

while (b) is called a memory switch. Both types were discovered by Ovshinsky and
named Ovonic devices. Thus (a) is an ovonic threshold switch (OTS) and (b) an
ovonic memory switch (OMS) [33].
7.B.l Ovonic threshold switch

This device has two stable states, one of high resistance and one of low resistance
symmetric with respect to voltage. Switching from a high to a low resistance state
occurs when a voltage greater than VT (the switching voltage) is applied. The low
resistance state can only be maintained by a minimum holding current I H • If the
current falls below IH the switch reverts to the high resistance state.
7.B.2 Ovonic memory switch

Again there are two stable states and Switching occurs from the high resistance to a low
resistance state when a critical voltage VT is applied. However, in this switch the low
resistance state is permanent and requires no holding current. Switching back to the
high resistance state can be achieved by applying a current pulse. A number of
explanations of this behaviour have been suggested.
(1) Thermal breakdown: the heating effect of the current reduces the resistance
of the semiconducting glass, to produce an avalanche effect. Ultimately
equilibrium is attained by a balance of power diSSipation and heat loss.
(2) Phase changes occur in the glass at various temperatures and the thermal condi-
tions cause thin highly conducting fIlaments to form between the end contacts,
at a particular crystallization temperature. A current pulse can subsequently
reheat this fIlament after which it is quenched to a high resistance phase. There
is substantial evidence for the formation of fIlaments and this explanation is
well confirmed for the memory switch.
(3) Electronic mechanisms: a purely electronic mechanism which can account for
the very fast SWitching times involved (less than 10-9 s) has been supported by
many workers. This explanation is based on the band model for amorphous semi-
conductors described above. If in an amorphous semiconductor the tails of localized
states are long enough, overlap of tails from adjacent bands will occur (Fig. 7.26).
1/1
.!
...~o
~
1/1
c::
Q)
C
Energy
Fig.7.26 Density of states as a function of energy showing the overlap of states in the energy gap
(amorphous state).
Electrons from the tail of the valence band fall into empty conduction band levels
to produce a set of positive and negative charges above and below the centre of the
mobility gap. In this situation the Fermi level EF is effectively pinned at the centre
of the gap. The mechanism of switching is then based on the idea that if space charge
neutrality prevails in the region, and all possible traps are full, the bulk of the material
is capable in prinCiple of carrying a high current even though nominally an insulator.
The details of the actual mechanism of switching is otherwise highly speculative at
present.
References
1. Meaden, G. T. Electrical Resistance of Metals, Heywood (1966).

2. Roberts, J. K. and Miller, A. R. Heat and Thermodynamics P 285, 5th edn., Blackie (1960).
3. Linde J. O. Ann. Physik. 14,353 (1932).
4. Linde, J. O. Ann. Physik. IS, 219 (1932).
5. Adler, R. B., Smith, A. C. and Longini, R.Introduction to Semiconductor Physics, Wiley
(1964).
6. Ray, B. 11- VI Compounds, Pergamon (1969).
7. Hilsum, C. and Rose-Innes, A. C. Semiconducting III-V Compounds, Pergamon (1961).
8. Welker, H. and Weiss, H. Solid State Physics, Vol. 3, p. 1, Academic Press (1956).
9. Ridley, B. K. Phys. Bull., August, 461-465 (1971).
10. Hutson, A. R. and McFee, J. H. Phys. Rev. Lett. 7,237 (1961).
11. Gunn, J. B. Sci. Am. August, 22 (1966).
12. Pamplin, B. R. Con temp. Phys. 11,1 (1970).
13. Hilsum, C. Brit. J. Appl. Phys. 01 (Series 2), 265 (1968).
14. Dalven, R. Infra Red. Phys. 9, 141-184 (1969).
15. Adler, D. Solid State Physics, Vol. 21, pp. 1-113, Academic Press (1968).
16. Austin, I. G. and Mott, N. F. Science 168,78-83..(1970).
17. Townsend, M. G. et aI. J. Phys. C4, 598 (1971).
18. Verleur, H. et aL Phys. Rev. 172,788 (1968).
19. Foex, M. C.R. Acad. Sci. (paris) 223,1126 (1946).
20. Austin, I. G. and Mott, N. F. Advan. Phys. 18,41-102 (1969).
21. Austin, I. G. and Elwell, D. Con temp. Phys. 11,455-476 (1970).
22. Methfessel, S. and Mattis, D. C. Encycl. Phys. 18/1, 389-462 (1968).
23. Holtzberg, F. et aI. Proceedings of the International Conference on Magnetism, Nottingham
1964.
24. Jayaraman, A. et aI. Phys. Rev. 82,3751 (1970).
25. Mott, N. F. Contemp. Phys. 14,401-413 (1973).
26. Mott, N. F. and Zinamon, Z. Rep. Progr. Phys. 33 (9), 881-940 (1970).
27. Davis, E. A. Endeavour 30 (110),55-61 (1971).
28. Owen, A. E. Con temp. Phys. 11,227-286 (1970).
29. Beyer, W., Mell, H. and Stuke, J. J. Non-Cryst. Solids 4,1 (1970).
30. Mott, N. F. Phil. Mag. 17, 1259 (1968).
31. Mott, N. F. Con temp. Phys. 10 (2), 125-138 (1969).
32. Simmons, J. G. Contemp. Phys. 11 (1), 21-41 (1970).
33. Ovshlnsky, S. R. Phys. Rev. Lett. 21,1450 (1968).
Questions
1. Show that the following two deftnitions of resistivity p are equivalent

. f b P x length of bar
(a) R eSlstance 0 a ar = .
cross section area
(b) =electric fteld across bar

p curren t denslty
. m . bar .
2. A copper wire of cross sectional area 5 x 10-6 m 2 carries a steady current of 50 A.
Assuming one free electron per atom calculate:
(a) the density offree electrons, and
(b) their average drift velocity.
[Pcu =8·9 X 103 kgm-3, atomic weight of copper =64, Avogadro's number =6·02 x
1026 kgm mor l .]
3. The electrical resistance of a piece of germanium is found to vary with temperature
as follows:
T(K) 312 330 354 385 420
R(a) 11'8 5·88 2'33 0·90 0·35
Show that this specimen is intrinsic in this temperature range and estimate the energy
gap in eV.
4. Classify the compounds of the transition metals as metals, semiconductors or
insulators and list those that show a metal-insulator transition.
S. The attraction between an electron and a hole distance r apart in a solid is described
by a screened potential VCr) where
_e 2
VCr) = - - exp (--yr).
41T€r€0
If €r = 12 and 'Y = 1010

m plot a graph of the force between the particles as a function
of r for the following values of r:
r = 0'5,1,3,5,10 and 100 A.
Consider the relevance of the graph to the Mott transition.
8 Dielectrics
8.1 Introduction
Electrical insulators have very few free electrons to take part in normal electrical con-
ductivity and so it is possible to conceive the ideal insulator which would have no free
electrons. Such a material has interesting electrical properties because of the ability of
an electric field to polarize the material to create electric dipoles. A dipole is an entity
in which equal positive and negative charges are separated by a small distance, the
electric dipole moment p being dermed as p = qr in the simple representation of
Fig. 8.1.
+
Fig. 8.1 Separated charges forming a dipole.
The electric dipole moment is a vector which is conventionally directed negative to

positive and the unit of electric dipole moment is the Debye (1 Debye =3·33 x 10- 30
Coulomb-metre).
As well as appearing in a material in the presence of a field, dipoles may be present
as a permanent feature of the molecular structure. Such dipoles are called permanent
dipoles. Materials in which polarization effects are important are called dielectrics. An
electric field produces electrical polarization within the material. The action of a
simple capacitor will illustrate the effect of dielectric polarization and enable the
topic to be introduced macroscopically without considering the details of what
happens on an atomic scale.
Consider two metal plates of area A separated in vacuum by a distance d and having
a battery of voltage V connected across them (Fig. 8.2). The electric field & between
++++++++
•
d
t
Fig. 8.2 Capacitor with yacuum dielectric.
the plates is directed as shown and has a magnitude V/d V m- 1 arising from the charge
density ± Q on the plates. The relation between Q and the field & is obtained by
introducing a dimensional factor EO, the permittivity of vacuum:
(8.1)
The value of Eo is 8·854 X 10- 12 Farad/metre. It is convenient to think of Q as a source
of electric flux lines in the space between the plates; the density of these flux lines is
called the electric displacement D.
D=Q=Eo8,· (8.2)
The need for D as well as Q should become clear in due course.
Now imagine that with the battery still connected a dielectric medium is introduced
so as to just ftll the space between the plates (Fig. 8.3). The medium becomes polarized
+ + + + + + + + +
vI I~ + + +
-
+
- +-
- -
+
-
-+ +-
-
1 I~
+
-±
+
-
±
-
+
-
-
+
-
±
-
+
-
±
-
+
-
±
-
+
-
± ;1
Fig. 8.3 Capacitor with a solid dielectric.
by the field 8, and dipoles appear throughout the material lined up in the direction of
the field. All dipole ends of opposite charge inside the material will cancel but there
will be an uncompensated surface charge, negative at the top, and positive at the
bottom. These surface charges will attract and hold corresponding charges of opposite
sign on the plates, because the latter, unlike dipoles, are able to move freely. The field
between the plates must be that appropriate to the voltage applied, irrespective of
whether a dielectric is present or not. Thus the field in the dielectric must still be 8,.
If the effect of some of the original surface charges has been neutralized by being
bound to surface dipole ends, 8, can only be maintained if more charges flow from
the battery to make up for those which have become bound. There is now more charge
density Q' on the plates some of which is tied up and is not contributing to the field 8,
in the dielectric. The amount of charge that is contributing to the field is the same as
before, and
(8.3)
where QB is the bound charge density. Q has been multiplied by a factor Er such that
~=~a ~~
By eqn (8.2) D is now given by
(8.5)
and by eqn (8.3)
(8.6)
The bound charge density is called the polarization P.

This is identical with the dipole moment per unit volume. Imagine a block of
dielectric having a bound charge QB per unit area on opposite faces of area A a dis-
Fig. 8.4 Polarized dielectric with bound surface charges ± QsA.

DIELECTRICS 155
tance d apart (Fig. 8.4). The total dipole moment =QBAd = QB x volume, i.e. the
surface bound charge density QB equals the dipole moment per unit volume P.
The geometry of the parallel plate capacitor is particularly simple but in general
vectors must be used to express the relations between D, 8 and P. Then eqn (8.6)
becomes
D =€o8+ P. (8.7)
Eqn (8.7) makes clear the need for the concept of D, it takes account of both free and
bound charge. These calculations could have been done under conditions of constant
charge instead of constant voltage and by considering the fields with and without the
dielectric, similar equations would be obtained. The ratio DII is called the permittivity
of the dielectric medium
DI8=€r€o =€.
€r is called the relative permittivity or dielectric constant of the medium. For vacuum
€r = 1 and € =eo.
Another way of looking at the above problem is to consider a field 8' in the di-
electric as being appropriate to the total charge Q' on the plates. This field is of course
different from and greater than the applied field 8 since 8' = 1+ P/€o where the
second term is due to the extra charge which flowed on to the plates whilst inserting
the dielectric. Inside the dielectric the field I' is opposed by another field, that due to
the surface charges on the dielectric itself (Fig. 8.5). This is P/€o and is opposed to the
+++++++++
Polarization
field P/Eo
+++++ ++ ++
Fig. 8.5 Polarization field in a dielectric.
field due to the plate charges. Thus the field in the dielectric =8' - P/€o = 8 + p/€o
- P/€o = 8 which was the result obtained previously. The presence of the dielectric
thus increases the capacity of the system for charge by the factor €r.
From eqns (8.5) and (8.7)
therefore
P=€o8(€r- I).
The ratio P/eo I is called the electric susceptibility X of the dielectric:
P/e o8=€r -1 =x, (8.8)
where X measures the ratio bound chargelfree charge =P/Q.
By utilizing the concepts developed above it is not necessary to inquire into the
detailed atomic and molecular processes giving rise to polarization in a dielectric. In
fact comparatively limited progress has been made in properly describing dielectric
phenomena on a microscopic scale. However, a number of important features of
physical behaviour can be explained using quite simple models.
8.2 Mechanisms of polarization
8.2.1 Induced polarization

On an atomic scale there are two ways in which an electric field can produce polariza-
tion. It can displace electron charge clouds with respect to their positively charged
centres (Fig. 8.6) leading to the formation of dipoles. It can be assumed that the
- - Electric field g'
Fig. 8.6 Electronic polarization.
atomic dipole moment p is proportional to the applied field 8. The constant of pro-
portionality is known as the polarizability a, in this case the electronic polarizability
p= a8. (8.9)
In equilibrium, the effect of the field is balanced by the attraction between the dis-
placed charges in the atom leading to the expression for the polarizability a of the
atom
a = 41T€or 3 , (8.10)
where r is the atomic radius. For hydrogen r = 0·53 x 10-10
m and ahydrogen =
1·66 x 10-41 F m 2 , hence for a field of lOS V m-1 Phydrogen = a8. = 10-36 C.m. The
dipole length d = pie = 10- 17 m, a distance small even compared with atomic dimen-
sions.
Induced polarization can also occur in an ionic crystal because the positive ions can
move slightly in the direction of the applied field and the negative ions move in the
opposite direction until new equilibrium positions are achieved. In an electric field 8,
an ionic polarizability aj can be measured from the dipole moment p due to ionic
displacements.
The contribution of ions to the Molar polarization (see eqn (8.27)) of the alkali
halides which are typical ionic solids is given in Table 8.1. Increasing ionic size and
separation reduces the binding between ions of opposite charge and so increases the
polarization, as shown by the figures in parentheses.
TABLE 8.1
Ionic polarization as a fraction of the total polarization for alkali halides,
and (in parentheses) the ionic polarization of each compound relative to
thato/LiF/l]
F Cl Br I
Li 0·680·0) 0·53 (3·22) 0·49 (1,96) 0·40 (2,09)

Na 0·65 (1-12) 0·50 (3,38) 0·440·82) 0·39 (2-13)
K 0·650·95) 049 (4·25) 0·46 (2·38) 0·38 (2·34)
Rb 0·62 (2-19) 0·52 (5-14) 0·44 (2-46) 0·38 (2-62)
DIELECTRICS 157
8.2.2 Orientational polarization
In some materials the structure of the molecules is such that they possess an inherent
dipole moment even in the absence of a field. Examples are given in Table 8.2.
TABLES.2
Molecular dipole moments
Molecule Dipole moment (Debye)
CO 0·1
H2 0 1·S7
HO 1·0S
CH 4 o
CH30 1·S7
CH3CHO 2·72
C2 HS OH 1-69
Such materials will not have a net dipole moment in the absence of a field because,
provided the molecules are free to move, thermal vibrations will ensure that the dipole
directions are random and the net moment averages to zero. In gases and liquids
individual dipole moments are usually free to rotate but in solids circumstances may
not allow it, for example if the temperature is too low or the close environment of
other molecules interferes with the motion.
In the presence of an electric field, an electric dipole behaves like a small magnet
in a magnetic field in wanting to line up with the field. This is called orientational
polarization. It is due to the torque applied by the field as shown in Fig. 8.7.
Fig. S.7 Torque on a dipole at an angle to the direction of an applied electric field.
Such an alignment is opposed by thermal agitation. At a given temperature T the

net moment has been calculated by Langevin and Debye for a collection of N dipoles
each of moment p. The result is that the average moment fi is given by
P= p (coth pl£./kT - kT/p8,). (8.11)
In many cases, particularly for moderate fields (-105 Vm- 1) at room temperature,
this expression simplifies to
P= p2 l£./3kT
and the orientational polarizability is given by
Q!o =pll£. =p2/3kT. (8.12)
This particular type of relationship showing a moment inversely proportional to the

absolute temperature is known as a Curie law by analogy with a similar problem in
magnetism.
The contribution of orientational polarization is illustrated vividly in nitromethane
by a sudden change in relative permittivity at its melting point (Fig. 8.8).
W 40
....>-
">
~ 32
E
a;
c.
Ol 24
>
:;:;
co
Qi
a: 16
0
-90 -60 -30 0 +30
Temperature (0C)
Fig. 8.8 Relative permittivity of nitro methane (at 70 kHz) as a function of temperature [1].
Of the commercial polymers polypropylene is non-polar but polyethylene·

terephthalate (PET), a polyester marketed as Terylene or Mylar, polyvinylchloride
(PVC) and polycarbonate are polar and show orientational effects when conditions
allow.
Summarizing, the total polarization in a static field can be made up of contributions
from electronic, ionic, and orientational polarization:
p = P electronic + Pionic + Porientlltionlll· (8.13)
Only one of these, the last, is temperature dependent and eqn (8.13) may be written
in terms of polarizabilities
P = N 8(aelectronic + aionic + OOrientationaD
= N 8(a el ec tronic + G'tonic + p2/3kT)
Hence using eqn (8.8)
€r - 1 =(N/€O)(aelectronic +aionic + p2 /3kT). (8.14)
A measurement of €r as a function of temperature can help to distinguish the contri-
bution of orientational polarization from the sum of the ionic and electronic parts.
8.3 The local field
Equation (8.14) is restricted in its applicability since the field acting on a dipole within
a liquid or solid is not the applied field because of the interaction between dipoles.
DIELECTRICS 159
Lorentz derived an expression for the actual field acting at a point in a dielectric known
as the local field 8 loc to distinguish it from the applied field 8 app' In a solid Lorentz
showed that
(8.15)
where P is the polarization of the medium. For most problems, only approximate
calculations of 8 loc are possible.
The need to distinguish between the applied field and the actual field acting on a
dipole within a material can be seen as follows. The field at a point within a dielectric
arises from the applied field and the cumulative effect of all the dipoles in the material
under the influence of that field. All these dipoles are interacting with each other and
with a dipole at the point in question. The exact calculation is thus extremely com-
plicated and cannot be done unless simplifying assumptions are made. In the following
calculation due to Lorentz, the main assumptions are (i) that the effect of most dipoles
at a distance from a given point 0 is given by the macroscopic polarization provided
they are some dipole lengths away from 0, and (li) the interaction of the dipoles near 0
is zero if the material has cubic symmetry about O. Fig. 8.9a shows a thin slab of di-
electric between two plates. The plates of area A have charges Q per unit area when
+QA
.
+ + + + + + + + +
~2at
+ + + +
~
+ + +
~P
+ +
I~ (~)
- -
l~b
·0
- - - -
- - - -QA
(a) (b)
Fig. 8.9 (a) Fields in a dielectric between charged plates. (b) Field in a spherical cavity about O.
the external applied field is 8 app' Let the polarization of the dielectric be P. What is
the field at the point 0 within the dielectric, that is to say the force on unit positive
charge at O?
The field arises from four parallel components
8 loc = 81 + 8 2a + 1l2b + 8 3 . (8.16)
Suppose the point 0 is surrounded by a sphere which is small compared to the size of
the dielectric slab but large compared with molecular sizes. The effect at 0 can be
divided into the effect due to the material outside the sphere treated macroscopically
and the effect due to material inside the sphere treated microscopically, that is with
the detail of dipole interactions being taken into account. Suppose the material inside
the sphere is temporarily removed. The four components of eqn (8.16) are
81 =field due to the charges on the plates;
1l2a =field due to charges on the surface of the dielectric (the depolarizing field);
8 2b = field due to charges on the surface of the spherical cavity (Fig. 8.9b); and
113 =field due to the dipole interactions of the material within the sphere when
replaced.
The effect of the plate charges is given directly by the Gauss theorem
(8.17)
Since the surface charges on the dielectric are given by the polarization P and their
field is oppositely directed to 8 1
(8.18)
There is always a geometrical factor in this type of calculation. Here the choice of a
thin cylindrical slab of dielectric with lines of force perpendicular to the surface of the
cylinder leads to a factor of unity. For a sphere the factor turns out to be 1/3.
To calculate 8 2b consider the sphere of Fig. 8.9 in more detail (Fig. 8.10a and b).
z z
+ +
8
~--I--X
~---+--X
(a) (b)
Fig. 8.10 Calculation of field It 2b at 0 due to charges on the surface of a spherical cavity
about o.
The field at 0 in the diiection of 8 app can be found by using Coulomb's law for the
effect of the surface charges at O.
The density of induced charge on the surface of the sphere is the normal component
of polarization Pn = P cos 8.
The radial field at 0 due to charges on surface element of area dA =PdA cos f) /41Teor2.
The component of this in the direction of 8 app is PdA (cos 8 /41Teor2) x cos f).
The integration over the surface can best be carried out by using an infinitesimal
element of area obtained by rotating dA about the axis OZ (Fig. 8.1 Ob). An elemental
surface ring is then formed of area 21Tr sin 8r df). The total field 8 2b is then given by
integrating over the range 8 = 0 to 1T.
f
1r
P cos 2 f) :2.
8 2b = :2 21Tr sm 8 d8 = P/3Eo. (8.19)
41TEor
o
This then is the field at 0 due to most of the dipoles in the material expressed through
the macroscopic polarization P, excepting only those within the sphere.
Finally the field 8 3 due to the material within the sphere is often very difficult
to calculate. If the material is assumed to have cubic symmetry the effect of the dipole
interactions averages to zero. For a symmetrical array of dipoles about 0 there is
always a cancellation at 0 of the effect of dipoles at corresponding points on the
opposite sides of the centre point. Thus, if this simplifying assumption is made, then
1t3 =0. (8.20)
The magnitude of the total internal field 8 10c is then the sum of the magnitudes of all
four components:
Q P P
~loc = - - -+-. (8.21)
eo eo 3Eo
DIELECfRICS 161
But
D=Eo&app +P=Q. (8.22)
Substituting eqn (8.22) into (8.21) gives
8 10c = 8'app + (P/ 3E o). (8.23)
This may be written vectorially since the three components are parallel.
8.4 The Clausius-Mosotti relation
The Lorentz equation for IJ loc leads quickly to other standard results. Since
P = Eo(Er - 1)8app
(8.24)
and P = No: Bloc where 0: is the total polarizability and N is the number of molecules
per unit volume, therefore
P=(~'T + 2) No: 8' app /3. (8.2S)
Combining these,
No:/3Eo = (Er - l)/(Er + 2). (8.26)
This is known as the Clausius-Mosotti equation which relates a microscopic property 0:
with an easily measurable macroscopic property, the relative permittivity Er .
If N is replaced by the expression Nop/M, where No is Avogadro's number,M the
molecular weight in kg and p is the density in kg m- 3 the quantity Noo:/3Eo obtained
by substituting in eqn (8.26) is the molar polarization or polarizability per mole:
NoO: M eEr - 1)
P
3Eo = (Er + 2) .
(8.27)
It must be remembered that this equation is approximate since it does not properly
take account of dipole interactions.
8.5 Dielectric relaxation
The effect of an alternating electric field on a dielectric will now be considered with
emphasis on low frequency response. The high frequency response is dealt with in
Chapter 10. By low frequencies is meant a region from zero up to about the micro-
wave region of the e.m. spectrum in which permanent dipoles can respond to an
applied a.c. field.
Water is an example of a substance with permanent dipole moments. The dipole
moment of the water molecule arises because of the attractive power of the oxygen
atom for electronic charge, leaving the hydrogen atoms with an effective positive
charge.
Considered microscopically, either in the liquid or solid state, the response of a
polar molecule to an a.c. field will depend on the 'viscosity' of the medium. Ability
to respond to an applied field is usually expressed in terms of a 'relaxation time' T.
Wo = l/T represents the angular frequency at which the viscous forces have their
maximum effect. Well above this frequency a particular polar molecule can no longer
keep up with the applied field and so is no longer orientated by it, and no longer con-
tributes to the permittivity of the medium. Such 'viscous' effects arise from the
influence of intermolecular forces and lattice vibrations. The idea that there is just one
such frequency at which this effect will occur, that is, a single relaxation time, is over-
simplified. Debye derived a model based on a single relaxation time which describes
the general trend of practical results.
Because of the possibility of a phase lag developing between the applied field arid
the instantaneous polarization, the relative permittivity is expressed in terms of real
and imaginary parts and€; €;',
where
, ."
€r = €r - J€r· (8.28)
As the frequency increases the displacement D changes from being entirely in phase
with the applied field tI to having components both in phase and out of phase with 8
(Fig. 8.11).
D~ out of phase
2
D
D Din phase
• •
Applied field g Applied field g'
(a) (b)
Fig. 8.11 Phase relation of vectors D and". (a) at a low frequency . (b) near the relaxation
frequency.
The Debye equations give the variation of both the in-phase and out-of-phase com-
ponents of €r as a function of angular frequency w for a polarization mechanism with
a single relaxation time r:
(8.29)
€ "- (€S - € .. ) WT •
r - 1 + w 2 r2
Here the factor € .. is the contribution to the relative permittivity at high frequencies
from electronic and ionic polarization and €s is the low frequency value of €r. Eqns
(8.29) are illustrated in Fig. 8.12.
When D varies with time, a displacement current density J flows in the dielectric
due to the fluctuating surface charges, where J =dD/dt in the absence of any ohmic
current; that is, for an ideal dielectric. Thus, referring to Fig. 8.13a, if D is in phase
with 8, J is exactly 90° out of phase.
Energy dissipation will arise in the relaxation process from Joule heating if there is
a component of J in phase with the field giving rise to a non-zero term J . 8. As long
as J is perpendicular to 8, clearly there is no energy loss; but when, as in Fig. 8.13b, D
gets out of phase with tI, J is no longer exactly perpendicular t~ 8 and so has a com-
ponent in the direction of 8.
DIELECTRICS 163
£.
r
Wo= lIT
Angular frequency
Wo
Angular frequency
Fig. 8.12 Real and imaginary parts of the relative permittivity as a function of angular fre-
quency (according to Debye-eqn (8.29».
J J J ~ out of ph.eo
.. -
2
.. >- J ~ out of phase >-
c:: .'!:: c·-
G! '"
E ii
G!'tl
G! '"
E ii
G!'tl
U .. u_
.!!!c .!!!c
.C-
'" ...:::I
e.G!
o'" :;...u
e.G!
U
D
.. Jon phase
Don phase
....
Applied field ~
Applied field g
(a) (b)
Fig. 8.13 Phase relationship of vectors J, D and I. (a) D in phase with 1 and (b) D out of phase
with I.
The energy dissipated per second is

21r/w
(w/21r) J J. 8 dt,
o
where w is the angular frequency ofthe field 8. If 8 = 8 0 cos wt, D = €r€O 8 0 cos (wt-
where 6 is the phase angle and J =-€r€O loW sin (wt - IS). Therefore energy dissipated
per second is
21T/W
(-W/21T) J w€o €r &0 sin (wt - 6)&0 cos wt dt.
o
Expanding sin (wt - 6) and multiplying out gives only one term which contributes to
the integral, i.e. the term in cosl wt. Therefore energy dissipated per sec:
21T/W
(w 2/21T) sin 6 J cos 2 wt €r€0&02 dt =(w/2)€r€0 sin c5 &0 2 . (8.30)
o
Figure 8.14 illustrates the relationship between the real and imaginary parts of €r and
the phase angle 6. It follows that for small /j where sin /j ...., tan 6 eqn (8.30) may be
written in the form
(w/2)e;'€0&02 a: tan 6, for small 6.
e"
Tan 8 = er
-~
t"r
er
Fig. 8.14 Relationship of real and imaginary parts of relative permittivity and loss angle 6.
Thus if J lags behind by a small angle /j, as is often the case, tan 6 is a measure of the
power loss and is known as the loss tangent given by tan /j =€;/€; (Fig. 8.14).
At higher frequencies the ionic and electronic polarizations show resonances and
these are discussed in Chapter 10. These occur respectively at approximately 10 12 and
1015 Hz, in the infra-red and ultra-violet regions of the electromagnetic spectrum. In
this region of the spectrum the relative permittivity is measured by the square of the
optical refractive index n. Table 8.3 compares the low and high frequency perrnittivities
and shows the effect of ionic polarization for alkali metal halides.
Orientational polarization occurs much more slowly, typical relaxation times for
polar molecules in liquids vary from 10- 10 to 10- 6 s, that is, in the microwave or radio
regions of the spectrum. Generally, in solids containing polar molecules, the interatomic
forces seriously restrict orientational polarization. In some materials commonly en-
countered in ceramic form, for example barium titanate, ionic polarization is common
and dipole orientation relatively unimportant. In polymers, losses can occur by the
movement of segments of large molecules and this leads to a distribution of relaxation
times.
DIELEcrRICS 165
TABLE 8.3
Compariron of the low frequency relative permittivity and the square of the optical refractive index
for alkali metal halides showing the effect of ionic polarization [1]
F Cl Br I
"r n2 "r n2 "r n2 "r n2
Li 9·2 1·91 11·05 2-68 12-1 3·04 11·03 3·55

Na 4-9 1·74 5·77 2·32 5·99 2-60 6·60 2·96
K 6·05 1·83 4·76 2-17 4·78 2·35 4·94 2-64
Rb 5·91 1·93 5·20 2-18 4·70 2·34 4·81 2·58
8.6 Applications
Dielectrics are used mainly as electrical insulators and in capacitors. Oils and wax
impregnated paper are used as insulators in transformers and steatite (a compressed
TABLE 8.4
Dielectric properties of materials
MateriJlI Relative permittivity Loss tangent

"r tan /)
f= 60 Hz 100kHz 1 MHz 100 MHz

O'ystals
Rutile Ti02 170 170 1\ caxis 10-4
90 901 caxis 2 x 10-4
Aluminium oxide Al203 10·6 10·6 II caxis 10·6
8·6 8·61 caxis 8·6
lithium niobate liNb0 3 30 II caxis 0·05
75 1 caxis
Ceramics
BaTi03 1600 150 x 10-4
Alumina 4·5-8·5 0·0002-0·01
Steatite 5·5-7·5 0·0002-0·004
Rutile 14-110 0·0002-0·005
Porcelain 6-8 0·003-0·02
Polymers
Polyethylene 2·3 2-3 10-4 -10- 3
Polypropylene 2-1 2·5 x 10-4
PI'FE 2-1 2-3 2-3 2 x 10-4
Polystyrene 2·55 5 x 10- 5
PVC 3-6 3-5 3·5 3·0 10-4
Polycarbonate 2·8 3 x 10-2
Polyester 4-5 0·02
Nylon 66 3·5 3·33 3-16 0·02
Glasses
Pyrex 4-6 0·008-0·025
Quartz 4 2 x 10-4
Vycor 3·8 9 xlO-4
Miscellaneous
Mica 5 3 X 10-4
Neoprene 6·3
mixture of talc, clay and barium and calcium carbonates) as an insulator for high
voltage terminals. For capacitors, dielectric materials include paper, plastic film and
mica sheet; oxides of aluminium, titanium and tantalum (electrolytic capacitors) and
a wide range of ceramic oxides which are often ferroelectric as well as dielectric. Poly-
mer materials used as commercial dielectrics are polyesters known as Mylar (PET),
polystyrene and polycarbonate. Polystyrene for example is a non-polar compound
with a relative permittivity of 2·55 at 25°C and tan [) less than 2 x 10- 4 over the
range of frequencies 100 to 1010 Hz. The square of the optical refractive index is 2·53.
Table 8.4 gives typical values of permittivity and loss factor for various materials at
room temperature. Fig. 8.15 shows the frequency dependence of €r and tan [) for poly-
carbonate.
~
0.Q12
..!!!.
eo
...>
·S 3.2 c 0.01
...
.;; ~
'§ 3.1 .... O.OOS
0
Q) 1:)
c. ~ 0.006
Q) 3.0
>
.;; III
III
III
a; 2.9 .3 0.004
a:
2.S 0.002
2.7 0 L..---'-_--'-_-'----'-_-'-_-"--_J..
10 2 10 3 10 4 10 5 10 6 10 7 10 8 10 9 10 10 10 10 2 10 3 10 4 10 5 10 6 10 7 10 8
Frequency (Hz) Frequency (Hz)
(a) (b)
Fig. 8.15 Frequency dependence of (a) relative permittivity €r and (b) tan Ii for polycarbonate.
8.7 Piezoelectric, pyroelectric and ferroelectric materials
These properties will first be defined and the discussion restricted initially to single
crystal materials. Piezoelectric materials have the property of becoming electrically
polarized in response to an applied mechanical stress. This property, known as piezo-
electricity has an inverse; when an electric stress (a voltage) is applied, the material
becomes strained. The strain is directly proportional to the applied field 8. The
existence of both the direct effect and its inverse is to be distinguished from a similar
property called electro-striction. Here the material becomes strained in an electric
field 8 but in a manner depending on 8, 2 so that there is 110 inverse of this effect. The
difference between the two effects is illustrated in Fig. 8.16.
Apyroelectric material is one which exhibits a spontaneous polarization in the
absence of an electric field and which changes its polarization on heating. If the change
of polarization is M' on raising the temperature by t:..T
M'=A.t:..T, (8.31)
where A. is the pyroelectric coefficient.
Afe"oelectric material is one which exhibits a spontaneous polarization in the
absence of an electric field which may be switched in direction by the application of
a field. Ferroelectrics show a hysteresis in the polarization-field relation.
DIELECTRICS 167
+
(a) Expansion
+
A A
,-,
+
(b)
.,
.2+, Contraction Expansion
- -
+
Fig. 8.16 (a) Electrostriction. Material expands for both directions of field. (b) Piezoelectric
effect. Material contracts for one field direction and expands for reversed field.
A material cannot be either piezoelectric, pyroelectric or ferroelectric unless its

crystalline symmetry is inherently asymmetric, that is, it lacks an inversion centre. A
basic principle due to Neumann is that any physical property exhibited by a crystal
must have at least the symmetry of the point group of the crystal. Thus, the above
properties which are inherently asymmetric can only arise in asymmetric crystals.
Of the thirty-two crystal symmetry classes, eleven have a centre of symmetry and
in one a combination of symmetries effectively provides such a centre, leaving twenty
32 Symmetry classes
/
11 Centrosymmetric
\
21 Non-centrosymmetric
120 piezoelectric)
10 Pyroelectric (polar)
/ \
11 Non-pyroelectric
/
Ferroelectric (polar)
\
Non-ferroelectric (polar)
Fig. 8.17 Symmetry classification of piezoelectric and pyroelectric materials.
classes which can have asymmetric properties. All the materials in these twenty classes
are piezoelectric. Materials in ten of these twenty classes have a unique polar axis where
none of the symmetry operations of the crystal point group will turn this axis round.
The existence of a polar axis in a crystal allows the appearance of a spontaneous
electrical polarization and these materials are pyroelectric. A restricted group of
pyroelectrics have the further property of being ferroelectric. Thus, all ferroelectrics
are pyroelectric and piezoelectric. All pyroelectrics are piezoelectric, but the converse
is not true. All piezoelectrics are not pyroelectric and all pyroelectrics are not ferro-
electrics (Fig. 8.17).
8.8 Piezoelectricity
To recapitulate, there are two effects both of which have important practical appli-
cations:
(a) Direct effect. The application of a stress to a crystal produces a strain which
results in a net polarization.
(b) Inverse effect. The application of an electric field produces a strain whose sign
depends on field direction.
These are both linear effects.
If a stress T is applied to a material resulting in a strain S, there are simple relations
between the two involving the elastic stiffness constant c and compliance s for the
material:
T = cS or S = sT. (8.32)
For a piezoelectric material the strain S also results in a polarization and eqn (8.32)
becomes more complicated.
The stress T will produce a polarization P = dT where d is a piezoelectric strain con-
stant. The dielectric displacement, in the presence of a stress therefore contains an
extra term:
D=e8+dT. (8.33)
For the inverse effect the corresponding relation may be written
S =sT +d8. (8.34)
These relationships are complicated by the fact that most crystalline materials are
anisotropic so that electrical or mechanical forces applied in one direction may produce
effects in other directions. This situation may be represented by a tensor notation based
on three convenient axes usually mutually perpendicular. A general stress can be
resolved into six components, three tensile stresses along the axes x, y and z and three
shear stresses about the axes x, y and z.
Consider the plane abcd (Fig. 8.18). A tensile stress acting on this plane in the x
direction is written Txx (or Tu ), the first subscript denoting the direction of the
stress and the second the direction of the normal to the plane. The shear stress shown
acting on the body abcdefgh acts in the y direction around the z axis on planes whose
normals are in the x direction. It is written Tyx (or T21)' Thus in general a stress is of
the form Tij
DIELECTRICS 169
z(3)
Tyx
9
Tyx
a
I
0,x e
y(2)
x{1 )
Fig.8.18 Notation for normal and shear stress.
For a body in equilibrium Tij = T ji . The notation is often simplified by writing tensile
stresses as T 1 , T2 and T 3 , and shear stresses as
T4 = T 23 = T32
Ts = T13 = T31
T6 = T12 = T21
therefore
The equation relating P and T now becomes

Pi =dikTko where i =1, 2, 3; k = 1,2, ... ,6.
If the array d ik has certain mathematical transformation properties on rotation of the
reference axes, it is known as a tensor. The constants d ik can be measured experi-
mentally for a crystal of given symmetry. If the matrix d ik is known, the resultant
polarization for a given stress can be predicted. For example, a tensile stress along the
y axis produces a stress along the x axis given by the relation PI = d 12 T2 and, know-
ing d 12 and the value of T 2 , PI can be calculated.
Alternatively strain is related to electric field by Sk = dikG,i (inverse effect). Thermo-
dynamic requirements ensure the equality of the coefficients in the two cases. The
symmetry of a crystal often makes many of the elements d ik equal or zero, so that the
number of independent piezoelectric strain constants is severely reduced. For a quartz
n
the array of numbers d ik is
2·3o -0·67 o
3 o o 0 0·67
o o 0 o
There are thus only two independent constants dl! and d l4 (d 26 = 2dl!)' As an example
suppose a tensile stress of 104 Nm- 2 is applied in the x direction. What are the
resultant polarizations in the x, y and z directions?
PI =d l1 TI = (-2·3 x 10- 12 ) (104 ) = -2·3 X 10- 8 Cm- 2,
P2 =d 21 TI = 0,
P3 =d 3I T I =0.
For ammonium dihydrogen phosphate (ADP) the array d ik appropriate to a par-
ticular set of axes is
~
0 0 0 0·17 0
( o 0 0 0 0·17 ) X 10- 11 CN-I.
o 0 0 0 0 5·17
Remembering that the last three columns of the array represent shear around the x, y
and z directions, then if an electric field of 103 V m- I is applied in the x direction
Sk =dlk&l.
Oearly there are no linear strains since d 11 = d 12 = d 13 = 0, but there is a shear strain
about the x axis
S4 =d I4 &1 =(0·17 x 10- 11 ) 103 =0·17 x 10- 8 •
To produce a shear strain about the z axis the field must be applied in the z direction
S6 =d 36 &3·
8. 8.1 Electromechanical coupling coefficient

An important quantity characterizing a transducer is the electro-mechanical coupling
factor K. It is defined in terms of K2 as
K2 = electrical (mechanical) energy converted to mechanical (electrical) energy.
input electrical (mechanical) energy
K2 is of course always less than unity but does not represent the absolute efficiency
of a device which is the ratio of useful converted power to input power. The latter
quantity may be lower than K2 at low frequencies but higher than K2 at a resonance.-
For most applications a high K is desirable, that is the ability of a transducer to convert
energy readily from one form to another. A measurement of K2 for a transducer may
be obtained by a simple a.c. resonance method.
A transducer may be represented by an electrical equivalent circuit (Fig. 8.19). The
inductance L represents the mass of the transducer, Co its electrical capacitance, C its
mechanical capacitance or stiffness and R the damping. If an a.c. signal is applied
between the terminals ab the impedance Z of the circuit varies as shown in Fig. 8.20.
+
o_ _ _
Transducer
--.JI
Co
R
C
Fig.8.19 Equivalent circuit of a transducer.

DIELECTRICS 171
N
QI
U
t:
IV
"0
QI
Q.
E
f, f.
Frequency f
Fig. 8.20 Impedance Z of the circuit of Fig. 8.19 as a function of frequency of an applied a.c.
voltage.
The maximum and minimum shown are called an antiresonance and resonance
respectively and occur at signal frequencies fa andfr. They arise from the resonance
of the mass of the transducer with its stiffness (fr) and from the resonance of the mass
with the electrical capacitance (fa). These frequencies can be measured using the
circuit of Fig. 8.21. The current in the circuit is monitored by a voltmeter across series
resistor R 1 and the frequencies at which the current is a maximum and minimum are
noted. These are the frequencies fr and fa. With reference to Fig. 8.19
Wr 1 = (27Tfr)l = 1ILC, (8.35)
(8.36)
r---------------~~~
V ~____~
J
Oscillator
~ ~
Transducer
I I
Fig. 8.21 Circuit for measurement of resonant and antiresonant frequencies of a transducer.
where C1 is the combined electrical and mechanical capacitance

1 1 1
-=-+-. (8.37)
C1 C Co
From eqns (8.35), (8.36) and (8.37)
w/ C1 Co frl
l
wa =(5= C+Co = fal'
whence
1_frl =_C_ (8.38)
fal C+Co•
But
Kl = mechanical energy stored = ! CVl = _C_
total energy stored ! CVl + !CoVl C + Co
therefore
(8.39)
8.8.2 Ceramic piezoelectrics [2]

So far only the anisotropic properties of single crystals have been discussed. Between
1940 and 1954 there occurred the discovery and development of a new form of material
which had piezoelectric properties, namely ceramics. Ceramics are oxide powders com-
pressed and sintered at high temperature to form a polycrystalline mass. Such a material
would be intrinsically isotropic because its properties would be averaged over all crystal
directions. However, if the ceramic is cooled in the presence of an electric field a lining
up of dipoles or poling occurs. A polar axis is thus effectively impregnated in the crystal
which may then show piezoelectric properties. The poling process was first elucidated
by R. B. Gray and this period of development ended with the discovery by B. Jaffe and
others of the important class of piezoelectric ceramics based on lead zircona te titanate
(PZT). Ceramic materials are cheap, easily made in various shapes, and their properties
can be tailored by varying the powdered constituents.
A poled ceramic retains its isotropy in a plane at right angles to the poled direction
and so has effectively a cylindrical symmetry about that direction. The d matrix then
becomes
=( ~ ~}
0 0 0 diS
d, • 0 0 diS 0
d 31 d 31 d 33 0 0
when the poled direction is the z axis.
8.8.3 Piezoelectric materials and their applications [3,4]

Of the wide range of materials which are piezoelectric many are also ferroelectric but
for the moment the latter property will be ignored. Considering single crystal materials,
quartz is notable for the temperature independence of some of its strain constants anci,
as with all single crystals, must be cut in a prescribed crystal direction for particular
vibrational modes to be enhanced. Natural quartz is now being replaced by synthetic
material grown by the hydrothermal process. Other important compounds have been
Rochelle salt, ammonium dihydrogen phosphate and lithium sulphate, all of which are
soluble in water. Many Group II-VI compound semiconductors, compounds of Zn and
Cd, with 0, S, Se and Te are strongly piezoelectric and GaAs and AlN, III-V compounds
more weakly so. lithium gallate has alternate li and Ga atoms surrounded by oxygen
tetrahedra and has a structure closely related to the wurtzite structure of the II-VI
compounds. The commercial ceramic materials are based on barium titanate or lead
zirconate and lead titanate. These all have the perovskite structure. Other piezo-
perovskites are niobates and tantalates; lead metaniobate has the tungsten bronze
structure and its composition has been tailored for specialist piezoelectric applications.
For example (Pb 3 Ba2)NblO 0 30 has a relatively low temperature coefficient of resonant
frequency, is moderately piezoelectric and has low internal damping. A recent develop-
ment is the use of piezoelectric semiconductors such as GaS, ZnO and CdS for amplifi-
cation of acoustic waves at ultrasonic frequencies [5]. The propagation of electrical
signals as acoustic surface waves in quartz and lithium niobate is the basis of a number
of signal processing applications at GHz frequencies [6,7,8]. Some practical applications
of commercial piezoelectrics are summarized in Table 8.5, and Table 8.6 gives some
constants for these materials.
DIELECTRICS 173
TABLE 8.5
AppliClJtions of piezoelectric materials
Application Material
Gramophone pick-ups Rochelle salt

BaTi03*
PZTS*
Air transducers Pb(Ti,Zr)03*
(earphones, hearing
aids, microphones) Rochelle salt
Accelerometers PZT
lead metaniobate
BiTi03
Ultrasonic flaw PZT8*
detectors lead metaniobate
Underwater sonar PZTS*
transd ucers
Filters PZT6* (Cr doped)
quartz
Resonators (for quartz
frequency control)
High voltage generation BaTi03*
(gas lighters)
Delay lines quartz
PZT*
* Indicates a ceramic; PZT 5, for example, indicates a

commercial modification of the basic compound.
TABLE 8.6
Properties of piezoelectric materials
Material Young's Piezo- Electro Maximum Density

modulus electric mechanical operating (103 kgm-3 )
(10 10 Nm-2 ) constant coupling temperature
(10- 12 CN-l) factor (K) ("C)
Quartz (X cut) 8
d 2l =2·25 0·1 550 2·65
d 33 =2·3
Rochelle salt
(45 0 X cut) d 14 =870 0·78 1·77
Barium titanate 11·8 d 3l =-75 0·48 70-90 5·6
PZT5 6·75 d 33 = 374 0·67 290 7·7
Lead
metaniobate 2·9 dD =85 0·42 500 5·8
lithium sulphate
(Y cut) dD =16 0·35 75 2·06
lithium niobate d 33 = -1 0·4 4·63
diS = 68
8.9 Ferroelectricity [9,10]
Ferroelectricity was discovered by Valasek in Rochelle salt in 1921. Since that time the
list of substances showing this property has continued to grow rapidly. Ferroelectric
materials are an important group not only because of the intrinsic ferroelectric
property, but because many possess useful piezoelectric, birefringent and electro-
optical properties (Chapter 10) which can be exploited in devices. Many early ferro-
electrics and newer ones may be obtained as single crystals, but, as was the case for
piezoelectrics, ceramic ferroelectric materials are becoming readily available.
The intrinsic ferroelectric property is the possibility of reversal or change in orienta-
tion of the polarization direction by an electric field. This leads to a hysteresis in the
polarization P, electric field & relation, similar to magnetic hysteresis. Hence the name
/e"oeiectricity has arisen from the analogy with ferromagnetism. Above a critical
temperature, the Curie point Tc, the spontaneous polarization is destroyed by thermal
disorder, and the permittivity shows a characteristic peak at Tc. These properties are
illustrated in Fig. 8.22.
p
f b
c
I
/
/
________~d~____~----~--------~W
a
(a)
&, p
c
....mo
UI
.~
m
(5
Q..
To To
Temperature T Temperature T
(b) (e)
Fig. 8.22 Ferroelectric behaviour. (a) P, & hysteresis loop. (b) Relative permittivity er versus
temperature showing a maximum at the Curie temperature Te. (c) Polarization as a function of
temperature.
DIELECTRICS 175
Figure 8.22a illustrates a typical ferroelectric hysteresis loop. A direct analogy may
be drawn with B-Hloops in magnetism. For small fields applied to an initially un-
polarized specimen, the P, & relation is linear, but at higher fields the polarization
saturates. When the field is reversed P follows bc, oc being the remanent polarization
for zero field. A reverse field od is required to reduce P to zero. On further increasing
the field in the negative direction saturation again occurs at e and fmally the path eab
is traced. The intercept of where the extrapolated saturated polarization cuts the P axis
is called the spontaneous polarization and od the coercive field.
The explanation of this behaviour is that the specimen consists of many small
regions called domains in which individual molecular dipoles are polarized in the
same direction. The field influences some domains to change their direction of
polarization. The details of this process will be discussed later.
The hysteresis loop is a manifestation of the key property of a ferroelectric, that
of switching of the direction of polarization by an electric field. The f r, T relation
shown in Fig. 8.22b is the simplest observed. The permittivity shows a characteristic
peak near the Curie point T e , and fr may become very large. This is a useful property
ofthese materials. Above Te the curve usually follows a Curie-Weiss law again by
analogy with magnetic materials (Chapter 9). The flO T relation is then of the form
fr - 1 =A/(T - 8),
where A is a constant and 8 is a constant called the Curie-Weiss temperature. This
result can be explained by assuming that there is some internal co-operative action
among the dipoles which modifies the applied field II app by virtue of the presence of
an internal field proportional to the polarization P. The 'actual' field II a is of the
form" app + 1P, where P = 'ENa"a, N being the number of dipoles per unit volume,
a the atomic polarizability and 1 a constant. Thus using eqn (8.14)
P LNa8 1
f -1=---= a 0:----
r follapp fo(8 a -1'ENa8a ) l-1'ENa·
Now if this co-operative effect is temperature dependent such that 1 'E No. -+- 1 as
T-+- Te, there will be a catastrophe as fr - 1 goes to infinity at Te leading to an
idealized form of the behaviour actually observed. Whatever the nature of the detailed
atomic interactions, the existence of a co-operative, temperature dependent polariza-
tion is crucial to any explanation of ferroelectricity. Fig. 8.22c shows how P behaves
as Te is approached. Above the Curie temperature the material is non-ferroelectric
but may of course still be piezoelectric. The change from the non-ferroelectric to the
ferroelectric state at Te , called a phase transition is always accompanied by a change
of crystal symmetry. At lower temperatures other symmetry changes may take place
at specific temperatures and the crystal may remain ferroelectric or change to a non-
ferroelectric phase. This behaviour suggests that the balance between the two phases
of different symmetries is a very delicate one. The minimum energy configuration of
the atomic or molecular units in the crystal structure is achieved by very small shifts
of atomic positions in the change from one state to another, as the temperature changes.
8.10 Oassification of ferroelectric materials
The list of known ferroelectrics is one which constantly increases in length and embraces
a great variety of materials, so that a rationalization is not easy. However there are a
few groupings which provide a degree of classification based on crystal chemistry.
(1) A large and varied group whose structures contain repeated oxygen octahedra
surrounding another type of ion. The simplest members are based on the mineral
'perovskite' CaTi0 3 [11]. They have the general formula AB0 3 and the best
known is barium titanate, BaTi03 Niobates and tantalates are also included as
well as important mixed compounds such as lead titanate and lead zirconate.
Pyrochlore compounds are based on the mineral 'pyrochlore', CaNaNb 20 6 F,
with the general formula A2 B2 0 7 • An important member is cadmium pyro-
niobate, Cd 2 Nb 2 0 7 • The structure contains Nb0 6 octahedra. The complicated
tungsten bronze structure, based on Ax W0 3 resembles that of the ferroelectric
lead metaniobate, Pbs Nb 10 0 30 , in which Nb0 6 octahedra may be recognized.
(2) A group of tartrates, hydrogen bonded crystals of which the best known is
Rochelle salt, one of the earliest known ferroelectrics. Rochelle salt is sodium
potassium tartrate, NaKC 4H4 0 64H 20, and the group also includes lithium
ammonium tartrate monohydrate, UNH4C4H406H20, and lithium thallium
tartrate monohydrate.
(3) Alkali metal dihydrogen phosphates, the most important being those of potassium
(KDP) KH 2P04 , and ammonium (ADP) NH4H2P04 . The structure ofKDP is
based on a framework of P04 groups linked by hydrogen bonds.
(4) Hydrated double sulphates of guanidinium and a trivalent metal. The best known
is usually abbreviated to GASH, guanidinium aluminium sulphate hexahydrate.
The general formula is (C(NH 2)3)(M(H 20)6XA0 4)2 where M = Al H , Ga 3+,
Cr 3+, y 3+; A = S or Se. These compounds decompose before the Curie point is
attained.
(5) Alums. General formula M1+M3+(R0 4h 12H20; M1+ = NH4 , CH 3 ; M3 + = Fe,
or Y, or In; R = S, Se. An example is ammonium iron alum, NH4Fe(SO)4)212H20.
(6) Triglycine sulphate (TGS), selenate and fluoberyllate. TG8 has the formula
(NH2 CH2 COOH)H2 804 .
(7) Many other miscellaneous compounds
8.11 Barium titanate
Because of its importance some further properties of barium titanate will be briefly
mentioned.
Its structure is shown in Fig. 8.23. Titanium atoms lie within the oxygen octahedra
and barium atoms squeeze into the interstices between the octahedra. Above the Curie
temperature of 120° C the structure is cubic. Distortions occur at this temperature and
at 5 and -90°C.
Structure: Rhombohedral Orthorhombic Tetragonal Cubic
Temperature (oC): <-90 >-90} > 5} > 120
< 5 < 120
The behaviour of the permittivity and polarization reflects these changes (Fig. 8.24a
and b). The ferroelectricity is thought to arise from the rattling of the Ti4 + ion between
two acentric positions within the oxygen octahedra.
The P, 8. hysteresis loop for a ferroelectric may be displayed using a Sawyer-Tower
circuit (Fig. 8.25a). Fig. 8.25b shows a hysteresis loop for barium titanate. This may
become more complicated near the Curie temperature and appear as a double loop.
DIELECTRICS 177
• Sa
• Ti
Fig. 8.23
o °
Cubic perovskite structure of BaTi03 showing oxygen octahedron.
N
Ie
..~
u
10000 ~ 20
o
'>
';e 8000 ~ 16
'E
~
a:'
Q) 6000 c: 12
c. o
Q) '';:::;
,~ 4000 ~ 8
co 'L
Q; co
a: 2000 (5 4
c.
'"~ o~~~~~~~~~~~----
-'"
0 0 0 0 0 0
0
0 N IX) .q- .q- ~ ~~~~g~o~gg~~
N I I co _ _ ...... 111 --
I I '7 +-'
c:
I 1 I
T em peratu re (OC I o Temperature(OCI

c.
(/)
(al (bl
Fig. 8.24 (a) Relative permittivity and (b) spontaneous polarization of BaTi03 as a function of
temperature.
8.12 Ferroelectric ceramics [12]
As well as barium titanate, already mentioned for its piezoelectric applications, other
ferroelectrics can be made in ceramic form relatively cheaply and easily. Again, poling
in an electric field is an essential part of the manufacture of a ferroelectric ceramic. For
example, barium titanate can be poled by applying a field of about 103 kVm- 1 for
5 min at 50°C with the sample immersed in silicone oil. PZT can be similarly poled
at 200°C in fields up to 4 X 10 3 kVm- 1 • Recently, ceramics based on solid solutions of
P
To X plates
Ferroelectric of oscilloscope
crystal rl.W
--------~~----~-W
Capacitor To Y plates
rl.P
(a) (b)
Fig.8.25 (a) Sawyer-Tower circuit. (b) Hysteresis loop for BaTi0 3 .
N
:I:
~ 800
u'
o
~ 600
...>-
.:;
'E 400
'E
Q;
c.
CD 200
>
'';:::
Qi
a:
'"
o 20 40 60 80 100 PbZr03
PbTi0 3 100 80 60 40 20 o
Composition (mole %)
Fig. 8.26 Relative permittivity of lead zirconate titanate (PZT) as a function of composition
(measured at 25°C, 1 MHz).
TABLE 8.7
Properties of fe"oelectric materials
MateriJJl Curie point Structure Fe"oelectric Saturation

(K) axis polarization
(x 1O-2 Cm -2)
Uthium niobate 1473 trigonal c 71

KDP 123 tetragonal c 4·95
Barium sodium niobate 833 orthorhombic c 40
Strontium titanate 28 tetragonal c
tetragonal
Barium titanate 393 { orthorhombic c 8
rhombohedral
Lead titanate 760 tetragonal c
PZT5A 638 ceramic 38
Rochelle salt 297 monoclinic a 0·24
Triglycine sulphate 321 monoclinic b 2·2
GASH none trigonal 0·35
Lead metaniobate 843 orthorhombic a+b
DIELECTRICS 179
PbTi0 3 and PbZr03 have been widely used. By varying the relative proportions of the
constituents, properties can be modified to requirements to some extent, Fig. 8.26
shows a graph of the permittivity of PZT as a function of composition. If thin enough,
ceramics may also be used for optical applications. Table 8.7 lists some properties of
ferroelectric materials.
8.13 Ferroelectric domains
A ferroelectric domain is a region in a crystal in which the direction of polarization is

uniform. A sample of a ferroelectric may be nominally a single crystal and yet contain
many domains in each of which the polarization and the crystal axes may have a
different direction. Domains are separated by domain walls. The domain wall is the
transition region in which the direction of polarization changes from one domain to
the next. Wall thicknesses in ferroelectrics are quite small, about 2 A in BaTi0 3 .
Domains exist because the overall energy is lowered by eliminating the free poles
which would otherwise exist, and internal depolarizing fields are reduced. Domains
arrange themselves so that there is no space charge at a wall. In Fig. 8.27 the polariza-
tion directions at the wall AB lie head to tail to eliminate free charge. Fig. 8.27 a shows
a 900 wall where the polarization directions are at 900 and Fig. 8.27b a 180 0 wall.
yf B +++++--
~ ~ >r
+ -
.. + -
+ + + +
(a) (b)
Fig. 8.27 Ferroelectric domain walls (a) 90° wall and (b) 1800 wall.
The small size of domain walls in ferroelectrics con~rasts sharply with dimensions of
the order of 100 A in magnetic materials where the major contribution to the energy
is from exchange (Chapter 9). In ferroelectrics there is a large anisotropy energy. It is
energetically favourable for the dipoles to point in opposite directions across a 1800
wall as quickly as possible, reducing the region in which they are at an angle, to a
minimum. The energy associated with a domain wall is about 10- 2 J m- 2 . The growth
and ordering of domains are responsible for the shape of the ferroelectric hysteresis
Sideways
--
growth
(a) (b) (e) (d)

Fig. 8.28 (a)-(d) Successive stages in the growth of a ferroelectric domain as a region of reversed
polarization in an applied field &.
loop. Growth of a domain proceeds from surface nucleation in spikes of reversed

polarity. Usually polarization reversal in an applied field occurs over a very narrow
field range giving rise to a much more rectangular loop than for magnetic materials.
In contrast to magnetic domains it is easier for new domains to nucleate and grow as
spikes than for growth to occur by sideways motion of the walls (Fig. 8.28).
8.13.1 Observation of domains

Domains can be revealed by etching the surface of a ferroelectric with a suitable
etchant. The negative ends of dipoles are attacked at a different rate from the positive
ends leading to an observable pattern of domain walls. Hydrochloric acid is often used
as an etch. Water can be used on Rochelle salt and TGS. The most important means of
study is by polarized light. Details of domain structure may be deduced from changes in
intensity of transmitted light as the plane of polarization of the incident light is varied.
Consider an example of tetragonal BaTi0 3 , the crystal axes being denoted by a and c,
the latter being the direction of the tetragonal distortion. A domain with its optic c
axis parallel to the direction of incident light is called a c domain. Suppose it is placed
between crossed polars as in Fig. 8.29. The direction of polarization of the incident
Polarization Polarization
direction direction
Incident
light
-pti
axis No
transmitted
light
Polarizer Analyser
Specimen
Fig. 8.29 Passage of polarized light in the direction of the optic axis in a c domain of BaTi03.
light is quite unaffected by its passage through the domain in this case, so, observed
through the analyser the domain appears dark. The section of the indicatrix (Chapter
10) perpendicular to the polarized beam is a circle, and whatever the direction of
polarization no light is transmitted through the analyser.
If however, in an adjacent domain, the light is not parallel to the optic axis, the
cross section of the indicatrix normal to the beam will now be an ellipse. The light
emerging from the crystal is now elliptically polarized and there will always be trans-
mitted light through the analyser. The intensity will vary with the direction of polariza-
tion of the incident beam, except in the special case where the direction of polarization
is parallel to one of the axes of the ellipse, when no light gets through the analyser. In
general, it will be possible to distinguish the two domains.
8.14 Pyroelectricity [13]
Normally the external electric field due to the spontaneous polarization of a pyro-
electric specimen is not easy to detect. The reason is that stray surface charges tend to
neutralize the effect of the polarization. If the polarization is made to change then the
external field can be detected for a short time. The pyroelectric coefficient Ais defined
as the change in polarization per unit temperature change of the specimen:
A = dP/dT.
DIELECTRICS 181
Thus, when the temperature of a specimen is changed it is possible to measure the
change of spontaneous polarization which is the pyroelectric effect. Knowing the
coefficient A the temperature change can be measured. Values for A for various
materials are given in Table 8.8.
TABLE 8.8
Pyroelectric coefficients
Material Whether Pyroelectric coefficient at 2(f C

fe"oelectric A (10-5 C m-2 deg- 1 C)
LiTa03 yes 19
BaO.27SrO. 73 Nb 2 0 6 yes 280
Gd 2 ( Mo04h yes 5
BLtTi3012 yes 12
GASH yes 14
PbTi03 yes 40
TGSe yes 300
LiNaS04 no 0·8
ZnS (wurtzite) no 0·03
NH4 I0 3 no 3
KLiS04 no 1·5
Tartaric acid no 3
PVC no 3
As it is possible to detect a charge of 10- 16 C with a suitable electrometer, tempera-

ture changes as small as 10- 6 °c can be measured using the pyroelectric effect.
A graph of the temperature variation of the spontaneous polarization Ps and the
pyroelectric coefficient dPs/dT for TGS is shown in Fig. 8.30. There are two simple
.
N
'E
N
u
I
o I
~
~ I
0...
.~
~
c: 10
l!l 8
,.
II 5
,. ~
~
";:
til dPs I • :e
6 dT, • '"
, ....%
(5
c.
V>
::J
I I!;
o 4
CD , I
c:
•
---- --
c:
til
2
o
enc. 0 '--_ _-'-_ _ _""'--_ _--'-_ _ ___
-150 -100 -50 o 50
Temperature IOC)
Fig. 8.30 Temperature dependence of spontaneous polarization Ps and pyroelectric coefficient

for TGS.
....
00
t-.)
TABLE 8.9
PropertielIofpyroelectric materillllI
Materilll Pyroelectric Relative SpeciFre DenlIity Thermal Curie Figure c;[ merit
coefficient permittivity heat capacity (p kgm m- 3 ) conductivity temperature ()../PlIe: x 109 )
~
)..(10-SC m- 2 deg-1 C) (er ) II (Jkgm- 1 deg-1C) K (Wm- 1 deg-1C) Tc ("C) ~
n
->
l""'
TGS 20-35 42 Bpolar 0·97 x 10 3 1·7 x 103 6 x 10-1 52 1·9-3·3
axis ;iI
BaTi03 20 160 Upolar 0·5 x 103 6·0 X 103 9 X 10- 1 120 0·53
axis ~
41001 polar d
axis 0·10 I:!l
en
NaN0 2 14 7·4 I polar 0·96 x 10 3 2·3 X 10 3 1·0 163 2·3 0
'"lj
axis
PZT ceramics 6-300 300-3000 0·4 x 103 7·4 x 103 1-1.5 320 0·12-1·85 s:
li2S04H2 7·8 10·3 0·4 x 10 3 2·05 X 103 1·7 2·96
liNb03 4 30 Bpolar 0·4 x 10 3 4·64 X 10 3 4·2 1190 0·39 ~
axis ~
751 polar 0·25
>
F;;
axis
DIELECTRICS 183
methods for determining the pyroelectric coefficient of a material. The specimen in
the form of a thin disc may be heated by incident radiation from a hot body and the
initial pyroelectric current is measured. If
incident radiant intensity = W,
area of specimen = A,
thickness of specimen = Z,
density of specimen = p,
specific heat of specimen = s,
then the equation for heat balance is
WA = z ps A dT/dt, (8.40)
where dTldt is the initial rate of rise of temperature of the sample. Since X = dPs/dT
the charge developed is given by
Q=A XdT
and the initial current
1= dQldt =A X dT/dt. (8.41)
Therefore from egn (8.40)
WA =z p sI/A,
i.e.
X =Izps/WA. (8.42)
Hence a measurement of I gives X directly if W is known. If the radiant source is a black
body of known temperature at a known distance from the sample, W can easily be
calculated. A blackened tip of a soldering iron is a convenient heat source in this experi-
ment. An alternative method is to heat the specimen in an oil bath and measure the
total charge released for a given temperature rise. The coefficient X is then given by the
gradient of the graph of charge released versus temperature.
8.14.1 Applications of pyroelectric materials

The pyroelectric effect is used to make very good infra-red detectors [14, 15] which
can operate at room temperature. It is often advantageous to be able to avoid the cool-
ing required for the alternative semiconductor infra-red detectors. A further develop-
ment has been the construction of pyroelectric image tubes for use in the dark [16].
TGS is the material most widely used because of a favourable combination of properties,
but others are being tried. A useful figure of merit of a pyroelectric material is XI PS€r 1/2.
Table 8.9 gives information about materials which are candidates for pyroelectric
applications.
TGS has a high figure of merit and is a good absorber of radiation in the wavelength
range 8-14 tlm. Pyroelectric ceramics based on barium titanate doped with strontium
or on the lead zirconate-titanate system are useful. General requirements for the
materials are a high pyroelectric coefficient, low relative permittivity, physical and
chemical stability, low piezoelectric response and if ferroelectric, stability against
depoling. The optical absorption should be in the right part of the spectrum.
References
1. Smyth, C. P. Dielectric Behaviour and Structure, McGraw-Hill (1955).

2. Jaffe, B., Cook Jr., W. R. and Jaffe, H. Piezoelectric Ceramics, Academic Press (1971).
3. Cockayne, B. and Jones, D. W. (Editors). Modern Oxide Materials, Academic Press (1972).
4. Jaffe, H. and Berlincourt, D. A. Proc. IEEE 53, October, 1372-1385 (1965).
5. Dransfeld, K. Sci. Am., June (1963).
6. Kino, G. S. and Shaw, J. Sci. Am, October, 51-69 (1972).
7. IEEE Trans. Microwave Theory and Techniques (Special issue on Microwave Acoustics)
Vol. MTT 17, No. 11, November 1969.
8. de Klerk, J. Physics Today, November, 32 (1972).
9. Jona, F. and Shirane, G. Fe"oelectric Crystals, Pergamon (1962).
10. Shirane, G., Jona, F. and Pepinsky, R. Proc. IRE, December, 1738 (1959).
11. Galasso, F. S. Structure, Properties and Preparation of Perovskite Type Compounds, Pergamon
(1969). .
12. Drei, M. Fe"oelectric Ceramics, Maclaren (1966).
13. Cady, W. G. Proc. IRE, 18, 1247 (1930).
14. Putley, E. H. Semiconductors and Semimetals, Vol. 5, pp. 259-285, Academic Press (1970).
15. Doyle, W. M. Laser Focus 6, July, 34-37 (1970).
16. Taylor, R. and Boot, H. Contemp. Phys. 14, January, 55 (1973).
Questions
1. The refractive index of water is 1'33, whilst its relative permittivity €r varies with
frequency f as follows
€r 81 3·3 2·8
f(Hz) 0 8·3 x 106 2·5 X 107
Explain these figures.
2. How much power is dissipated per unit volume in polystyrene if a signal of 1 V peak
amplitude at a frequency of 106 Hz is applied to a capacitor having this material as
dielectric? At this frequency the relative permittivity of polystyrene is 2·6 and the
dissipation factor, tan 0 = 7·0 X 10- 5 •
3. Show that the heat dissipation in a dielectric is half its maximum value at the
frequency at which €/" the imaginary part of the relative permittivity, is a maximum.
Assume that the dipoles have a single relaxation time.
4. The polarizability P per kilogram mole of a substance as a function of temperature
Tis given by
P = a + (biT) where a and b are constants.
Calculate the electric dipole moment of each molecule if b has the value 15 m 3 •
5. Ice at _6°C has a static relative permittivity of 80. Its frequency dependence of
tan 0 shows a peak value of 2·93 at a frequency of 104 Hz. Use this data to deduce
the infra-red refractive index of ice and the relaxation time of the dipoles at _6°C.
6. A piezoelectric material is subjected to a tensile stress in the x direction. By consider-
ing the electrical energy stored for polarization in the z direction show that the appro-
priate electromechanical coupling factor K 13 is given by
KI3 =( d 31 2 )1/2
€33 S 11
7. The amplitude of an electric field increases linearly with time from -&0 to +&0'
Compare the current-time response to this field of (a) a loss-free dielectric, (b) a
pyroelectric, and ( c) a ferroelectric material.
9 Magnetic Properties
9.1 Introduction
In Chapter 1 the basic principles of atomic magnetism were described. When atoms
come together to form solids their intrinsic magnetism acts in various ways to give
these solids magnetic properties. Because the balance of magnetic interactions
between atoms is such a delicate one, various types of magnetism are possible and here
the main features are discussed together with some important applications.
In the presence of a magnetic field in vacuum the magnetic induction or j7ux density
B is given by
B=J.LoH, (9.1)
where J.Lo is the permeability of vacuum.

When a magnetic material is in a magnetic field H with a magnetization (or dipole
moment per unit volume) M the magnetic induction in the material B is
B = J.Lo(H + M) = J.LoJ.LrH, (9.2)
where J.Lr is the relative permeability of the material (= 1 for vacuum).

Hence
J.Lr = I + (M/H) = 1 + X, (9.3)
where X is the magnetic susceptibility of the material. B, M and H are vectors; the
unit of B is the tesla or weber m- 2, while M and H have the same units of ampere per
metre. Hence X has no units.
9.2 Classification of magnetic materials
There are five classes into which magnetic materials may be grouped;
(a) diamagnetic,
(b) paramagnetic,
(c) ferromagnetic,
(d) antiferromagnetic, and
(e) ferrimagnetic.
Table 9.1 summarizes features of each.
TABLE 9.1
Type Magnitude of Temperature Examples

susceptibility dependence
X ofx
(a) Diamagnetic small and independent atoms of solids possessing

negative closed shells and some
--I<r6 metals Au, Ge
C .
(b) Paramagnetic small and x= T"Cune law atoms possessing odd
positive number of electrons;
-1<r6 C many miscellaneous
or= - - compounds, e.g. ionic
T- 6
Curie-Weiss law crystals
small and independent Pauli paramagnetism due
positive to conduction electrons
in metals
(c) Ferromagnetic very large and (X-+ 00) iron, cobalt, nickel,
positive gadolinium
(d) Antiferromagnetic small and X decreases with salts and oxides of
positive temperature transition metals, e.g.
NiO, MnF2
C¥-chromium
(e) Ferrirnagnetic large and (x-+ 00) ferrites, e.g. Fe304
positive
9.3 Diamagnetism
The diamagnetism of solids is a consequence of the diamagnetism of the constituent

atoms (Chapter 1). It is a property of all materials, but is often masked by larger
magnetic effects. The formula for the diamagnetic susceptibility Xdia of a solid with N
atoms per unit volume and atomic number Z is
(9.4)
where f2 is the mean square distance of electrons from the nucleus. The long diamagnetic
bar ab (Fig. 9.1a) repels flux lines and becomes magnetized by the induced effect with
two north poles together. The stable position which the bar assumes in the field is
shown in Fig. 9.1b.
a
n s
n s
3 E
n s
n s
n s
n s
n s
n s
b
(a) Unstable (b) Stable
Fig. 9.1 Idealized situation of long diamagnetic bar in a magnetic field.
MAGNETIC PROPERTIES 187
9.4 Paramagnetism
In Chapter 1 the source of paramagnetism of atoms has been described. Leaving aside
for the moment the case of ferromagnetic materials which become paramagnetic above
a certain temperature (see below) solids exhibit paramagnetism if they contain para-
magnetic atoms in dilute solution, that is, one such atom or ion must be far enough away
from another, with diamagnetic atoms in between, so that there is no direct magnetic
interaction between them. These paramagnetic atoms form a collection of non-interacting
magnetic dipoles. The direction of these dipoles is normally random because of thermal
vibrations. The magnetization of the solid is thus zero until an external field is applied
when the dipoles tend to line up with the field. The resultant susceptibility varies
inversely as the absolute temperature
X=C/T. (9.5)
Eqn (9.5) is known as Curie's law. C is a constant, the Curie constant.

The net magnetization M of a paramagnetic solid in a field H at temperature Tis
given by an expression due to Langevin
M =Nil
,..
(COth p.H _ kT)
kT p.H'
(9.6)
where p. is the magnetic moment of the paramagnetic atoms and N the number per unit
volume.
When p.H/kT ~ 1 the expression in parentheses Simplifies to p.H13kT giving a Curie
law with constant C =Np.2 13k. This is often the case in moderate fields at room tem-
perature. Eqn (9.6) is modified when quantum mechanical effects are considered but
Curie's law is still the main feature of behaviour unless the applied field is large or the
temperature low.
'"m; _
~ --~;,,--_",,::
Spin-up band Spin-down band

H=H
t Unstable
H=O
(a) (b)
(e)
Fig.9.2 Distribution of spins in the band model of a metal at T =O. (a) Zero applied field. (b)
Applied field H. (c) Electrons flow to equalize the Fermi level to give excess of spin-up over
spin-down.
9.4.1 Pauli paramagnetism

In metals, where the free electrons can be treated by band theory, their magnetism
leads to a temperature independent paramagnetism named after Pauli. Referring to the
potential well model of a metal (Appendix I), at T =0 the electrons, each of moment
p., may be divided into two equal groups, one with spin up, the other spin down (Fig.
9.2a). In the presence of a magnetic field H the spin-down electrons increase their
energy relative to the spin-up by M = 2p.H (Fig. 9.2b). Some of those at the top of
the distribution can find lower energy states with spin up and this process continues
until the Fermi levels are equalized (Fig. 9.2c). There is now an excess of electrons
with spin up giving a net magnetic moment.
Since the fraction of electrons which have changed their spin is T/T F, where TF is
the temperature of the Fermi level and the magnetization is given by M - Np.2 H/kT,
the resultant magnetization M - p.2 H/kT F is independent of T. The associated sus-
ceptibility is typically 10-6 to 10-8 •
9.5 Ferromagnetism
Ferromagnets become very strongly magnetized in a weak external field and may
possess a spontaneous magnetic moment even in zero field. Ferromagnetism only
exists below a certain temperature, the Curie temperature Te above which the sub-
stance becomes paramagnetic. In this paramagnetic state, a modified Curie law
is obeyed known as the Curie-Weiss law:
X=C/(T- 8), (9.7)
where 8 is a constant. Fig. 9.3 compares the susceptibility-temperature dependence of
a paramagnetic and ferromagnetic material.
x X 1
x
-;-
>
~ ~ ~
;e
(J
ii ii '';::;
a.
Q)
'';::;
Q. Q) X very
E. Q)
c
Cl
01
.
Q) (J (J
(J
'":l large X:C'T_ 6 '":l E
'"
:l
'" '"
0
'"
(J
(J
'';::;
.!:1 Gi
u..
:;::; Q) Qj
Q) c c
c Cl Cl
Cl 01 01
01
~ ~
~
T Tc = 6 T T
Temperature Temperature Temperature
Fig. 9.3 Temperature dependence of magnetic susceptibility x for (a) a paramagnet; (b) a ferro-
magnet above and below Curie point Te; and (c) l/x versus T for a ferromagnet above and below
Te.
One of the characteristic features of a ferromagnet below its Curie temperature is

the relation between magnetization M or magnetic induction B and the applied field H
which shows a hysteresiS. Thus a susceptibility cannot be defined uniquely below a
temperature equal to () without knowing the state of the specimen. A typical hysteresis
curve is shown in Fig. 9.4 and refers to a ferromagnetic specimen being initially de-
magnetized and in an initial state corresponding to the point O. As H is increased
positively, the path OA is followed and subsequently as H is reduced and increased
negatively ABCD is traversed. The susceptibility at any point is the slope elM/dH.
For the corresponding B-H curve, dB/dH will be the instantaneous permeability. The
slope at the origin is called the initial susceptibility or permeability.
M ___ ~A
Magnetic
field H
Fig. 9.4 Magnetization M versus applied field H for a ferromagnet showing typical hysteresis
loop.
The field corresponding to the point C is that required to reduce the magnetization
to zero and is called the coercive force while the magnetic induction appropriate to the
point B is the remanence.
Energy is dissipated when the loop is traversed and the work done is given by the
area of the loop
work done = J H dM
ABCDEA
=..!.. fH dB.
JJ.o
(Compare the work done in compressing a gas p dv. Here the driving 'force' p is the
field H.) The loop can only be traversed in an anti-clockwise direction. In practice a
hysteresis loop may be plotted on a recorder or oscilloscope screen using the circuit
of Fig. 9.5.
Y plates
Fig. 9.S Circuit for displaying a magnetic hysteresis loop of a toroid on a CRO.
The temperature dependence of the magnetization of a ferromagnet below the Curie

point is important, as it is a convenient test of a theory of ferromagnetism to reproduce
this behaviour (Fig. 9.6). The curve closely follows a mathematical expression known as
a Brillouin function, Bs(y), where
B (y):::: (2S + 1) coth {(2S + I)Y) _ .!.. coth L.

s 2S 2lJ2S 2S
Here, S is the total spin quantum number and y :::: gSIJp,HjkT.
Ci)
.'!:
c:
:::l 50
...
>-
....~ 40
:c...
..e
30
~
c:
0
:;::; 20
IU
N
:;::;
GI
c: 10
Cl
IU
~
0 100 200 300 400 500 600 700
Temperature (K)
Fig. 9.6 Spontaneous magnetization of nickel as a function of temperature.
9.6 Magnetic anisotropy
In general the properties of magnetic materials vary with direction. This is most easily
shown by considering low index crystallographic directions in single crystals. Iron has
a b.c.c. structure and the main crystallographic directions are shown in Fig. 9.7a while
the corresponding magnetization as a function of applied field for these directions is
given in Fig. 9.7b.
The curves show that there are pre/erred directions of magnetization in the crystal,
so it costs more in energy to choose some directions for magnetization rather than
others. The crystal is said to show magnetic anisotropy. The anisotropy of a crystal is
usually expressed in terms of anisotropy constants K. In a crystal such as the one
mentioned above there will be an easy direction of magnetization. Suppose extra
energy E is needed to magnetize the crystal in another direction making LO with the
easy direction. If the crystal is uniaxial, that is one having a single easy direction,
E can be expressed as a series of sin 2 6
(9.8)
Usually only the first term need be considered and K 1 is called an anisotropy constant.
Eqn (9.8) does not contain odd terms in sin 6 because it must reflect the crystal sym-
metry and E must not change sign when 6 changes sign. In a cubic crystal the expression
'E 2
<{
<D
o [100]
~ 1.5
~
c
o
''::;
<II
III
:;;
CD
C
g> 0.5
~
[100] a 8 16 24 32 40
(a) Applied field H (x1 03Am- 1)
(b)
Fig. 9.7 (a) Principal crystallographic directions in a cubic crystal. (b) Magnetization versus
field for these directions in a single crystal of iron.
for E involves the cosines of the angles which the magnetization direction makes
with the cube edges. If these direction cosines are al> a2 and a3
E=K 1(a1 2a2 2 +a22a32 +a12a/)+K2(a13a23a33). (9.9)

The anisotropy of cobalt is illustrated in Fig. 9.8. In cubic iron, the easy directions
are cube edges [100] and the hard directions are the diagonals [Ill]. In hexagonal
cobalt the one easy direction is the c axis perpendicular to the base plane, and around
'";" 1.5
E
~
o
.-
~
~ 1.0
c
o
''::;
<II
N
.~ 0.5
c
CJ)
<II
~
16 32 48 64 80
Applied field H (x 104Am-l)
Fig. 9.8 Magnetization curve for a cobalt single crystal.
this axis there is cylindrical symmetry in magnetization. Another quantity used to

describe anisotropy is the anisotropy field HK. This is the magnetic field required to
rotate the magnetization from the easy direction to a given direction.
(9.10)
where Ms is the saturation magnetization for the specified direction at a given tempera-
ture. Eqn (9.10) is obtained by equating the torque due to the applied field to the
torque on Ms due to the anisotropy. Some values of K 1 and HK are given in Table 9.2.
TABLE 9.2
K1(J m-3 ) HK(Am- 1 ) Easy

direction
Iron 4·8 x 104 4·5 x 104 [100)

Cobalt 53 x 104 5·9 x 10 5 c axis
Nickel -0·45 x 104 1·5 x 104 [111]
9.7 Magnetostriction
When the magnetic dipole moments in a solid are rotated into alignment, the fields of
the dipoles influence the interatomic spacing. Therefore the shape and volume of a
ferromagnetic solid changes as it is magnetized. The principal change is a positive or
negative reversible strain along the axis of magnetization. This is called the 11'Ulgneto-
striction. The magnetostriction coefficient Ais the fractional change in length Mil
associated with a change in magnetization from zero to saturation.
The magnetostriction is anisotropic partly because the magnetization itself is
anisotropic and partly because the elastic constants are anisotropic. Conversely an
induced strain will result in an anisotropic magnetization.
For iron in the [100] direction A has the value 20·7 x 10-6 and in the [111]
direction -21·1 x 10-6 , the negative sign indicating a contraction.
9.8 Ferromagnetic domains [1,2,3]
An unmagnetized piece of iron can be readily magnetized strongly by a weak applied

field and a magnetized material may retain its magnetization in zero field. These pro-
perties are described by the hysteresis loop. What is the explanation of these effects?
Weiss was the first to suggest the basic idea which provides a satisfactory picture, that
of magnetic domains. He proposed that a magnetic material comprised a number of
distinct regions called domains each of which was magnetically saturated in a different
direction. Fig. 9.9 shows the situation schematically. Although each domain is fully
magnetized the material as a whole may have a net zero magnetization as shown.
The effect of an external applied field is to align domains so that there is a net
moment. At low fields this alignment occurs through the growth of some domains at
the expense of less favourably orientated ones and the intensity of magnetization in-
creases rapidly. Domain growth ceases as the saturation region is approached and
rotation of the remaining unfavourably aligned domains occurs. Domain rotation
requires more energy than domain growth and hence the slope of the M-H curve
decreases at this stage. This explains the initial magnetization curve but not the
hysteresis. Hysteresis is explained as follows. Most materials contain large numbers
of imperfections which act as obstacles to domain rotation and domain wall motion.
When the field is increased the obstacles are overcome by the energy supplied by the
field. On removal of the field the defects prevent the walls returning to their previous
positions. Thus, to return the domain structure to a random array, with zero net
Fig.9.9 Random arrangement of magnetic domains in un magnetized material.
moment, it is necessary to supply more energy. The idea of domains postulated by

Weiss in 1907 was not confirmed until more than 25 years later when colloidal iron
oxide was used to render domain boundaries visible under a microscope.
9.8.1 Origin of domains

If a solid sample (e.g. a single crystal) were a single domain it would have a large magnetic
moment even in the absence of an applied field. There would be a large external magnetic
field associated with this magnetic moment and hence a large magnetostatic energy. This
magnetostatic energy can be reduced by dividing the specimen into domains as shown
in Fig. 9.10. However, it costs energy to create boundaries between domains and there
are a number of contributions to this energy.
Fig. 9.10 Domain structure in a cubic crystal (e.g. iron) with magnetization along easy axes.
There will be a strain energy due to magnetostriction which is roughly proportional

to the volume of domains. This can be decreased by increasing the number of domains.
The contribution from anisotropy energy depends on sin 2 <p, where <p is the angle
between adjacent spins, and favours <p = 0 or 1T for minimum energy.
9.8.2 Domain walls

In a domain boundary, there are many moments aligned in 'non-easy' directions and a
considerable anisotropy energy is associated with these moments. This energy can be
minimized if the alignment of magnetic moments in adjacent domains is arranged as
shown, for example, in Fig. 9.10. Between domains there exists a very thin wall region.
When the directions of the magnetic dipole moments are antiparallel the boundary is
called a 1800 wall. The domains at the ends of the specimen shown in Fig. 9.1 0 are
called closure domains and these have 90 0 walls. Notice that there is no net magnetiza-
tion normal to domain walls.
However, there is another factor which dominates energy considerations in magnetic
domain walls, the exchange energy. Exchange energy depends on the cosine of the angle
between adjacent spin moments and is expressed as
(9.11 )
where i and j are neighbouring spins and </>i; is the angle between them. This is a mini-
mum for </>i; = 0 and so because of exchange energy spins like to be parallel. When there
is a change of angle between spin directions in adjacent domains, exchange dictates
that this change should be spread over a wide region (Fig. 9.11) while anisotropy
energy requires it to occur quickly, leading to a thin wall.
!/ I
y
,1 /1 "'\ x
1 1800 domain w
__al_I_ ___
-x
(a) (b)
Fig.9.11 (a) Rotation of successive spins to form 1800 domain wall. (b) Coordinate system for
angle ( 1 - <1>2) between successive spins.
In magnetic domain walls exchange energy is most important and leads to walls of
the order of 100-1000 A thick. The walls are known as Bloch walls after the man who
did much of the early work on the subject. The boundary energy per unit area is
typically 10- 3 J m- 2 . Notice the coordinate system of Fig. 9.11 indicates that the spins
turn out of the plane of the page so that the azimuthal angle </> is changing. For </> small
eqn (9.11) can be written
by expanding the cosine term as a series and neglecting higher terms. Thus, Eex ex </>2
so if the change in angle is I:l</> for a distance a in the x direction through the wall
I:l</> = a d</>/dx
and
where A is a constant which includes the constant J. The total energy 'Y of a domain
wall may now be written
(9.12)
that is, the sum of the exchange and anisotropy contributions to the energy. Eqn (9.12)
can be minimized to find the optimum conditions and this leads to the result that
'Y = 4(AKd l/2
and the effective width of the boundary [j = 1f(A/K 1 )112.
9.8.3 Domain patterns

The simplest way to observe domains is to develop Bitter patterns by using a colloidal
suspension of magnetite. The suspension is spread on the polished surface of the speci-
men and field gradients at domain walls produce characteristic patterns. In specimens
having a cubic structure, when a surface diverges a few degrees from planes containing
the easy axis, 1800 boundaries are decorated by fir tree patterns. These arise from a
closure domain structure which forms to reduce free pole effects arising from the
misorientation.
Another method of observing domains relies on the fact that the plane of polariza-
tion of incident polarized light is rotated either on reflection (Kerr effect) or on trans-
mission (Faraday effect) by an amount which depends on the magnetization of the
sample. The analyser can then be adjusted for maximum optical contrast between
domains magnetized in different directions. The Faraday effect is only useful for thin
fllms, of the order of 10- 2 J.,Lm thick, because of absorption of light in the sample.
Electron microscopy is also used to examine fine detail in domain structures. Here
the contrast between domains is obtained through different electromagnetic Lorentz
forces, due to the magnetization of the domains causing preferential directional scatter
of the electron beam.
9.9 Microscopic explanation of ferromagnetism
In 1907 Weiss explained ferromagnetism by postulating the existence of an internal

field, strong enough to line up the dipole moments in a material. At the Curie tempera·
ture thermal agitation can overcome the aligning effect of the internal field and
randomize the atomic magnets.
No satisfactory fundamental explanation of the Weiss field was forthcoming until
the advent of quantum mechanics, and the exchange interaction discussed in Chapter 1.
This is a pair interaction between nearest neighbour atoms. In iron, for example, the
overlap of the d electron wave functions of each iron atom has the effect of reducing
the overall energy if the net spins are parallel. This leads immediately to all net atomic
moments being parallel in the absence of any thermal agitation, that is, at T =O. Since
this effect depends very critically on overlap the interatomic distance is crucial, and
only within narrow limits does ferromagnetism or its antithesis, antiferromagnetism,
the ordered array of antiparallel moments, exist. Recall Fig. 1.12, a graph of the
exchange constant against interatomic distance. Only for a narrow range of r and
for a positive exchange constant does ferromagnetism exist and thus only iron, cobalt
and nickel of the transition elements are ferromagnetic.
9.10 Applications of ferromagnetic materials
For technological purposes ferromagnetic materials fall into two groups. Those which
are easy to magnetize and demagnetize called soft materials and those which retain their
magnetism and so are more difficult to demagnetize known as hard materials. For
permanent magnets a hard material is needed with a high saturation magnetization, high
remanence and high coercivity. Such a material is characterized by a fat hysteresis loop,
and the shape of the loop in the second quadrant is often used as a measure of the
effectiveness of a material as a permanent magnet. The product BH is plotted as a
function of H and the maximum value of this product which is a measure of the maxi-
mum amount of stored energy is used as an index. Fig. 9.12 shows a demagnetization
curve in the second quadrant of a B-H graph together with the corresponding B-BH
curve plotted in the first quadrant.
1.4
1.0
0.8
(,,)
0.6
:;;
Q)
c: 0.4
Ol
co 0.2
~
-64 -48 -32-16 a 4 8 12 16 20
Field H (x 1 03Am- 1) Energy product BH (xl 04Jm-3)

Fig.9.12 Demagnetization curve and a B-BH curve for Alnico V.
Carbon steel magnets were known as early as the thirteenth century. More recently
a variety of compositions have developed which are known widely by their commercial
names such as Ticonal, Alnico and Alcomax. Typical properties are summarized in
Table 9.3. These materials are alloys of iron, nickel, aluminium with other elements,
TABLE 9.3
Properties of hard magnetic materials
Material Composition Coercive Remanent (BH) max

(% by weight force He induction Br (Jm- 3 )
remainder Fe) (Am-I) (Wbm-2 )
1% carbon steel 1 C, 0'5 Mn 4'1 x 10 3 0'9 1'59 x 103

5% tungsten steel 5 W, 0'7 C 5'6 x 10 3 1'05 2'63 x 10 3
Alnico V 8 AI, 14 Ni 24 Co, 3 Cu 49'3 x 10 3 1'25 4'2 x 104
Platinum-cobalt 76'7 Pt, 23'3 Co 34'2 x 104 6'45 7'6 x 104
such as cobalt and copper. Some, such as Ticonal, are manufactured so as to have
anisotropic properties leading to a large magnetization in one particular direction.
Alnico is an alloy made in such a way as to precipitate very small particles of magnetic
material (an iron rich phase) into an essentially non-magnetic matrix based on alu-
minium. The tiny magnets are too small for domain walls to form, and they remain as
single domain particles having a large anisotropy associated with their shape. By suitable
heat treatments high values of (BH), coercivity and remanence can be achieved in such
materials.
Soft magnetic materials are needed for electromagnets, and for transformer and
inductor cores operating up to high a.c. frequencies. Apart from the need for these
materials to lose their magnetism easily on removal of the field, another problem arises
in practice, that of eddy current losses. These are the losses due to electrical Joule
heating which is proportional to (current)2, and are basically due to the presence
of free electrons able to carry current. In transformer cores, laminations insulated
from one another are used to increase the electrical resistance for low frequency
applications while at high frequencies the core is made of iron dust mixed with an
insulating binder. Typical soft magnetic materials are nickel-iron alloys known as
Permalloy, silicon-iron alloys, iron cobalt and nickel alloys and pressed alloy powders.
The purpose of the silicon in silicon-iron is again to increase resistivity. A summary of
the properties of some soft magnetic materials is given in Table 9.4.
TABLE 9.4
Properties of soft magnetic materials
Material Composition Permeability Ilr Coercive Saturation Curie

(% by weight force He induction temperature
remainder Fe) Initial Maximum (Am-I) (Wbm-2 ) Te (0C)
Iron 0'05-0'2 200-5000 104 -2 x lOS 4-80 2-2 770

(impurity)
Silicon-iron 0'5 Si 280 3000 71'6 2'1 765
Silicon-iron 3-25 Si 290 8000 55'7 2'0 740
Permalloy 45 Ni 3500 5 x 104 5'6 1'6 440
Permalloy 78 Ni 15000 lOS 4 1-1 580
Mumetal 5 Cu 4 Mo 77 Ni 5 x 104 17'5xlO4 1'1 0'7 355
Superpermalloy 5 Mo 79 Ni 650 104 0'32 0'8 400
9.11 Antiferromagnetism
Consider the compound manganese oxide, MnO. The Mn2+ ions each have a net moment
of 5 Bohr magnetons. The arrangement of magnetic moments in the lattice of single
crystal MnO is shown in Fig. 9.13. Information about spin arrangements is obtained
from neutron diffraction experiments. Within a given (l11) plane the magnetic
moments of the Mn2+ ions are aligned parallel but alternate (111) planes have their
moments antiparallel. Moments of Mn 2+ ions linked by oxygen ions are also antiparallel.
This arrangement was interpreted as being due primarily to an exchange coupling
between next to nearest magnetic ions which are separated by large intervening oxygen
ions. The direct exchange between nearest neighbour magnetic ions plays only a minor
role. The mechanism of coupling which involves overlap of the electron charge clouds
(III) Planes of parallel spin are shown dashed

Fig. 9.13 Antiferromagnetic spin arrangement in single crystal MnO. (For clarity only the
Mn2+ ions are marked and the spin direction, actually [112], is arbitrarily drawn as [001)).
of the Mn2+ ions via the oxygen ions is known as superexchange. Consider the simple
line of ions
0 2- - Mn 2T - 0 2 - - Mn 2 + - 0 2 -.
The outer electrons of the 0 2- ion exert their influence through the operation of
Hund's rules and the Pauli principle to force the net moment of the Mn 2+ ions to be
antiparallel. For other magnetic ions having a d shell which is less than half full, ferro-
magnetic alignment can result. For manganese oxide the net magnetic moment of the
compound is zero because of the antiparallel arrangements of moments. The material
is said to exhibit antije"omagnetism. The simplest model of an antiferromagnet is based
on a structure of two interleaved sublattices the individual moments on each being
ferromagnetically aligned but with antiparallel coupling between the two sublattices.
The net moment is thus zero. If the moments of the two sublattices are unequal there
is a resultant magnetic moment and the material is called a jemmagnet. The actual
alignment is a result of competition between superexchange and direct exchange inter-
actions within and between sublattices which may number more than two in com-
plicated cases.
Above a critical temperature, the Neel temperature, TN, thermal energy is sufficient
to disorder individual moments in antiferromagnets and they become paramagnetic.
The magnetic susceptibility of a typical antiferromagnetic oxide is shown in Fig.
9.14. The dashed curves refer to the behaviour of a single crystal where measurements
are made with the applied field parallel (II) or perpendicular (1) to the easy axis of
magnetization; the full curve refers to powdered material. Above TN, X obeys the
following equation:
X = C/(T + 0) where C and 0 are constants. (9.13)
-~-------
TN
Temperature T
Fig. 9.14 Susceptibility-temperature curve for a typical antiferromagnetic oxide.
9.12 Antiferromagnetic compounds
The simplest compounds to show antlferromagnetism are oxides and halides of the iron
group. The oxides are all cubic above the Neel temperature but the structure becomes
slightly distorted in the antiferromagnetic phase. For example NiO contracts slightly
along the [111] cubic axes to become rhombohedral. The halides have rather low
Neel temperatures and become ferromagnetic in large fields. The group encompasses
both dihalides and trihalides.
TABLE 9.5
Surface Structure Crystal symmetry

(above nn
NiO rock salt 523 cubic

CoO rock salt 291 cubic
MnO rock salt 122 cubic
NiCl2 CdCI2* 50 trigonal
FeCl2 CdCl2 24 trigonal
MnC12 CdCh 1'96 trigonal
NU2 CdCl2 75 trigonal
CrCl3 Cdl2 17 hexagonal
MnF2 rutile 72 tetragonal
ex Cr203 corundum 307 trigonal
FeTi0 3 ilmenite 68 trigonal
KCuF 3 perovskite 243 tetragonal
LaMn03 perovskite 100 orthorhombic
LaFe03 peroskite 750 orthorhombic
Cr b.c.c. 312 cubic
CrSb nickel arsenidet 723 hexagonal
* The CdCl2 structure is the f.c.c. lattice of NaCl with alternate

(111) layers of cations removed.
t The NiAs structure consists of alternate hexagonal close packed
layers of Ni and As displaced with respect to each other.
°
Chromium oxide, Cr2 3, has the hexagonal structure of corundum, Ah 0 3 , with a
unique three fold axis. Ilmenite, FeTi0 3 , has another important structure closely
related to corundum. The difference lies in the ordering of the two different cations
into alternate (111) planes. Ilmenite itself is antiferromagnetic. Other important
compounds have the perovskite, CaTi0 3 , structure (Fig. 8.23) usually in a distorted
form; examples are KCuF 3 and KCrF 3' Some orthoferrites with the general formula
MFe03 also have this structure, for example LaMn03 and LaFe03' In LaMn03 the
La3+ ion occupies the cube comers, the Mn 3+ ion occupies the body centre and oxygen
ions occupy the face centres. Table 9.5 summarizes information on typical antiferro-
magnetic compounds.
9.13 Antiferromagnetic domains

Because there is no net magnetic moment in an antiferromagnetic crystal the presence
of domains is not so easily demonstrated as in ferromagnetic materials. A fact which
has assisted their observation is that the transition through the Neel point to the anti-
ferromagnetic state is usually accompanied by a crystalline distortion which is closely
associated with the magnetic interactions. Most work has been done on domains in the
oxides of nickel, manganese and cobalt. Domains in nickel oxide, NiO, will be discussed
as typical.
It has been pOinted out already that the magnetic structure of such an oxide (Fig.
9.13) is an array of antiparallel sheets of magnetic moments lying in (I 11) planes. Two
possibilities exist for an antiferromagnetic domain wall to occur. First, there can be
a rotation of moments within a (I 11) plane or the magnetization direction can change
by rotation in adjacent ferromagnetic sheets, with the plane of the wall perpendicular
to the [111] direction. These are called S walls. Secondly, there can be a change in
orientation of (111) planes characteristic of twinning. The twin wall is the domain wall
and has no thickness. These are called T walls after Roth [4]. Two types of T wall are
illustrated in Fig. 9.15. In (a) each region is joined by a (I 00) plane and in (b) by a
(110) plane.
Twall
(a) (100) wall (b)(11 0) wall
Fig. 9.15 Twalls separating domains (the rhombohedral distortion is exaggerated for effect).
9.13.1 Observation of antiferromagnetic domains
There are no intense local fields associated with these domain walls so direct techniques
used for ferromagnets are not applicable. Fortunately the crystallographic distortion
associated with T wall domains particularly enable them to be observed by three
techniques:
(a) Transmitted polarized light. Each rhombohedrally distorted domain is a uniaxial
crystal with the optic axis (Chapter 10) coinCiding with the contraction axis.
The domain therefore exhibits birefringence and domains can be observed by
rotating the crystal between crossed polars (plate 6).
(b) Specular reflection. This method relies on small angular misorientations at the
surface where T walls emerge.
(c) X-ray topography (Chapter 4). Photographs of domains in NiO are shown in
Plate 7 which also illustrates the variation of lattice distortion with temperature
[5].
9.14 Ferrimagnetism
If the net magnetization of magnetic sublattices is not zero, the material exhibits ferri-
magnetism and possesses a net magnetic moment. This moment disappears above a
Curie temperature T c ' analogous to the Neel temperature, at which thermal energy
randomizes the individual magnetic moments and the material becomes paramagnetic.
The most important compounds are ferrites having the formula (M2+02-)(Fe2 0 3 )
where M is a divalent metal ion which mayor may not be magnetic. The structure is
based on that of naturally occurring spinel, MgOAh 0 3 , Spinel occurs in two forms,
normal and inverse, which have identical crystal structures and simple ferrites take both
forms.
9.14.1 Normal spinel

This structure can be considered as two sublattices A and B. The sites for metal ions on
the A sublattice (A sites) are surrounded by four 0 2 - ions in a tetrahedral coordination
(Fig. 9.16a) while B sites are surrounded octahedrally by six 0 2- ions (Fig. 9.16b). In
normal spinel the divalent ions appear only on A sites and the trivalent Fe3+ only on
B sites. Zinc ferrite (Zn 2+)A 0(Fe~+)B03' is a normal spinel; note that the zinc ion is
diamagnetiC.
9.14.2 Inverse spinel

This is the structure of the majority of ferrites. Here, half of the Fe 3 + are on A sites
and the other half on B sites while all the divalent metal ions are found on B sites.
Examples are manganese and nickel ferrite. The formula for the former may be written
(Fe 3+)A 0(Mn 2+Fe3+)B 0 3'
The important magnetic interactions are of the superexchange type occurring in
A -O-A, B-O-B and A -O-B bonds. The dominant effect is an antiferromagnetic
alignment between magnetic moments on A and B sites. Thus in manganese ferrite
the moment of the Fe3+ ion is 5J.1B and that of the Mn2+ is 5J.1B so that the arrange-
ment of moments per molecule in (Fe 3+)A 0(Mn2+Fe3+)B03 is
•
Metal ion
o
Oxygen ion
(a)
(b)
Fig.9.16 Metal ions in (a) tetrahedral and (b) octahedral coordination.
There is a net magnetic moment per molecule of 5 Bohr magnetons. In a normal spinel
such as zinc ferrite the magnetization of the A sublattice is zero since the Zn 2 + ions are
diamagnetic and so the normally dominantA-B interactions are zero here. The
important interaction is now B-B and this is antiferromagnetic too. Thus the Fe 3 +
ions on the B sublattice arrange themselves antiferromagnetically to give zero moment
at T = o. It follows that the normal spinel zinc ferrite is not ferrimagnetic and the weak-
ness of the B-B interaction is shown by its low Neel temperature of 9 K, below which
this material is antiferromagnetic.
There are other atomic arrangements which lead to a net moment. For example,
there could be unequal numbers of identical moments on the two sublattices. It is also
possible to mix normal and inverse ferrites and achieve a stoichiometric adjustment. If
zinc ferrite is added to an inverse ferrite, the Zn 2 + ions are found only onA sites and
this has the effect of displacing Fe 3 + ions. The net result may be written as follows:
(I - x)Fe~+O(Fe3+M2+)B03 + xZn;tOFe~B03 = (Fet.x Zn2 +)A O(Fe~~+1-xMi~x)B03
inverse ferrite normal ferrite mixed ferrite
Here, a fraction x of a normal ferrite reacts with (1 - x) of an inverse ferrite to form a
new compound, a mixed ferrite. The net moment per molecule of the latter is obtained
by adding the moments remembering that the A and B sub lattice moments are anti-
parallel. Thus the net moment per molecule of mixed ferrite = {5(l - x) -
5(1 + x) - mel - x)} J.IB where m is the magnetic moment of the M2+ ion. As the
proportion of zinc ferrite increases the magnetic moment of the A sublattice is diluted
leading to an increase in magnetization of the substance as a whole.
The earliest magnetic material known, lodestone, is an inverse ferrite, ferrous ferrite
(Fe 3 +)A 0(Fe2+Fe3+)B03. The net magnetic moment per molecule is just equal to that
of the Fe 2+ ion, 4J1B. Barium ferrite, BaFe12019, has important commercial applica-
tions; its crystal structure is hexagonal and is derived from the spinel structure. The large
magnetic anisotropy makes this material suitable for permanent magnets. It is one of
a group of hexagonal ferrites with the general formula AB 12 0 19 where A is divalent
(Ba, Sr, Pb) and B is trivalent (AI, Ga, Cr, Fe).
Other ferrimagnetic materials with more complicated structures are the substituted
garnets based on natural garnet, Mg 3Alz(Si0 4 h. The ferrimagnetic garnets have the
formula M3Fe2Fe3012 where M is a rare earth element or yttrium. Yttrium iron garnet
(YIG) is an important material for applications at microwave frequencies. The yttrium
ions are trivalent and diamagnetic, so that the Fe 3 + ions are the only magnetic ions
present. The structure can be analysed in terms of three sublattices comprising 'A' sites
which are occupied by some Fe 3+ ions surrounded octahedrally by oxygen ions, 'D'
sites occupied by other Fe3+ ions surrounded tetrahedrally by oxygen ions and 'C'
sites surrounded dodecahedrally by oxygen ions. Thus in YIG only the 'A' and 'D'
sublattices are magnetic and their moments are arranged antiparallel.
Various substitutions of other ions can be made in YIG and one of the most impor-
tant is when the diamagnetic y3+ ion is replaced by a paramagnetic rare earth ion.
For example, if gadolinium is used, gadolinium iron garnet, Gd 3 Fes 0 12 , is formed.
This has three magnetic sublattices with the moment of the rare earth ion being
coupled antiparallel to the net moment of the iron ions. The structure is represented
by the formula (Gd3)(Fe2)(Fe3)012 with the magnetic moment per molecule =
(3 x 7) + (2 x 5) - (3 x 5) = 16J1B.
Ferrimagnetic materials become paramagnetic above a Curie point T(! and in this
region the inverse susceptibility X-I versus T curve is a hyperbola (Fig. 9.17). The
constant 0 is the 'asymptotic' Curie temperature. The equation to the curve is ex-
pressible in the form
1 T 0 S
-=-+-- - - , (9.14)
X C C T-¢J
where C, 0, S and rf> are constants. In the limit of large T the last term disappears and the
asymptotic equation is given by the remaining terms.
9 Tc
Temperature T
Fig. 9.17 Inverse susceptibility of a ferrimagnetic material above its Curie point.
Below the Curie temperature the presence of non-equivalent sublattices leads to a

variety of behaviour of the net magnetization M as a function of temperature since
each sublattice has a moment with its own temperature dependence. In the two sub-
lattice case, examples of the temperature dependence of M which can occur are given
in Fig. 9.18. In Fig. 9.18d M drops to zero at P as well as at the Curie temperature. P
is called a compensation point. The form of these curves has been explained by Neel in
terms of an internal field for each sublattice. Table 9.6 summarizes some properties of
typical ferrimagnetic materials.
~ ~
c
.g., c
0
,!:!
.,
'';::;
;c
N
ic
.,Cl .,Cl
~ ~
To T To
(a) Temperature (b) Temperature T
~ ~
c c
0
0
.,
.;::; .,
'';::;
N
N
.~
-.;::;
Ql
C C
Cl Cl
~
'" ~'"
(e) Temperature T (d) Temperature T
Fig. 9.18 Examples of possible temperature dependence of magnetization M in a two sublattice

ferrimagnet; (d) shows a compensation point P.
TABLE 9.6
Properties olle"ites
Material Observed Curie Saturation Initial

magnetic temperature magnetization permeability
moment per Tc(°C) (Wbm-2 )
molecule (JJ.B)
MnFe204 4'6 300 0'49 250

Fe304 4'1 585 0'6 70
NiFe204 2'3 585 0'34 10
MgFe204 1'1 440 0'15 10
ZnFe204 0 -264
9.15 Ferrimagnetic domains-magnetic bubbles [6,7]
Ferrimagnetic domains in certain materials have attracted considerable interest because of

the possibility of altering their shape with externally applied fields in such a way as to
create domains which can be used for storage of information. The materials of interest
are the rare earth orthoferrites and the rare earth iron garnets.
The orthoferrites are not ferrimagnets but antiferromagnets in which the directions
of the sublattice magnetizations make a small angle with each other giving rise to a
magnetic state called weak ferromagnetism. Their structure is based on an orthorhombic
distortion of perovskite and the ferromagnetic moment is usually directed along the c
axis. The Neel temperature is typically about 400°C. Platelets of these crystals with the
c axis perpendicular to the surface show interesting magnetic properties. The field
required to saturate the crystals is about 4000 Am -1 but 20 x 104 Am -I is required to
reverse the magnetization. This reversal occurs by nucleation and growth of domains
of reversed magnetization and the magnetized state is very stable. Domains once
formed can be moved through the sample by a field of only 80 Am-I . The domain
pattern shown in Fig. 9.19a can be modified, by applying a field normal to the crystal
(-) (b)
Fig. 9.19 (a) Domain patterns in bubble domain material change to magnetic bubbles (cylindrical
domains). (b) An application of a field along c axis normal to a crystal face.
face, to become a set of individual cylindrical domains (Fig. 9 .19b) known as magnetic
bubbles. Sometimes both types may be seen simultaneously (Plate 8).
The stability of a bubble domain depends on minimizing the contributions to its
energy E. These contributions are from (a) the domain wall Ew; (b) the demagnetiza-
tion field within the domain Ed; and (c) the applied field H, EH.
Etota! = Ew - Ed + EH · (9.15)
For a domain of radius r and height h
E total = 2rrrhow - Ed + 2MsHrrr2h, (9.16)
where 0 is the wall energy density and Ms is the saturation magnetization. Differentiating
eqn (9.16) to find the value of r for minimum Etota! and rearranging
oEtotatior / oEd/or
-="-- = ow 2rMs - + H. (9.17)
4rrMsrh 4rrMsrh
(a) (b) (c)
Written in this way the numerator of the left-hand side represents a force and each
term on the right-hand side represents a field. Term (a) signifies a reduction in wall area
and (b) an increase in size of domain. Thus if the right-hand side is greater than zero a
decrease in energy is achieved and the domain collapses and if less than zero the domain
prefers to expand. Fig. 9.20 shows the competition between these effects graphically
and the radius rB of a stable domain.
Applied field
contribution
Total energy
.
>
Cl _1,
Q)
c:
w
'- ........
I
- .,,"
I Domain wall
I contribution
I
I
Magnetostatic
energy
fB
Radius r
Fig. 9.20 Contributions to eneIgY of a magnetic bubble domain. A stable domain has radius fB'
Bubble domains may also be seen in thin (5 J..Im) epitaxial layers of rare earth iron
garnets, for example Er3FesOl2 (erbium iron garnet or ErIG), holmium iron garnet or
substituted derivatives with complicated stoichiometry such as Y2'18 Ybo'3Gdo,s2Fe3'9-
Gal'l 0 12 , These materials are usually grown on a substrate of non-magnetic rare earth
garnet, gadolinium gallium garnet (GdGaG), (ErGaG), (yAlG), etc.
Hexagonal ferrites BaFel2019 and PbFe12 0 19 have also been used as domain materials.
The commercial importance of magnetic bubbles arises from the fact that the movement
of bubbles can be controlled by currents through permalloy ftlms laid down by photo
techniques on the surface of the magnetic crystal. This allows the storage and mani-
pulation of large amounts of digital information which can be easily accessible. The
presence or absence of a bubble may be interpreted digitally as '0' or '1'. In the futme,
arrays of magnetic bubble material may replace magnetic tape.
9.16 Magnetic ceramics [8]
Although most of the compounds mentioned have been obtained in single crystal form,
one of the advances which has extended the use of ferrimagnetic materials is their
manufacture in the form of pressed and sintered ceramic powders. Anisotropic pro-
perties may be obtained in such a powder by applying a magnetic field appropriately
during the firing and cooling processes. Being relatively easy and cheap to manufacture,
these materials may be used for all applications of metallic magnets with the particular
advantage of high resistivity and low eddy current losses.
9.17 Applications of ferrimagnetic materials
There are four main headings under which ferrimagnetic materials, primarily ceramic
ferrites, may be grouped for applications. They are:
(1) magnetically hard ferrites for permanent magnets;
(2) magnetically soft ferrites for transformers and inductors;
(3) rectangular loop ferrites for data stores; and
(4) ferrites and garnets for microwave applications.
9.17.1 Permanent magnets

Materials used for this application are barium ferrite, BaFe12 0 19 , and strontium ferrite,
SrFe12 0 19. These are hexagonal ferrites having the crystal structure of magneto-
plumbite, PbFe12019.The materials are characterized by a high value of the uniaxial
anisotropy field and a high coercive force. In addition the resistivity is high, typically
106 ohm m. The high coercive force allows these materials to be used where there are
strong demagnetizing fields, for example as focusing magnets for television tubes. The
high resistivity permits their use as permanent magnets where there is additional
alternating high frequency magnetic flux, without eddy current losses. Typical values
of the important parameters of barium and strontium ferrites are given in Table 9.7.
Commercial names for barium ferrite permanent magnet ceramic materials are
Ferroxdure, Magnadur and Feroba.
TABLE 9.7
Properties of ferrites for permanent magnet materials
SrFe12019
Anisotropic
Isotropic Anisotropic
(BH)max(Jm- 3 ) 8 24
Remanence (Wbm- 2) 0·21 0·38 0·39
Coercivity (Am-I) 14000 13 500 18500
9.17.2 Soft ferrites [10]

The applications under this heading account for a major use of ferrite materials. They
include inductor cores, transformer cores, particularly line output transformers in
television sets, and rod aerials.
The essential requirement is for materials of high permeability, low coercive force,
low eddy current losses and ability to operate up to frequencies of 10 MHz with
special requirements extending to 1000 MHz. The initial permeabilities of manganese
and nickel ferrites are rather low, about 250 and 10, respectively. If, however, these
materials are combined with zinc, the anisotropy is lowered and the permeability in-
creases to about 1000 for manganese zinc ferrite and 700 for nickel zinc ferrite. The
latter has the higher resistivity and lower losses.
The frequency response of the permeability is determined by residual losses since
eddy current and hysteresis losses are small. These residual losses are reminiscent of
the relaxation and resonance effects of dielectrics but domain wall motion is also
involved. The relaxation effects here are of course due to electron spins and the effect
on the permeability JJ.r is represented by treating Ilr as a complex quantity Ilr' - ill/'
to take into account the fact that B is out of phase with the alternating applied field
H. The imaginary part of Ilr is a measure of the dissipation. The behaviour of Ilr' and
Ilr" as a function of frequency is shown in Fig. 9.21 for typical nickel-zinc ferrites.
!J.~
~~
ca
1000 100
.=~;E
Q)
E C-
.- iii 100 10
--
"C+:
lii :s
-~ 0
~!Il
-;;t: 10
Q) ca
a:C-
1 L-_ _L-_ _...L.-_ _....L._ _...L.----J 0.1

0.1 10 100 1000
Frequency (MHz)
Fig. 9.21 Permeability spectra for Ferroxcube IV (Ni-Zn Ferrite NiO: ZnO 25 : 25).
A familiar commercial name for ferrites for these applications is Ferroxcube. For
very high frequencies of 200 to 1000 MHz other compounds known as Ferroxplanas
are used [11]. These are materials called Y compounds (Ba2Me2Fe12022) and Z
compounds (Ba3 Me2 Fe24 0 41 ) where Me is a divalent ion from the first transition
series or zinc or magnesium. These materials which have complicated structures are
hexagonal ferrites with the easy direction of magnetization in the basal plane, and not
parallel to the hexagonal axis as it is in barium ferrite (M compound). There are two
anisotropies associated with this arrangement, one for the movement of the magnetiza-
tion vector in the basal plane and one for movement out of it. The former is low and
the latter high, and Ilr is determined by the lower and the upper frequency limitation
on Ilr by the higher. Fig. 9.22 compares the frequency response of Ilr for Ferroxplanas
with nickel zinc ferrite. Table 9.8 summarizes properties of soft ferrites and Table 9.9
gives information on Y and Z compounds.
9.17.3 Rectangular loop /errites

Some ferrites have hysteresis loops which are almost rectangular in shape. This property
makes them suitable for use in a magnetic memory core. The principle of operation of
such a core can be discussed by reference to Fig. 9.23. This shows an ideal rectangular
hysteresis loop ABCDEF. The points Po, PI represent two stable states of magnetiza-
tion of a ferrite material which is usually in the form of a small toroid. These states
can represent a zero and a one in digital storage of information.
The loop can only be traversed in an anti-clockwise direction and the state Po can
be changed rapidly to PI by the application of a field greater than or equal to H A •
Similarly PI can be changed to Po by the application of a field less than or equal to
-HD • The switching time is about 1 IlS and is an important parameter.
100~-------------------------------,10
,,_-..... h..
/ ----,!).
/\ fl'!"",
, Nickel zinc e "
!_ ferrite /
10 --:ID:=;':f -:7'
~_~:~ e ·1
,. II . ' ,, " \
,.. " ,
I
,/ /. "
0.1
10 100
Frequency (MHz)
(a)
100 10
/ ' - ..... , / ............

/ },
I "
,
I
I /'
Nickel zinc
'
10 - -
rfIr'
---.-;-;;.;-.=;,..::;--.
,__
e-.
• __ ferrite
,
I ' ".
e-~.~---'.~.
I " ."
n" I " .
rr
I
, I '
"
'
I '
/
/ 100 1000
Frequency (MHz)
(b)
Fig. 9.22 Comparison with nickel zinc ferrite of the frequency response of the real and imaginary
parts of the permeability of sintered samples of Ferroxplanas (a) cobalt Z compound and (b)
magnesium Y compound (12).
Figure 9.24 shows a two-dimensional array of ferrite cores wired as a matrix to store
information. If current corresponding to the field HA /2 is passed through an X and a Y
wire, only where they intersect will the field be of sufficient magnitude to switch that
core should it be in state P0(0). If in state (1) already it will stay in that state. A
negative current corresponding to a field -HD/2 in both wires will cause the core at
the intersection to change from (1) to (0) if in state (1) but will have no effect if in
state (0). By this means information can be read in and out in digital form in three-
dimensional matrix arrays of ferrite cores. In practice a third wire is required to detect
the current pulses due to the flux change when there is a change of state (0) to (1) or
TABLE 9.8
Composition (mole %) Curie Saturation Initial relative Coercive Resistivity

temp (OC) induction permeability force (Urn)
(Wb JJl2) (ILr) (Am-I)
Ferroxcube A
MnFe204 ZnFe204
48 52 100 0'33 1400 15'9 0'2
79 21 210 0'51 700 39'7 0'8
Ferroxcube B
NiFe204 ZnFe204
36 64 125 0'36 650 31'8 10 3
80 20 400 0'36 45 333'5 10 3
TABLE 9.9
Me Saturation induction at 20°C (Wb m- 2 )
(Y compounds (Ba2Me2Fe120n or 2BaO' 2MeO 6Fe203)

Mn 0'21 290
Co 0'23 340
Ni 0'16 390
Zn 0'28 130
Mg 0'15 280
(Z compounds (Ba3Me2Fe24041 or 3BaO 2MeO 12Fe203)
Co 0'33 410
Cu 0'31 440
Zn 0'39 360
P
c 8
0 A H
D
E Po F
Fig. 9.23 Ideal ferrite hysteresis loop.

r
r ,... r r
x, f.J iJ .J .J
X2
r r r (
f.J f.J ..; J
:>--- f--
X3
r r r r
f.J f.J f.J ..;
X4
r r r (
f.J W f.J .J
t IHA/2
Y, Y3
Y2 Y4
Fig. 9.24 Two-dimensional matrix of ferrite cores as information store.
(1) to (0) in reading out. Also the read-out destroys the information already present and
this information must be written back electronically. A fourth wire is used to inhibit
the reading in of states which are not required.
Ferrites commonly used for this application are manganese magnesium ferrite,
manganese copper ferrite and lithium nickel ferrite. Ideal loops are not attainable in
practice and an actual loop looks like Fig. 9.25. The departure from the ideal is mea-
sured by the ratio of the induction at H m/2 to the maximum induction B m. This
quantity is called the squareness ratio for the loop. Table 9.10 gives some properties
of square loop ferrites.
----~----~~~~-------H
Fig.9.25 Typical hysteresis loop of ferrite in a matrix store.

TABLE 9.10
Magnetic properties of square loop ferrites
Material Maximum * Remanent Coercive Maximum Hm Tc(°C) Permeability IJ.r

flux flux force squareness (Am -I) Initial Maximum
density density (Am-I) ratio
(Wbm- 2 ) (Wb m':2) atHm
Mn/Mg/Zn 0'25 0'21 23'8 0'95 43'7 160 260 4500

ferrite
Mn/Mg/Cd 0'24 0'2 15'9 0'92 27'S 150 200 4700
ferrite
* Hm = 794 Am-I.
9.17.4 Microwave!e"ites [13]

The applications involved here are those in which some processing of e.m. waves is
done in the frequency range 1 to 100 GHz. This processing depends on the interaction
of the e.m. waves with precessing spin magnetic moments in the ferrite. The discussion
is restricted to one of the most important of these processes known as Faraday rotation.
This is the rotation of the plane of polarization of a plane e.m. wave as it travels through
a ferrite in the direction of an applied magnetic field.
The two basic steps in the argument are that a plane polarized wave is equivalent to
two circularly polarized waves, polarized in opposite senses. These two waves interact
differently with precessing spins and so encounter different permeabilities. The different
permeabilities influence their velocities and the two waves undergo different phase shifts
in travelling a given distance. The phase shifted waves are equivalent to the original
plane polarized wave with its plane of polarization rotated.
The precession of spin magnetic moments in an applied field comes about because
of the angular momentum J of the electron. If the electron spin axis is deflected by an
angle () from its alignment with the magnetic field a restoring couple JJil sin () acts to
oppose the change. Due to its angular momentum the electron spin axis will not return
immediately to its position of eqUilibrium but will behave like a top and precess about
the direction of H.
To understand the mechanism of precession consider a vector diagram of the be-
haviour of the resolved component J in the (x, y) plane as viewed along the z direction,
Fig. 9.26b. Initially this resolved component is represented by the vector OA. By
Newton's law the rate of change of angular momentum equals the couple applied. In
this case the couple JJil sin () (M is here the spin magnetic moment J.I of a single electron)
acts to produce a change of angular momentum in the (x, y) plane, in time ~t, of
JJil sin () ~t represented by vector AB. Note that the direction of AB corresponds to a
couple tending to realign the spin axis with H. The resultant of OA + AB is OB which
means that J sin () has precessed an angle ~I/> clockwise, as viewed along directions +z
and H, in time ~t.
From the diagram
AB =J sin (}~I/>
therefore
JJil sin () ~t =J sin (}~I/>.
H
('---- ---- ... , M

........... _-
z
/L,
(0)0 0H
lL,
y
(a) (b)
Fig. 9.26 (a) Precession of a magnetization vector M in presence of field H applied in the z
direction. (b) Motion of component of angular momentum vector J in the xy plane.
Since dt/>/dt = Wo the precessional angular velocity

Wo =1JlIfJ, (9.18)
where Jl.fJ is a constant, the gyromagnetic ratio 'Y whose value for electron spin is
r
35 kHz (Am- 1 1 •
Suppose a ferrimagnetic material is saturated having magnetization M. If the align-
ment of M is disturbed, it precesses, representing the motion of all electron spins pre-
cessing together. Consider a magnetic material with saturation magnetization M Wb m-2
in the presence of a field H applied in the z direction, with a high frequency magnetic
field whose amplitude is small compared to H applied in the xy plane (Fig. 9.26). There
is a precession of the magnetization vector M clockwise about H when viewed along
the direction of H and at angle 0 to H.
Suppose that the alternating field h is clockwise circularly polarized with maximum
amplitude h.. By analogy with mechanical forced vibrations, h. rotates in phase with
M sin 0 for w < wo, the resonant angular velocity, and as w increases 0 increases. At
the resonant frequency the rotation of M sin 0 and h. get out of phase. The clockwise
circularly polarized alternating magnetic flux density b+ is given by
b+ = Jl.oh. + M sin 0 (9.19)
and the corresponding relative permeability is
Jl.oh. +Msin 0 MsinO
Il+= = 1+--. (9.20)
Jl.oh. Jl.oh.
By contrast an anticlockwise h.. does not couple to the clockwise precession of M and
the corresponding permeability J.L is almost constant and equal to unity over the fre-
quency range of interest.
In practice, to explore the frequency response of the permeability Jl.ro it is usual
to keep the high frequency field at a fixed w and vary the applied field H, because
Wo ='YH. The results are given in Fig. 9.27 which shows the high frequency perme-
ability of a ferrite to Circularly polarized waves. This is the graph of the real part Jl.r'
of the complex permeability. The absorption of energy is indicated by the value of the
imaginary part f..lr". The absorption occurs at resonance, the sharpness of the resonance
being measured by the width at half power points.
,
[1.±
[L'- _ _ ~
Resonant Ho =~
field I~I
Fig. 9.27 Radio frequency permeability of a ferrite to circularly polarized waves. (Ilf± and Il;
are plotted as a function of H with w constant.)
Now suppose that a plane polarized high frequency e.m. wave is travelling along a
piece of ferrite in the direction of an applied field H. This wave is equivalent to two
circularly polarized waves (Fig. 9.28a). It has been shown that these encounter different
permeabilities and since the velocity in the medium v = C/l1r€r and the phase constant
~ = (W/C)l1r€r (where c is the free space velocity of the waves) the waves will travel with
fV\ (]
_~~o)
6 h_(z~d)
0~
zaxis
(Ld
(a) (b) (e)
Plane z =0
z=O z= 0
(d)
Fig. 9.28 Phase relationship of two circularly polarized waves h± travelling a distance d in a ferrite
along the direction of the applied field H (z direction). (a) At z = O. (b) h+ at z = d. (c) h_ at z = d.
Cd) Resultant of h+ and h_ at z =d.
TABLE 9.11
Properties of microwave ferrimagnetic materials
Material Initial Saturation Frequency g Curie tem· KdJ1.oMs Linewidth Frequency Relative Dielectric
permeability magneti- of max J1." factor perature Tc AH(Am- 1 ) (GHz) permittivity loss tangent
zation Ms (MHz) (OC) (Er) (tan Ii)
(Wbm- 2 )
Single crystals at room temperature

MnFe204 0·52 2 ± 0·01 300 -71 4456 9·1 s:
NiFe204 0·34 2-19 585 -236 5968 24·2
>-
0
CoFe204 0·14 2·43 (90°C) 440 2070 3183 9·0 Z
t!1
51:e2033Y 20 3(yIG) 0·17 2·005 287 - 45 2467 24·0
5Fe2033Sm203(SmIG) 0·17 1·95 -185 19·1 x 104 9·0 ~
5Fe203 3Er203 (ErIG) 0·11 1·73 283 - 95 93·9 x 10 3 9·0 '"C
~
Ferrites (typical commercial ceramics) 0
'"C
t!1
Nickel ferrite 0·3 2·3 575 27·9 x 10 3 18·6 0·006 ~
Nickel (AI) ferrite 0·145 2-5 440 23·9 x 10 3 9·5 0·005 ""'l
Nickel ferrite 0·02 250 t!1
12 rn
-
Nickel (Mg) ferrite 9 0·007 80
Nio·3Zno·7 Fe204 3800 0·018 0·5
Magnesium (Mn) ferrite 0·16 2·0 51·7 x 10 3 9·5 0·005
Magnesium (Mn)(AI) ferrite 0·06 2·0 63·7 x 10 2 11·2 0·0005
Garnets (commercial)
YIG 0·17 2·0 275 47·7 x 10 2 14·5 0·003
YI(Al)G 0·03 2·05 125 43·8 x 10 2 11·7 0·002
YI(Al, Gd)G 0·07 2·0 200 95·5 X 10 2 14·2 0·002
N
......
Vl
different velocities and get out of phase in travelling a distance d. The clockwise
component is retarded by {3+d rad in travelling a distance d (Fig. 9 .28b) while the anti-
clockwise component is retarded by {3_d rad (Fig. 9.28c). The result (Fig. 9.28d) is a
net rotation of the original plane polarized wave through a clockwise angle ({3- - {3+)/2
per unit length of travel in the ferrite.
Faraday devices are best operated in the region of low loss between the resonance
absorption 14' (Fig. 9.27) and the low field losses where the ferrite is not magnetically
saturated. In this region /1:'" > /1~+ and so f3- > {3+. The direction of rotation depends
only on the direction of the applied field and not on the direction of propagation, so
a reflected wave continues to have its plane of polarization rotated clockwise. This is
said to be a non-reciprocal property. The magnitude of the rotation is essentially
determined by the saturation magnetization and relative permittivity of the ferrite. A
typical value is 104 deg m-I •
The most direct application of Faraday rotation is to use waveguides just as one
uses polarizer and analyser in optics, to accept or reject plane polarized waves. Thus,
unwanted reflected signals are prevented in isolators and rotations of the plane of
polarization are achieved in gyrators. More complicated operations are carried out in
phase shifters and circulators. Typical properties of microwave ferrites are listed in
Table 9.11.
References
1. Tebble, R. S. Magnetic Domains, Methuen (1969).

2. Isaac, E. D. and Carey, R. Magnetic Domains, English University Press (1966).
3. Craik, D. J. and Tebble, R. S. Ferromagnetism and Ferromagnetic Domains, North-Holland
(1965).
4. Roth, W. L. J. Appl. Phys. 31, 2000 (1960).
5. Vernon, M. W. Phys. Stat. Sol. 37, KI-K3 (1970).
6. Bobeck, A. H. and Scovil, H. E. D. Sci. Am. 244,78-90 (1971).
7. Bobeck, A. H. Bell System Tech. J. 46, 1900-1925 (1967).
8. Smit, J. and Wijn, H. P. J. Ferrites. Philips Technical Library (1959).
9. Snelling, E. C. Proc. Brit. Ceram. Soc. 2, 151-174 (1964).
10. Snelling, E. C. Soft Ferrites. Properties and Applications, IliCCe (1969).
11. Jonker, G. H., Wijn, H. P. and Braun, P. B. Philips Tech. Rev. IS, 145-154 (1956).
12. Jonker, G. H., Wijn, H. P. and Braun, P. B. Proc. lEE I04B, 249-254 (1957).
13. Lax, B. and Button, K. J. Microwave Ferrites and Ferrimagnetics, McGraw-Hill (1962).
Questions
1. Anhydrous nickel chloride, NiCh, has a paramagnetic susceptibility of 78·5 x 10-8

kfl at 20°C. The atomic weights of nickel and chlorine are 58·7 and 35·5 respectively.
Using the Simplified Langevin formula calculate the magnetic dipole moment of the
NiH ion in Bohr magnetons.
2. The saturation induction of nickel is 0·65 Wbm- 2 • If the density is 8906 kgm- 3
and its atomic weight is 58'7 calculate the magnetic moment of the nickel atom in
Bohr magnetons.
3. The Curie temperature of iron is no°e. Estimate the magnitude of the Weiss internal
field.
4. A 180° magnetic domain wall, N atoms thick, lies perpendicular to a [100] direction
in a simple cubic lattice of atomic spacing a. Show that for the equilibrium situation
of minimum energy, the anisotropy energy 'YK per unit area of wall is equal to the
exchange energy Eex per unit area of wall and is given by
where J is the exchange constant, S the total spin quantum number and K the anisotropy
constant. (Hint: assume that 'YK is K per unit volume of domain wall.)
s. Calculate the net magnetization per molecule of
(a) manganese ferrite (Mn 2+Fe 3 +)B(Fe 3 +)A 0 4 , and
(b) yttrium iron garnet (Y~+)A (Fe~}B(Fe~+)C012'
where the arrangement of ions on sublattices A, Band C is indicated by the subscripts.
(Assume a simple antiferromagnetic arrangement of spins on the relevant sublattices.)
10 Optical Properties
10.1 Introduction
When a material is illuminated with light there are several processes that can occur as a
result of the interaction between the light and the material. Some light may be lost
and the energy transformed into heat in which case it is absorbed. Some, however, may
pass through without loss, i.e. transmitted,or scattered back from the surface of the
material, Le. reflected.
Different optical materials exhibit each of these phenomena. Absorption is the basic
mechanism needed for the detection of light, reflection is required for mirrors and
transmission is essential for optical components such as lenses and prisms. It is there-
fore of fundamental importance to understand how these phenomena arise.
The basic interaction which gives rise to all optical properties is that between the
electromagnetic (e.m.) field of the light (particularly the electric vector) and the charges
contained in the material. This is always the basic process but its precise form depends
very much upon the nature of the charges and their distribution, that is whether they
are electronic or ionic, whether they are free as in a metal or bound as in a semicon-
ductor or insulator.
To appreciate the material parameters which dictate the optical properties it is
necessary to understand this basic interaction. To do this requires not just a knowledge
of the charge distribution but also a description of the light. Unfortunately there is no
single way of representing light which provides a suitable description of all the optical
properties of interest, and so it will be necessary to adopt two distinct approaches.
Where propagation is of prime importance, as in transparent media, the optical para-
meter of most importance is the wavelength. For these situations the classical model
of a continuous transverse electromagnetic wave of wavelength Aand velocity C is
adopted. In this chapter the properties discussed will be confined to the region of wave-
length between 0·1 J,Lm (1000 A) in the ultra-violet and 50 J,Lm in the infra-red. It is
worth noting that the visible region occupies the range 0·4-0·65 J,Lm.
Wherever absorption is involved the energy carried by the e.m. wave becomes
important, and for these situations it is necessary to adopt the quantum approach and
to consider the light as consisting of many individual particle-like packets of energy,
i.e. photons. Each photon possesses an energy E where
E =hv =hC/A, (10.1)
v and h being the frequency of the light and Planck's constant respectively. In energy
terms the region of interest (0·1-50 J,Lm) corresponds to approximately 12-0·025 eV.
OPTICAL PROPERTIES 219
10.2 Refractive index
The various charges which make up a solid will all respond in some measure to the
incidence of an e.m. wave. The electric vector of the wave will force the charges to be
displaced with respect to their initial positions and so produce a dipole. The net
polarization produced will be the sum effect for all charges but will not comprise equal
contributions from every charge. The tightly bound electrons making up the core of
an ion will, if at all, be only very weakly polarizable, whereas the free electrons of a
metal and the weakly bound outer shell electrons of a semiconductor will contribute
much more.
Since the electric vector of the e.m. wave is oscillatory, so will be the induced dipoles,
providing the charges are able to follow the rapidly fluctuating field. The heavy ions
are able to follow the field only at and below infra-red frequencies and so contribute
little to the polarization in the visible region, whereas electrons only experience
difficulty in responding at frequencies corresponding to the ultra-violet part of the
spectrum. If it is assumed that there is a negligible energy loss by the oscillating dipoles,
then they will eventually re-radiate at the same frequency as that of the excitation. In
other words, the presence of the charges and the interaction with the e.m. wave has
not caused any energy loss but has merely delayed its transmission. The material will
exhibit transparency but the 'delaying' action reduces the effective velocity of the
light. The material is said to possess a refractive index n where
velOCity of light in vacuum
n= . (10.2)
velocity of light in the material
The refractive index thus derives from the polarization of the material. The greater the
polarization the more will be the delaying action, and hence the greater the value of n.
It is a result of e.m. theory [1] that for non-magnetic materials
n = (€r)1/2. (10.3)
A medium containing no polarizable charges would obviously have a value of €r of
unity; there would be no delaying action and n = 1. For a material generally, the
greater the density of dipoles the higher will be €r and hence n. The more massive an
1.8
). =0.58 I'm
)(
CD
"tI 1.7
.5
CD
>
~
u
co
....CD
~
a: 1.6
1.5 L - ........._ _...J...._ _ _- " -_ _ _- - '

2.000 3.000 4.000 5.000
G lass density (kg m -3)
Fig. 10.1 Refractive index as a function of density for a range of Chance-Pilkington optical glasses.
atom the more electrons there are per atom and so it is to be expected that a dense
glass, for example, will contain more electrons per unit volume than a less dense glass.
Variations in density will thus produce a variation in refractive index and this is
shown in Fig. 10.1 for a selection of commercial glasses. Glasses, like most ionic
materials, have a refractive index between 1 and 2 whereas the more polarizable semi-
conductors can have indices greater than this. Table 10.1 shows the values for some
semiconductors, with a few more commonplace materials for comparison.
A discussion of refractive index as defined by eqn (10.2), and the various phenomena
associated with the propagation of light through a material is only meaningful at
frequencies for which the material is transparent. The range of transparency for
different materials will be discussed in section 10.3.
TABLE 10.1
Refractive indices
Ice 1·31 at 71. =0·59 /lm

KG 1·49 at 71. =0·59 /lm
Quartz 1·54 at 71. =0·59 /lm
Diamond 2·42 at 71. =0·59 /lm
Ge 4·09 at 71. = 2·15 /lm
Si 3·45 at 71. = 2-15 /lm
GaAs 3·30 at 71. = 5 /lm
InSb 3·96 at 71. =10 /lm
PbS 4·10 at 71. = 3 /lm
PbTe 5·35 at 71. = 3 /lm
ZnS 2·37 at 71. =0·59 /lm
As2 S3 2·38 at A = 2-15 /lm
10.2.1 Birefringence
Ordinary glass is completely isotropic in its properties. Many important optical materials
however, such as single crystal KDP(KH 2 P04 ), or BaTi0 3 are anisotropic. Atomic and
hence dipole density vary with crystal direction and as a result the polarization is
electric field direction dependent. It follows that if €r is dependent upon direction then
so is the refractive index. However, the refractive index for a given light path in a
material is determined by the value of €r associated with the value of II which is in a
direction perpendicular to this path, since the e.m. wave is a transverse wave, with its
electric vector II oscillating in a plane perpendicular to the wave velocity direction
(Fig. 10.2). So that if €r is direction dependent within this perpendicular plane, the
refractive index will be dependent upon the plane of polarization of the light. This is
an important phenomenon and one which is utilized in many optical devices. It is
termed birefringence and occurs naturally in some materials such as KDP and BaTi0 3 •
Birefringence may be enhanced by the application of external forces such as electric
and magnetic fields and even induced by the same means in otherwise non-birefringent
materials. Birefringence might not seem dramatic since n only changes by the order of
2 per cent (in KDP n ranges from 1-47 to 1·51) but the discussion in sections 10.5 and
10.6 will show this to be a very significant change.
z
Fig. 10.2 Birefringence: the velocity of light in direction z, and hence the refractive index n,
depends on the value of €r in the plane perpendicular to z.
10.2.2 Dispersion
In Chapter 8 it was shown that when a material possesses permanent dipoles the per-
mittivity is not a constant at low frequencies but varies with frequency as a result of
relaxation processes. These have no effect in the optical region but the processes of
induced dipole formation do. As a result of the frequency dependence of Er in the
optical region, the refractive index is dependent on frequency. This is referred to as
optical dispersion and is an essential property for many applications in optical instru-
mentation, since without it the prism in a prism spectrometer, for example, would be
ineffective in splitting white light into its various wavelengths or colours.
Optical dispersion is-of particular importance for the transparent glasses such as fused
Si0 2 and arises from the interaction between the e.m. wave and the bound electrons
and ions which make up the glass_ As a consequence of the forces of binding, each
charge can be characterized by a natural resonant frequency, Vo given by eqn (10.4),
where m is the mass of the bound charge and G is the force constant.
vo 2 = G/4rr'lm. (lOA)
The mechanics of the forced oscillation of such charges is treated in many texts [2,3].
For frequencies well below resonance the induced dipoles have little difficulty in
following the applied field whereas above it there will be very little induced polariza-
tion since the variations in the electric field will be too rapid. The resonant frequencies
calculated from eqn (1004) are such that for electrons they lie in the ultra-violet and
for ions they lie in the infra-red. For a glass in the visible region the refractive index
will therefore be primarily due to the bound electrons since the frequency of the light
will be well above that of resonance for the ions, but below that of the electrons.
As the optical frequency is increased towards the electron resonant frequency, the
greater will become the amplitude of the excited electron motion. As a result the
amplitude of the oscillatory polarization produced will increase with frequency with a
consequent increase in the refractive index. The increase of n with v (decrease of n with
A) is known as normal dispersion and is shown in Fig. 10.3 for fused silica. It is found
that the dependence upon A can be represented approximately by
n'l =A + B/A'l + C/A4 , (10.5)
1.54
1.52
~
"
.s
CD 1.50
~
f!
~1.48
1.46
0.2 0.3 0.4 0.5 0.6 0.7 0.8

Wavelength (I'm)
Fig. 10.3 Optical dispersion in fused silica at 20°C.
where A ~ B ~ C In addition to the normal dispersion shown in Fig. 10.3 there will
be a corresponding region of normal dispersion on the low frequency side of the ionic
resonances, which will occur in the infra-red.
In the immediate vicinity of a resonance frequency the refractive index decreases
with frequency. This property is not normally utilized for instrumentation and is termed
anomalous dispersion (see Fig. 10.4).
Radio frequencies Infra red Visible U.V. v

(a)
(b) v
Fig. 10.4 A schematic representation of the frequency dependence of (a) refractive index and
(b) absorption, for a material containing permanent dipoles, bound ions and bound electrons.
The complete spectral variation of optical dispersion resulting from bound electrons
and ions is shown schematically in Fig. 10.4. The true picture is much more complicated
because of the many possible resonant frequencies that exist, particularly in the ultra-
violet. For comparison with the discussions of Chapter 8, Fig. 10.4 also shows the
behaviour at much lower frequencies where the relaxation of permanent dipoles be-
comes important. It might be thought misleading to think in terms of refractive index
for these low frequencies, in which case the vertical axis can be considered as (€r)1/2.
The most important point about Fig. 10.4 is that every polarizable charge contributes
fully to €r and hence n, at frequencies well below its particular resonance frequency.
As frequency is increased, first the permanent, then the ionic and finally the electronic
dipoles become unable to respond. There is a general tendency for n to decrease with
increasing frequency, finally reaching the value of 1.
10.3 Absorption
The complete absorption spectrum will derive from the effect of all the energy loss
mechanisms that can result from the interaction between the light and the charges con-
tained in the material. The possible absorption processes comprise three types, not
necessarily all present in every material. The processes depend on whether the charges
are:
(a) tightly bound as are the inner shell electrons of the lattice ions, or the lattice
ions themselves, ,
(b) loosely bound such as the outer shell electrons of the lattice ions, or
( c) free as are the conduction electrons in a metal or semiconductor.
Charges of type (a) are those giving rise to optical dispersion and are characterized by
a resonance frequency given by eqn (10.4). By arguments similar to those given for the
dielectric relaxation process in Chapter 8, excitation by light of frequency near reson-
ance leads to a pronounced absorption (energy dissipation). The presence of both
bound electrons and ions thus leads to absorption in the ultra-violet and infra-red
regions of the spectrum. These absorptions extend over relatively narrow bands of
wavelengths and are shown (schematically) in Fig. 10.4 for electronic and ionic charges.
The absorptions corresponding to the ionic resonances are referred to as Restrahlen
absorptions.
The loosely bound charges of type (b) are best described by the electronic band
theory (Chapter 1) and absorption results from interband excitation. It can only occur
between occupied and unoccupied states of energy. If these states are separated by an
energy M, absorption will only occur provided the photon energy equals M (see Fig.
10.5), i.e.
V = Mlh (10.6)
hence
A = helM.
This fundamental absorption is characterized by a very broad spectrum since the broad
energy bands give a wide choice of transitions. The most important transitions for non-
metallic materials are those between the valence band and the conduction band. Every
material is characterized by an energy gap Eg so that a minimum photon energy exists
which will give excitation resulting in absorption. From eqn (10.6) this leads to a
critical wavelength
A=helEg (10.7)
at which there will be a sharp edge in the absorption spectrum. To the long wavelength
side of this edge the material will be transparent.
Conduction
band
11
IIe
c::
Il.E
Eg
1j
CD
W
Fig. 10.5 The absorption of a photon by a valence electron.

Finally, there may be free electrons in a material and these are very polarizable
interacting readily with an incident e.m. wave. They do not move completely indepen-
dently of the lattice structure but may, in their motion, interact with a phonon. A loss
in energy may result before the charge re-radiates the light and hence absorption occurs.
This free carrier absorption obviously increases with the number of electrons but
equally important it can be shown [4] that the absorption coefficient a increases
approximately as the square of the wavelength, becoming more significant in the infra-
red, i.e.
a =constant X2 • (10.8)
If light of intensity lois incident on a slab of thickness x, and light of intensity I is
transmitted, the absorption coefficient a is defined, neglecting reflection losses, by
1=/oe- ax . (10.9)
Having discussed the three absorption processes individually it is useful to consider
how they combine to give the observed absorption spectra of ionic, semiconducting
and metallic materials. The effect of imperfections will also be considered. Whether
they are deliberately introduced impurities, or lattice defects, they can severely modify
the absorption spectrum.
10.3.1 Ionic materials

Ionic materials contain no free charges and the absorption processes that can occur are
those through ionic resonance in the infra-red, electronic polarization in the ultra-violet
and interband absorption. The last also occurs in the ultra-violet since a considerable
energy is required to free the outermost electron from an ion such as a-in KCl (i.e.
Eg is very large). Ionic materials, then, are transparent over a broad spectral region from
the ultra-violet to the infra-red. The extent of this transparent 'window'is determined,
in the infra-red limit, by eqn (10.4). For example, the transparency of CsI extends
further into the infra-red than KCl because of the more massive ions (larger m in
eqn (10.4». Similarly the harder the material (i.e. larger G), the less extensive is the
'window'.
A list of ionic materials and their spectral ranges for use as optical media is given in
Table 10.2.
10.3.2 Semiconductors
Semiconductors possess charges of all kinds, bound and free and so exhibit some of
the optical properties characteristic of each. The most important charges are those
OPTICAL PROPER TIES 225
TABLE 10.2
The transparent window of some ionic TTIIlterials (jlm)
Optical glass 0·3-2·7

Quartz 0·15-5·0
liF 0·11-6·0
NaO 0·19-15·0
KO 0·20-21·4
KRS-5 (TIBr-TIl) 0·5-37·5
CsI 0·24-50·0
MgO 0·4-9·7
CaF 2 0·13-9-1
Al2 0 3 0·2-5·5
associated with the valence band and their excitation by interband transitions to the
conduction band. All semiconductors will possess a characteristic absorption edge
given by eqn (10.7) corresponding to the onset of interband transitions, on the long
wavelength side of which they will be transparent. Table 10.3 includes a range of semi-
conductors, their energy gaps and absorption edges. A typical example is ZnSe
which appears yellow in transmission since its edge occurs in the visible region whereas
InSb is opaque since its edge occurs in the infra-red. The net result of the interband
transitions is to give rise to free electrons and holes, which mayor may not recombine
at a later time.
The exact nature of the absorption edge depends very much on the particular semi-
conductor and does not necessarily occur at exactly the same photon energy as the
thermal energy gap E g • The reason for this lies in the availability of conduction band
energy states relative to the valence band, and requires reference to the energy-
momentum (E, k) diagram. Appendix I shows that the theoretical E, k dependence
for a one-dimensional array of regularly spaced atoms is parabolic. However, a real
TABLE 10.3
Semiconductor absorption edges
Eg (eV) A (jlm)
InSb 0·2 6·2

PbTe 0·22 5·6
PbS 0·4 H
PbSe 0·5 2·5
Ge 0·7 1·65
Si 1·1 1·1
GaAs 1·4 0·89
GaP 2·2 0·62
CdS 2-4 0·52
ZnSe 2-6 0·48
Zns 3·7 0·34
crystal is three dimensional and there must be a separate E, k dependence correspond-

ing to each of the dimensions. For the simple cubic structure it is parabolic for each
direction and the maximum in the valence band lies at the same value of k as the
minimum in the conduction band. For many semiconductors, however, the crystal
structure is more complex. The E, k dependence may not necessarily be parabolic and
may vary with crystal direction. Furthermore, the minimum in the conduction band
does not necessarily lie at the same value of k as the maximum in the valence band.
Some semiconductors (for example, GaAs) possess a band structure in which the
minimum in the conduction band does lie directly above the maximum in the valence
band, and these are called direct gap semiconductors (Fig. 10.6). Others (for example,
Ge, Si) have the minimum displaced, and these are called indirect gap semiconductors
(Fig. 10.7). The thermal energy gap Eg in each case is defined as the minimum energy
>-
Cl Conduction band
Q;
t:
Q)
...
<\I
...
1~
t:
Q)
0
Q.
t:
...e
0
Q)
iii
Fig. 10.6 Optical interballd transitions in a direct band gap semiconductor.
Fig. 10.7 Optical interband transitions in an indirect band gap semiconductor.
difference between bands irrespective of k, but the onset of intense interband absorption,
i.e. the absorption edge, is represented by the minimum energy difference for a con-
stant k. The reason for this is that the most likely optical transition is one for which
there is a negligible change in k. Momentum must always be conserved and since the
photon momentum is very small in comparison with electron momentum, the most
likely transitions are represented by vertical lines in Figs 10.6 and 10.7, i.e.
(10.10)
where k j and kf are the initial and final momenta of the electron taking part in the
transition. These are referred to as direct transitions. In Fig. 10.7 a smaller energy
10
I
.§.
..
c:
Gl
~ 10
o
..g...
u
103
Co
o
~ 10
0(
1 0 I:--~---:-I~--:-L:--~,:",
0.6
Photon energy h" (eV)
Fig. 10.8 Optical absorption in Ge at 77 K [5].
photon is required to excite an electron from the maximum of the valence band to the
minimum of the conduction band but eqn (10.10) is not obeyed and it is necessary
for a third body to take part in the photon-electron interaction for momentum to be
conserved. A lattice phonon may be absorbed and this less likely process is known as
an indirect transition.
Hence the absorption edges of indirect gap semiconductors possess a second weaker
absorption edge to the long wavelength (low energy) side of the first edge due to the
possibility of indirect transitions. Fig. 10.8 shows this for Ge.
In addition to the mechanism of interband transitions, absorption also occurs in the
ultra-violet due to electronic polarization. This can be very intense but since it occurs
at shorter wavelengths it does not influence the position of the absorption edge. If
the semiconductor is a compound one with a degree of ionicity in its bonding, there
may be an ionic resonance in the infra-red with an accompanying restrahlen absorption
band. As a result of thermal excitation there are many free carriers in a semiconductor,
1.5
I
E
'"o
x
.. c:
Gl
1.0
·u
~o
u
c: 0.5
..;::;o
...Co
oIII
.c
0(
Fig. 10.9 Free carrier absorption in InSb doped N-type [6].

both electrons and holes. These also absorb and for very narrow band gap materials,
such as InSb, the carrier concentration and hence the absorption in the infra-red can
be large (Fig. 10.9).
Except where expressly mentioned, the discussion of semiconductors so far has
related to single crystals. If the long range crystalline order is missing, as in amorphous
semiconductors, the optical properties are modified [7]. There is still an absorption
edge with intense absorption on the short wavelength side of it, but the edge itself is
normally less abrupt than for single crystals. The dependence of the absorption
coefficient upon photon energy is found to be exponential in the region of the edge.
This might be due either to a smearing of the density of states at the edges of the
conduction and valence bands into the otherwise forbidden energy gap or the broaden-
ing effect of localized electric fields on the energy gap.
The structure to the high energy side of the edge is also smeared in the amorphous
state. This is thought to be due to a breakdown of the momentum condition of eqn
(10.10). Due to the atomic disorder the electrons cannot be characterized by well
defined values of k and it is possible for non-vertical transitions to occur. These
transitions are referred to as non-direct.
The optical absorption in the single crystal and amorphous state of a typical com-
pound, CdGeAs 2 , is shown in Fig. 10.10.
--,,,
,,
',Amorphous
....
_-- ........
-
.....
....
o 4 6 8 10 12
Photon energy (eV)
Fig. 10.10 Optical absorption in amorphous and crystalline CdGeAs2 [8).
10.3.3 Metals
A metal differs from all other materials by the presence of a very large concentration
of free electrons. These electrons lead to a free carrier absorption which, according to
eqn (10.8), is especially large at infra-red wavelengths. As the wavelength decreases
from the infra-red the free carrier absorption decreases, but at ultra-violet wavelengths
absorption increases again due to the possibility of interband transitions. Dependent
upon the energy band structure of the particular metal, the interband and free carrier
processes may overlap to give absorption throughout the optical region, or there may
be a small 'window' where absorption is much less.
10.3.4 Impurities
In ionic materials, the presence of foreign ions can give rise to absorption in the other-
wise transparent window of the host material, the absorption increasing with impurity
concentration. The process of absorption is a localized one. For example in Tl doped
KCI, the Tl + ion substitutes for K + and introduces localized energy states into the for-
bidden energy gap of the host material. The absorption will not be limited to a very
narrow wavelength region, however, since at any instant all ions will not be in identical
energy states. There is a strong dependence of these energy states on the distance of
the impurity ion from the nearest host ions. This dependence can be represented as in
Fig. lO.1la where the ground and first excited states are shown. As a result of thermal
vibration, ion-impurity separations and hence the energy states are constantly changing.
First excited
Configurational coordinate -
(mean separation of impurity ion
(a) from nearest host ions)
Conduction band
e e
>-
~
II ..trio.,
~
G) _
hv
-+....-
......_ _....,,&.:()...-_ _ _...... Donor level
Acceptor
c level
...o
'0G)
iii
(b) Valence band

Fig. 10.11 Optical absorption transitions in (a) a localized impurity ion in an ionic material,
e.g. KCI:TI; and (b) a doped semiconductor.
Since absorption transitions occur in a time short compared to the time taken for
the lattice ions to move, they are represented as vertical lines. At a temperature T K
the ions in the ground state might be anywhere betweenA t andA 2 and so the possible
absorption transitions can range from A t B 1 to A 2B2 , giving rise to an absorption band
centred on the wavelength equivalent to A oB o. Reducing the temperature reduces the
range of likely transitions and so narrows the absorption band.
The effect of impurities upon crystalline semiconductors depends on whether they
act as donor or acceptor atoms in the host lattice and the magnitude of the electron or
hole ionization energy (Le. position in the forbidden energy gap). Optical absorption
will occur giving rise to impurity ionization if the impurities are not already ionized.
This will be the case for wide gap materials at room temperatures and below, but not
for narrow gap materials unless the temperatures are very low. This photo ionization
of impurities creates free electrons and holes (Fig. 10.11 b). The spectral position of
these extrinsic absorption bands can be chosen for a particular host material, by using
different impurity atoms. Table 10.4 indicates how various impurities could be used
in germanium to extend its use as an infra-red detector, based on absorption and sub-
sequent photo conduction.
TABLE 10.4
Performance of doped germanium detectors [9, 10]
Impurity Temperature (K) Wavelength cut-off (~m)
None 77 1·4
Fe 77 3·6
Ni 77 5·7
Mn 77 7·8
Au 60 8·8
Hg 30 14
Cu 15 30
Zn 6 40
B, In 2 120
To summarize, a choice of host material and impurity can be made to provide an

optical absorption, and hence a means of light detection, for any wavelength in the
visible and infra-red spectral regions.
10.3.5 Colour centres

When an otherwise transparent insulator is irradiated with high energy (> 104 eV)
photons or particles it is found that selective absorption bands are produced, which in
the visible region can result in a colouring of the host material. The radiation produced
imperfections responsible for this are termed colour centres.
The simplest colour centre is the F centre in an alkali halide and consists of an
electron trapped at a negative halogen ion vacancy. Upon irradiation the ion is
+ + Conduction band
.////////////////////// >
Cl
F ------------------- "-
F_IF .b:<P
, CD
..
c:
,
/
I \ CD
\
+ + ti: _ _ iii
'- \ e/eI e e_
' ... _ c:
....
....oCD
Q.
+ + c:
....e
u
CII
iii
+ + I//, Valence band ~
///////////~ W
(a) (b)
Fig. 10.12 The F centre. (a) The lattice configuration. (b) The F -band transition in KCI.
energetically removed, to leave the vacancy which then subsequently traps a free
electron. The resulting localized centre (Fig. 10.12) behaves very much like an impurity
ion with an energy level structure which can be represented by Fig. 10.11a or Fig.
10.12b. The associated characteristic F·band absorption arises from the excitation
between the ground and first excited states.
The F centre is by no means the only type of colour centre. More complicated centres
consisting of aggregates of F centres may be produced by heating or irradiating with
light a sample containing simple F centres. The resulting centres give rise to a more
complicated absorption spectrum (Fig. 10.13).
Photon energy (eV)
2 1.5
6
.........- (a)
--(b)
5
I
~
··· ...
~4 :F.
CQ)
:!l 3
o~~ .....
~ ..... ~~ .....
~ .....
~~~~ .....
~--
0.4 0.6 1.0

Wavelength (ILml
Fig. 10.13 Colour centre absorption in KCl at 95 K [12]. (a) Due to F centres. (b) Following
illumination of the crystal in (a) at 300 K with light absorbed in the F band.
There is also the hole analogue of the F centre in which a hole is trapped by a
positive alkali ion vacancy. These so·called V centres [11] in alkali halides absorb in
the ultra·violet. Colour centres are not restricted to the alkali halides. They also occur
in other ionic materials such as CdS which always possesses a concentration of Cd 2 +
vacancies. Like V centres, these are attractive to free holes and consequently act as
hole traps giving rise to a characteristic absorption spectrum.
Although high energy radiations prove extremely effective in producing colour
centres this is only one way of producing them. Alkali halides can be coloured simply
by heating them in the presence of an alkali metal vapour [11]. The act of heating
generates vacancies within the alkali halide and the metal vapour, condensing on the
surface, acts as a source of electrons which diffuse and become trapped to form F
centres.
10.3.6 Excitons
For both impurities and colour centres, optical absorption is produced by a transition
within an existing imperfection. Light can also be absorbed in an insulating material by
a transition which actually generates an imperfection called the exciton [13].
Conduction band
/////1(//(1//(////«(((
>
~
CD == ====~ ~ -_-_-_-_-_-_-_-~ }EI~~~?Sn
Ii
c:
c.
eo
C)
"0
o c:
c. eo
c: ID
o....
....
(,J
.!!?
~j~55~za
UJ
(a)
Fundamental edge
'I
Jo 3
Fig. 10.14 Excitons. (a) Exciton energy levels. (b) Exciton absorption in CU20 at 4 K [14].
An exciton is formed when an electron, having been excited insufficiently to escape

the influence of the positive hole it leaves behind, is able to exist in a stable state in
which it does not recombine with the hole. The electron and hole pair are held together
by their mutual Coulomb attraction, and, as in a hydrogen atom, the separated charges
can exist in one of a series of quantized energy states. The allowed exciton states lie
within the forbidden energy band gap of the host material (Fig. lO.l4a) and give rise
to narrow absorption bands close to the fundamental edge of the host material. Fig.
10.14b shows the exciton absorption spectrum for CU20, and, as will be noted, the
absorption resulting from exciton production is very intense.
10.4 Reflection
The illumination of a material with light gives rise to the polarization of charges near
to the surface and if the energy of the polarization is not dissipated by interactions
with the lattice atoms, the light is re-radiated, as from an oscillatory dipole (section
10.2). However, the re-radiated light from the polarized charge could well be emitted
into the direction from which the incident light had come. If the surface contains a
high density of easily polarized charges which readily interact with the incident light a
very large proportion of the beam will be reflected. This arises since even the re-
radiation which is directed further into the material will interact again with a high pro-
bability of being re-radiated back towards the surface. The processes are not simple
but the overall effect will be the reflection of a portion of the incident light.
It is a result of electromagnetic theory that the proportion of an incident light beam
which is reflected normally at the surface of a material of refractive index n, is given
by the reflection coefficient
R = {(n - 1)/(n + 1)}2. (10.11)
A material like glass does not present a high density of easily polarizable charges to
a beam of visible light and so reflection is small (~4 per cent). On the other hand, a
metal possesses a very dense gas of free electrons and penetration by the light is very
small. Thus, the metal acts as an almost perfect reflector.
It is found that whatever the material, for wavelengths at which there is intense
absorption there will usually be a strong surface reflection. This occurs for example in
the visible region for a semiconductor where there is interband absorption and in the
infra-red for ionic materials at the ionic resonance frequencies.
10.S Natural birefringence
For a transparent isotropic medium the refractive index is related to the relative per-
mittivity according to the relation €r =n2 , where €r is a scalar quantity. For an
anisotropic medium it must be a matrix €ij where, using the notation of Chapter 8
Dj =€o€ij8j: Pi =€O(€ij -1)8j
€ij =(::: ::: :::). (10.12)

€31 €32 €33
This implies that an electric field applied parallel to the x direction will induce not only
a polarization Pi parallel to itself given by €O(€l1 - 1) IJ 10 but also polarizations
paralleltothey andz directions given by P2 =€O(€12 -1)81 andP 3 =€O(€13 -1)81
respectively. Since the matrix is symmetric it is possible to fmd a set of axes within
the crystal for which only the diagonal terms are non-zero. These axes are called the
principal axes and the diagonal terms the principal permittivities €1, €2 and €3
€ij =(€~ €~ ~\. (10.13)

o 0 €J
An electric field parallel to a principal axis will only produce a parallel polarization
but in general the three permittivities €1, €2 and €3 will be different. This variation in
€ is the origin of birefringence. Anisotropic crystals can be characterized by the three
principal refractive indices nx , ny and nz , the subscript relating to the direction of
polarization of tpe light wave, not the direction of propagation.
For optical purposes, anisotropic crystals are subdivided into two classes. Hexagonal,
tetragonal and trigonal crystals are all characterized by a principal axis (z axis by con-
vention) along which the permittivity is €3 but perpendicular to which € is independent
of direction (Le. €1 = €2). Such crystals therefore have two principal refractive indices
only. The z or c direction is unique along which the velocity of propagation is indepen-
dent of light polarization. Such a direction is termed an optic axis. Crystals of this first
class have only one optic axis and are said to be uniaxial. The difference between nx and
nz is a measure of the birefringence and is said to be positive or negative dependent on
whether nz is greater or smaller than nx . Some examples are shown in Table 10.5.
TABLE 10.5
Room temperature birefringence in some uniaxial crystals
A(/lm) nz nx a.n
ADA (NH4H2As04) 0·5 1·529 1·585 -0·056

ADP (NH4H2P04) 0·5 1·483 1·530 -0·047
KDA (KH2As04) 0·5 1·524 1-574 -0-050
KDP (KH2P04) 0·5 1-472 1·514 -0-042
Calcite (CaC03) 0-5 1-489 1-665 -0-176
Rutile (Ti02) 0-58 2-919 2-621 +0-298
Quartz (Si02) 0·59 1·553 1-544 +0·009
liTa03 0·5 2-221 2-216 +0-005
liNb03 0-5 2-245 2·344 +0·099
Ba Ti03 0-55 2-365 2-437 -0-072
KTN (KTao'6sNbo-3S03) 0-55 2-312 2-300 +0-012
Crystals of lower symmetry possess two optic axes and therefore are said to be
biaxial; examples are Rochelle salt, gypsum and feldspar. These axes are not coincident
with any of the principal axes and nx , ny and nz therefore have different values_
The application of Maxwell's electromagnetic theory equations to an isotropic
medium shows that light of any polarization can be propagated in any direction_ For
anisotropic crystals, however, this is not so, and it can be shown [2,15] that as a result
of birefringence only two states of plane polarization can be propagated for any crystal
direction. These planes of polarization are at right angles to each other and except
when propagation is parallel to an optic axis they possess different refractive indices.
The values of n and the states of polarization for a particular direction of propagation
can be determined from a three-dimensional spatial representation of the refractive
index, known as the index ellipsoid or optical indicatrix_ Its form can be derived as
follows. The energy density W in a dielectric is given by
W=~D-8 (10.14)
and hence from eqns (10.12) and (10.13)
DI2 D22 D3 2
W=-- +-- +--. (10.1S)
2EoEI 2EoE2 2EoE3
A constant energy (W) surface then takes the form, in a three-dimensional space where
dielectric displacement D is the coordinate, of an ellipsoid.
Dividing both sides by Wand rewriting DI2 /2Eo W as Xl , etc_ leads to a simplified
expression
x 2 y2 Z2
1 =-+-+-. (10.16)
n x 2 n y 2 nz 2
This equation represents an ellipsoid of semi axes nx , ny and nz _ For a uniaxial crystal
nx = ny =1= nz and the optical indicatrix for such a crystal is shown in Fig_ 10.1 S.
x
Fig. 10.15 The refractive index ellipsoid or optical indicatrix for a uniaxial crystal.
It is normal to refer to the index nx(= ny) as the ordinary refractive index no and to
n z as the extraordinary refractive index ne. Hence for uniaxial crystals
(10.17)
For propagation in a general direction OP (Fig. 10.15) at an angle e to the optic axis
(z axis) the electric vector always lies in the plane at right angles to OP (shown shaded).
The refractive index varies from no to a maximum value n(J ; n(J lies between ne and no
and depends on e. For () =0, n(J =no and for () =1rj2, n(J =ne. The two plane polariza-
tions which can be propagated correspond to the maximum and minimum refractive
indices given by the indicatrix construction. Hence for propagation parallel to the optic
axis, there is no birefringence since the section of the ellipsoid perpendicular to this
direction is a circle. For propagation in the x direction perpendicular to the optic axis,
birefringence will be a maximum and the permitted polarizations will be parallel to
the y axis with refractive index no and parallel to the z axis with refractive index ne.
10.5.1 Double refraction

When conSidering the refraction of light by an anisotropic crystal it is necessary to con-
sider the various modes of propagation possible in the refracting medium. In section
10.5 it was deduced that propagation with a refractive index no was possible for every
direction. This leads to the first and simplest mode where refraction occurs just as if the
material were isotropic. The refraction takes place according to Snell's law (nl sin () I
= n2 sin ()2) and the refracted beam is known as the ordinary or O-ray (hence the
refractive index is termed no). The O-ray is polarized and the plane of polarization can
be determined from the index ellipsoid.
A second refracted beam results from the mode of propagation whose index is
direction dependent. The direction of this beam can be determined using a Huyghen
construction equivalent to the superposition of the secondary refracted wavelets [16],
the velocity of which will be direction dependent according to the index ellipsoid.
The beam direction will be that for which the wavelet from the neighbouring points
on the surface of the refracting material combine to give a wave front. If the incident
beam has a plane wave front, so will the refracted beam. The wave direction will not
necessarily be perpendicular to this front but will depend upon the orientation of the
optic axis relative to both the crystal surface and to the incident beam direction. This
is the extraordinary or E-ray. It does not obey Snell's law and its index will lie between
no and ne (hence the origin of extraordinary index). The two rays are shown in Fig.
10.16 for a uniaxial crystal which is cut at various angles to the optic axis, light being
incident normally. If wavelets are emitted at 0, the ellipse and circle represent relative
shapes of the wave fronts for the ordinary and extraordinary wavelets. The shapes of
these wave fronts follow from the index ellipsoid remembering the phase velocity
v = c/n.
>- >-
I"' I"'
>-
~
I OUJ
~
~"
0
~v
o~%,
/"'b+~
O -ray
wavefront "E- ray
wavefront
Crystal Crystal
9~
aXIs
Air Air
C
Q) E
cQ) E
"u
"0
"'
Q)
.0
"0
'0
c
"'
Q)
.0
.E
(a) (b)
Fig. 10.16 Double refraction in a positive uniaxial crystal, i.e. ne > no for the crystal surface
cut at (a) an arbitrary angle, and (b) parallel to the optic axis.
It can be seen that in general (Fig. 1O.l6a) the two rays, both linearly polarized,
are spatially separating. This is 'double refraction', and given an adequate thickness of
material the rays can be completely separated. For the crystal cut parallel to the optic
axis (Fig. 10.16b) no spatial separation of the rays is achieved for normal incidence
although they do travel at different velocities.
Double refraction can be utilized for producing plane polarized light, as for example
in the calcite Nicol prism. The crystal is cut such that the extraordinary and ordinary
rays are spatially separated (Fig. 10.17). The ordinary ray is totally reflected at a thin
layer of Canada Balsam cement between the two halves of the prism, this cement has a
refractive index intermediate between that of calcite for the E- and O-rays. The angle
E-ray
• •
Fig. 10.17 The Nicol prism.

of the prism is such that the O-ray is totally internally reflected at the calcite-cement
interface, leaving the plane polarized E-ray. Nicol prisms provide excellent polarizers
and analysers.
10.6 Induced birefringence
Birefringence can be enhanced in an already birefringent material or induced in an

otherwise isotropic material by the application of an external electric or a strain field.
Each field changes the shape of the refractive index ellipsoid as a result of changing
the permittivity tensor €jj.
Relative to the principal axes the natural ellipsoid is represented by eqn (10.16).
After deformation of the ellipsoid, however, these axes will no longer be the principal
t
axes and the ellipsoid must now be represented by the more general equation
(nI2) 1 x 2 + (nI2) 2y2 + (nI2)3 Z2 + 2 (n1i yz + 2 (nq 5 xz + 2 (nI2) 6 xy = 1. (10.18)
This modified ellipsoid will have a new set of principal axes relative to which eqn (10.18)
can be rewritten in the form of eqn (10.16). In general, however, these new axes will
not coincide withx,y or z.
The effect of a particular field upon the index ellipsoid of eqn (10.16) is represented
by the changes it produces in the six terms (l/n 2 );, where i = 1, 2, ... , 6. This gives the
ellipsoid the form of eqn (10.18).
10.6.1 Linear electro-optics

The linear electro-optic or Pockel's effect arises from the fact that permittivity and
hence refractive index are electric field dependent. For small fields the dependence is
a linear one, and eqn (10.12) can be rewritten in the form
D=€o€jj(1 +a&)&. (10.19)
This is only possible for crystals lacking an inversion (or symmetry) centre. The linear
electro-optic materials are therefore also piezoelectric.
The effect of the electric field upon the index ellipsoid is represented as the change
produced in the six terms of the ellipsoid relative to their values in eqn (10.6). They
are given as
Ll ( n12) j = r;j &j, i = 1, 2, ... ,6; j = 1,2,3, (10.20)
where rjj is the electro-optic matrix, containing eighteen independent electro-optic

coefficients. For most materials of interest the symmetry of the crystal structure
reduces the number of these significantly [15]. As an example the matrices rjj for ADP
and quartz are shown in Fig. 10.18. Some electro-optic data is given in Table 10.6 for a
range of materials.
10.6.2 Intensity modulation

One of the principal applications of the Pockel's effect is to the modulation of light.
The principle of intensity modulation can be described with reference to Fig. 10.19.
The electric field is applied parallel to the optic z axis which is also the direction of
propagation. The incident light is polarized parallel to the principal y axis.
'ij = 0 0 0 'ij = '" 0 0
0 0 0 -'11 0 0
0 0 0 0 0 0
'41 0 0 '41 0 0
0 '41 0 0 -'41 0
0 0 '63 0 -2'11 0
(a) (b)
Fig. 10.18 The electro-optic tensor for (a) ADP and (b) quartz.
TABLE 10.6
Electro-optic data, ,(x 10-12 mV-l)
ADP '41 = 24 see Fig. 10.18a

'63 = 8·5
KDP '41 = 8·6 see Fig. 10.18a
'63 = 9·5
Quartz '41 = 0·2 see Fig. 10.18b
'11 = -0·47
ZnTe '41 = '52 = '63 = 4·3 all other terms zero
GaAs '41 = '52 = '63 = 1·6 all other terms zero
BaTi03 '33 = 23 all other terms zero
'13 ='23 = 8
'42 = '51 = 820
KTN '33 = 1400 all other terms zero
'13 ='23 =1000
'42 = '51 = 10 000
LiNb03 '13 = '23 = 9 all other terms zero
'22 = -'12 = -'61 = 6·6
'42 = '51 = 30
'33 = 30
Output
Input
light beam
light beam
Analvser
Polarizer
-----~
Optic aKis
Fig.l0.19 Longitudinal light intensity modulation.
In the absence of a field there will be no birefringence because the propagation is

parallel to the optic axis and so if the crystal (say ADP) is placed between crossed
polarizers, no light will be transmitted by the system as a whole.
Upon the application of the electric field (8. 3 ) the principal axes of the crystal are
changed. For ADP the z axis remains a principal axis but is no longer an optic axis
whilst the new principal axes, equivalent to x and y, are rotated through 45° . These
axes are of unequal length in the ellipsoid and it can be shown that for ADP and
crystals of the same structure, the birefringence for propagation parallel to the z
axis is
(10.21)
Resulting from this birefringence the two modes of propagation polarized parallel to
the new principal axes will become out of phase by an amount l1cp, dependent upon
the length of crystal L, given by l1cp = Ltln (2rr/X), i.e.
(10.22)
The two polarized modes are of the same amplitude and combine on leaving the
crystal to give rise in general to elliptically polarized light. There will therefore be a
component of the emerging light which will be polarized perpendicularly to the plane
of polarization of the incident light. If the crystal is between crossed polarizers, this
component will be transmitted. As the electric field (8. 3 ) and hence l1cp increases, the
amplitude of this component increases, with a consequent increase in the intensity of
the transmitted light. When the phase difference amounts to rr, the emerging light is
plane polarized perpendicular to the plane of polarization of the incident light and
complete transmission is achieved. The voltage for this is termed the half wave voltage
V1/ 2 • Since
(10.23)
It can be seen that the combination of varying the electric field and using the crystal
between crossed polarizers has the effect of modulating the intensity of the light beam.
This has application to optical shutters [17,18] . Some values for Vl/2 are given in
Table 10.7.
The electro-optic effect described is known as the longitudinal effect, since the
applied field is parallel to the direction of propagation. Although simple in principle,
TABLE 10.7
Electro-optic modulation data
Material Effect Modulation Vl/ 2 (kV)
ADP linear longitudinal 8·2

ADP linear transverse 6·56
KDP linear longitudinal 7·6
KDP linear transverse 6·08
ZnTe linear transverse 0·78
GaAs linear transverse 1·92
BaTi03(400 K) quadratic transverse 0·265
KTN (310 K) quadratic transverse 0·22
Note: all data are given for a crystal 4 mm wide by 1 em long,

at a wavelength of 0·5 ",m.
because there is no natural birefringence, it is difficult to use. The tranwerse

effect is technically simpler. Here the field is applied perpendicular to the direction
of propagation.
For light of wavelength X directed parallel to the x direction, retaining the electric
field parallel to the z direction, the birefringence induced in ADP is only half that
given by eqn (10.21). The half wave voltage is then given by
X L
V1/2 =-3--' (10.24)
no r63 I
where L and I are the crystal width and length respectively. In contrast to the longitudinal
effect, the value of V 1/ 2 for the transverse case depends on crystal size. An increase in
the length of the crystal and hence the optical path, incre,!1ses the birefringence induced
for a given field and so has the effect of reducing the half wave voltage.
With transverse modulation, there are problems caused by natural birefringence,
since propagation is not parallel to an optic axis. These can be overcome by using an
identical, unbiased crystal, in series in the optical path to compensate for the natural
birefringence. Alternatively certain cubic crystals, such as GaAs and ZnTe, can be used
for which there is no natural birefringence; V1/ 2 for these are shown in Table 10.7.
10.6.3 Quadratic electro-optics

The quadratic electro-optic, or Kerr effect, arises from a quadratic dependence of the
permittivity upon electric field, i.e. it arises from the term b It.? in a modified eqn
(10.18)
(10.25)
For non centro-symmetric crystals the quadratic coefficient 'b' is very small in com-
parison with the linear coefficient 'a' but in centro-symmetric crystals there is no linear
effect and the quadratic effect becomes important.
The effect is characterized by the dependence of the index ellipsoid upon dielectric
polarization, i.e.
(10.26)
where gikl is a 36-term tensor but the crystal structure reduces many of these terms to
zero.
The most important materials here are the paraelectric perovskites (e.g. BaTi0 3
above its Curie temperature) for which it can be shown that if light is directed parallel
to the x axis and is plane polarized at 45° to the y and z axes, then for an electric field
&3 the phase lag after a length I is given by [10]
i1t/>=(1fn3/X)(gU -g12)P3 21. (10.27)
The most useful material is KTao.65 Nb O•35 0 3 (known as KTN) since it can be operated
just above room temperature, the Curie temperature being only 301 K. Some values
of V1/ 2 obtained with the quadratic effect are shown in Table 10.7.
10.6.4 Elasto-optics [18]

The elasto-optic effect arises from the birefringence induced as a result of the order
imposed upon an amorphous material by straining it. The discussion of the piezoelectric
effect showed that the application of stress changes the electrical polarization of a
material, and this inevitably affects the optical properties. The changes induced by the
strain can be characterized by
(10.28)
where Pij is a 36-term matrix of strain-optical coefficients.
One of the earliest uses of elasto-optics was in the analysis of stresses in structures.
A model is made in perspex which, when subjected to stress, exhibits birefringence.
Analysis of this birefringence provides an understanding of the stress patterns in the
original structure and facilitates improved structure design. Dynamic measurements of
birefringence can also be made in rubbers and has led to an understanding of the
molecular motions.
10.7 Non-linear optics
When an e.m. wave represented by 8. = 8. oe- iwt interacts with an outer electron of an
atom, at a frequency well below resonance, a polarization P is produced which, provid-
ing the electric field intensity is low, will be in phase with the excitation and pro-
portional to it, i.e.
(10.29)
where Xl is the susceptibility (Xl = €r - 1) and is in general a tensor.
Should the electric field be very large however (~1010 V m- l ), comparable with the
electric fields associated with the atoms, the polarization will not be linearly pro-
portional to 8., but will contain higher order or non-linear terms, i.e.
P=€OXI8. oe- jwt + €oX2(8. oe- jwt )2 + €oX3(8.oe-iw~3 +.... (10.30)
The first, second and higher order susceptibility terms become progressively smaller,
but at high fields the presence of the power terms in 8, give rise to a significant con-
tribution to the polarization. The most important effect is that as a result of non-
linearity, the polarization contains components characteristic of higher harmonic
frequencies of the fundamental exciting angular frequency w. Rewriting eqn (10.30)
in the following form shows that the second order term produces a component of the
polarization characterized by an angular frequency 2w:
(10.31)
The fields necessary to observe non-linear effects can only be produced in a laser
beam. As a result of the appearance of the higher harmonics in the polarization, some
of the atoms will, after irradiation, emit photons of twice or even three times the
exciting frequency. The number of these photons will however be small in comparison
with those still of the fundamental frequency.
The production of light of angular frequency 2w by a non-linear material, from a laser
beam of angular frequency w, is known as second harmonic generation and can be
readily achieved in the non-centro symmetric crystals such as quartz, ADP and KDP
[15,19]. Centro symmetric crystals produce a zero effect because X2 is zero.
10.8 Secondary processes
Optical absorption can give rise to many secondary effects, the majority of which are
useful as means for the detection of light. The principal processes are photo emission,
photoconduction and photoluminescence.
10.8.1 Photoelectric emission

The basic photoemission process is one in which a light photon interacts with an
electron and loses all of its energy. This energy is used partly in overcoming internal
binding forces acting on the electron and the remainder is converted into electron
kinetic energy. Should this kinetic energy be sufficient for the electron to reach the
surface of the solid and overcome the surface barrier forces, photo emission will occur.
The photo-release of an electron finds its principal application in the sensitive photo-
cathode of a photomultiplier tube. Photocathode characteristics of prime technical
importance are the spectral response (Le. dependence on wavelength) and the quantum
efficiency (Le. the number of electrons emitted per incident photon) and these factors
are very material dependent.
The spectral response of a material is determined by the availability of electrons to
be excited and their location in the electronic band structure prior to excitation. For
metals the photon with the smallest energy necessary to cause emission will correspond
to the release of an electron from the Fermi level (Fig. 10.20a) and hence unless the
photon energy hv is in excess of the work function cf;i eV, no emission* will occur, i.e.
for emission
hv = he/A ~ ecf;i. (10.32)
Vacuum ---,,--_ _ _....-_ "7'"O"7'7"T7"T'?"'T7"7"'T':~ Vacuum

level level
eCfi hv
Fermi
level
Fermi
level
~
/.Conduction bang ~
all////////// / /Valence band~
/////////~://%
(a) (b)
Fig. 10.20 Photoelectric emission from (a) metal and (b) a semiconductor.
Substituting for the constants in eqn (10.32) indicates the emission will only occur
for wavelengths shorter than the critical wavelength Ao where
1'24
AO =-;;; microns. (10.33)
Common metals possess work functions from 2 eV upwards and are sensitive, there-
fore, only to visible and ultra-violet radiation (see Table 10.8).
For intrinsic semiconductors emitted electrons must originate from at least the
depth of the valence band and so in this case (Fig. 10.20b) the photon energy must
exceed the sum of the electron affinity Ea and the band gap E g , i.e.
(10.34)
Many semiconductors are characterized by photoemission only in the visible and near
* This is not strictly true since with the Fermi distribution there will be some electrons above
the Fermi level at T> 0 K. There will therefore be a tail in the excitation spectrum to wavelengths
greater than AO'
ultra-violet regions but there are some composite evaporated materials which are
sensitive in the near infra-red, for example Ag-O-Cs is sensitive to 1·2 Jlm.
It might have been expected that the narrow band gap materials like InSb would
have exhibited photoelectric emission when illuminated with infra-red radiation, but
this is not so, due to their large electron affinities.
Quantum efficiency depends on a combination of the probability of an electron
interacting with a photon and the probability of the electron, once excited, reaching
the surface and escaping. In any electron-photon collision it is necessary to have con-
servation of momentum but for free electrons this cannot occur unless a third body
(an ion or phonon) takes part. The momentum of a light photon is not sufficient to
provide the momentum consistent with the energy of the electron, and the deficiency
has to be met by the third body. The conduction electrons in a metal are free and
since the chance of a photon-electron collision occurring in the presence of a third
body is small, the quantum efficiency will be small, of the order of 10- 3 per cent.
A second factor which reduces the efficiency in a metal is the very limited range
that the excited electron possesses. Collisions with impurities and lattice phonons
occur to degrade the kinetic energy of the electron such that unless the initial excita-
tion occurs within about 30 A of the surface, there is little chance of escape.
In semiconductors the excited electrons come from bound locations in the valence
band and so there are no momentum problems. Furthermore, once excited, the electrons
experience few interactions with conduction electrons since the number of these is
relatively small. An interaction that can occur, however, is that between an excited
valence electron and an unexcited one, but the importance of this process depends on
the relative sizes of the electron affinity Ea and the band gap E g. If Ea < E g, (Fig. 10.20b)
a photon of just sufficient energy to produce emission (i.e. hv = Ea + Eg) will give rise
to an excited valence electron with kinetic energy Ea. insufficient to produce further
electron-hole pairs. As a result these electrons will have a large range, perhaps 250 A,
and the materials will have a high quantum efficiency. A material of this type is CS 3 Sb
for which Ea is 0-45 eV and Eg is 1·6 eV giving a quantum efficiency as high as 25 per
cent. Properties of this and other materials are shown in Table 10.8.
TABLE 10.8
Photoelectric emitters
<p(eV) Ea(eV) Eg(eV) Ao(/oIrn) Quantum efficiency at

peak response (%)
Cs 1·94 0·64 < 10- 2

Na 2·28 0·54 < 10- 2
W 4·54 0·27 < 10- 2
Ag 4·70 0·26 < 10-2
Ge 3090 0·72 0·27 0·1
Na3Sb 2·00 1-10 0·40 2
CS3Sb 0·45 1·60 0·61 25
(NaKhSb('bialkali') 1·0 1·0 0·62 30
(N aKh Sb-Cs('trialkali') 0·55 1·0 0·80 40
Ag-02-Cs 1·20 0·6
If Ea > Eg the excited valence electrons will have sufficient kinetic energy to produce
further electron-hole pairs. This process and possible subsequent ones would degrade
the kinetic energy, and even if no other collision occurred would remove the possibility
of overcoming the surface barrier forces. For this case the range can be as low as 30 A
and the quantum efficiency is consequently low. A material of this type is Na3 Sb for
which Ea is 2·0 eV and Eg is 1·1 eV; its quantum efficiency is only 2 per cent.
Figure 10.21 shows the spectral response of quantum efficiency of some com-
mercially available photodetectors for the visible and near infra-red regions.
24
~
>-
(.)
c: 16
cP
·13
....cP
~
12
E
.ac:
II>
:::l
8
d
0
0.8 1.0 1.2
Wavelength (I-lm)
Fig. 10.21 The spectral variation of quantum effidency for a range of EMI photocathodes [20].
10.8.2 Photoconductivity
The last section showed that for photo emission to occur, relatively large photon energies
were necessary, and as a result there are no known photoemitters for wavelengths
beyond the near infra-red region of the spectrum. In semiconductors, however, rela-
tively small photon energies are capable of producing electron-hole pairs internally, and
hence of increasing the carrier concentrations and the conductivity of the material. This
photo-induced conductivity can be used for light detection from the ultra-violet through
into the infra-red spectral region.
The conductivity of a semiconductor can be written in the form
a = nel1n + pel1p, (10.35)
where nand p are the free electron and hole concentrations, I1n and I1p are the electron
and hole mobilities, and e is the electron charge. Under illumination a change will occur
which can be expressed as
(10.36)
where both tl.n and Ap will depend upon the light intensity.
For intrinsic semiconductors the photo response only occurs for wavelengths shorter
than a threshold corresponding to the energy gap, and by a suitable choice of material
a wide range of spectral sensitivity can be achieved. For GaP the threshold is at 0·55 11m
since Eg is 2·24 eV, whereas, for InSb it is at 6·9 11m since Eg is 0·18 eV. This shows
that narrow gap materials are infra-red sensitive but it is important to remember that
any photo-induced increase in conductivity must be distinguishable from the dark
thermally produced conductivity. For this reason it is necessary to cool infra-red photo-
conductive detectors to nitrogen or helium temperatures, in order to reduce the dark
conductivity to an acceptable level. Not only does this improve the signal to noise
ratio but it changes the spectral response, since Eg is sensitive to temperature. As an
example, for PbTe the threshold is 3·4 J,tm at 300 K but is 5·9 J,tm at 20 K.
The spectral response of photoconductivity of an intrinsic semiconductor detector
can be extended to longer wavelengths by doping with an impurity. The impurities
put donor or acceptor states in the otherwise forbidden energy gap and these can be
ionized to produce photo conduction. Unlike the intrinsic photoconduction, only one
carrier is excited in extrinsic photoconduction (Fig. 10.11 b). Fig. 10.22 shows how
germanium, whose normal threshold is 1'4 J,tm at 77 K, can have its spectral response
extended to 9 J,tm by the inclusion of various acceptor impurities.
,.. ....
~
I
I
I
Mn'
I
I
J
,
I
I
Ni
Photon energy (eV)

Fig. 10.22 Photoconductivity spectra at 77 K of doped Ge. Each spectrum is labelled with the
appropriate dopant [9).
In addition to spectral response, factors of importance in photodetectors are sen-

sitivity and response time. These two are very closely related so that modifying a
material to improve one does so at the expense of the other. A compromise solution
is therefore necessary.
Sensitivity depends not only on the ability of a material to absorb but also on the
ability of generated carriers to remain free. If T is the mean carrier lifetime, and the
rate of generation is f, the average photo-induced concentration will be given by
t1n = fT. (10.37)
The larger T, the greater will be t1n. In a practical device the sensitivity is expressed as
a gain G, this being the ratio of the number of photoelectrons crossing the photo-
conductor to the number of photons absorbed. This can be shown to be related to the
transit time of the carriers in the device, T, and the lifetime by
G = TIT. (10.38)
Pure materials are characterized by small 1"(-10- 6 s) due to the high chance of electron-
hole recombination, and hence are relatively insensitive. Careful doping however can
suppress recombination and hence increase T and the sensitivity. An example is that of
CdS, in which the addition of iodine has the effect of increasing T to 10- 3 s. The
process is represented in Fig. 10.23. Iodine, substituting for sulphur, acts as a donor,
Conduction band
6-
o 0 0 0 0 0 0 0 0 0 0 ,-
hv
~
o 0 0 0 0
o 0 Cd 2+ Vacancies
Fig. 10.23 Model for the enhancement of electron lifetime in CdS as a result of doping with
iodine.
giving CdS N-type properties. To fit into the divalent ionic lattice the iodine atom
should accept two electrons. However, it displays a strong affinity for one but the
second is only weakly bound and easily removed thermally. In this state the singly
ionized iodine represents an imbalance in the charge of the CdS, and to compensate
for this, Cd 2 + vacancies are generated at a rate of one per two iodine donors. These
vacancies act as efficient hole traps and so upon photo excitation the holes are readily
trapped, but the electrons have an enhanced lifetime due to the now reduced chance
of meeting a hole and recombining. The conduction in this case is purely N-type.
The response time of a photoconductor is a measure of the time for the photocurrent
to reach apprOximately 70 per cent of its final value following the onset of illumina-
tion. For quick response times, short rather than long lifetimes are required so that an
end to illumination is followed rapidly by an end to photo-induced current. Response
times however are governed not only by any recombination centres present, and their
1270
/ Recombination
1280 _____ Shallow traps
Q)
o
; 1290
ti
"iii
Q)
II:
1300
Fig.l0.24 The decay of photoconductivity in Si after the termination of illumination [211.

OPI'ICAL PROPERTIES 247
ability to reduce T, but also by the presence of carrier traps which merely act as tem-
porary locations for the charges and cause a delay in the processes of charge move-
ment. These traps can result from crystal defects such as dislocations, vacancies and
impurities and must be kept to a minimum for rapid response times. As an example
Fig. 10.24 shows the decay of the photoresponse of Si following the termination of
illumination.
Response times can differ between low and high light intensities. For low levels it
may take some time for an equilibrium to be set up between the charge trapping and
the charge emptying processes. If the trap concentration is large in comparison with
the carrier concentration, the response time will be long. For high levels however these
traps will be quickly occupied, and an equilibrium set up, and so the response will be
quicker.
Table 10.9 shows some data for a range of current photoconductive materials.
TABLE 10.9
Commercially available photoconductors
Operating temperature (K) Spectral range Response time (ps)

for detection (pm)
CdS 293 visible-O·9S 10 5

PbS 293 visible-3·S 100
InSb 293 visible-7 ·5 0·1
InSb 77 visible-S ·6 4
CdHgTe 77 3-14 1
Si 293 visible-1·2 0·1
Ge 293 visible+8 100
Ge (doped with Cu) 4·2 visible-2S 1
10.8.3 Photoluminescence [22]

Optical absorption increases the potential energy of a material as a result of the pro-
duction of electron-hole pairs or perhaps excited impurity ions. This state will not
last indefinitely since there will always be a tendency to revert to the original state.
The de-excitation involves the release of energy and this can occur in either, or a
combination of, two ways. The energy may be transmitted to the lattice as thermal
vibrations or be emitted as light.
Such light emission is termed photoluminescence and usually has a longer wave-
length (lower energy) than that absorbed. The balance is transmitted to the lattice as
heat. If the emission occurs almost immediately following absorption, i.e. within 10- 8 s,
it is termed fluorescence and if there is some delay, perhaps hours, it is known as
phosphorescence.
Most materials can be considered as operating by one of two basic mechanisms,
dependent on whether the material is, or is not, a significant photoconductor.
Insulators such as the alkali halides do not exhibit appreciable photoconductivity
but they luminesce when doped with an activator ion. An example is KCI doped with
about 10- 4 per cent Tl (the absorption by the Tl+ ion was discussed in subsection
10.3.4). Following the absorption by the range of possible transitions AlB 1 to A 2B2
(Fig. 10.25) which gives a sudden infusion of energy into the ion, the lattice ions
close by relax, and the excited state of Tl + moves towards the minimum Co. Due to
thermally acquired vibrational energy from the lattice, however, there will be a spread
in the exact location of the excited ions at any given instant. This will range from C 1
to C2 where the energy difference above the minimum is of the order of kT. Follow-
ing this relaxation, the excited ion may de-excite to the ground state by luminescence
emission. The transition will be instantaneous and represented by vertical lines in
Fig. 10.25 but will vary between different ions over the range C1D1 to C2 D 2 •
t
>-
Cl
~
CD
c:
w
Ground
state
Configurational co ordinate -
(mean separation of impurity ion
from nearest host ions)
Fig. 10.25 Photoluminescence by an impurity ion in an insulator, e.g. KCl: Tl.
Emission will, therefore, be observed as a band, centred on the wavelength equivalent

to the transition CoDo. The equilibrium ground state is finally reached by a further
lattice relaxation, of the type DoA o. KCI is also activated to luminesce by the presence
of F centres. Fig. 10.26 shows the absorption and emission bands for F centres in KCl.
The de-excitation does not have to occur by luminescence emission however. A few
ions will have sufficient thermal energy to take the path back to the ground state
represented by the broad arrow in Fig. 10.25. In this case the process is thermally
activated, and the probability of the process occurring will increase with temperature.
In a non-radiative de-excitation the energy is all transmitted to the lattice.
Not all luminescent emissions occur within the same centre as the absorption. For
example in Ca(P04h (Ce, Mn) the absorption is due to the cerium ion (the sensitizer)
and the emission is due to the manganese ion (the activator). For this to occur there
must be a transfer of energy between these, and this is found to be the case only if
the centres are very close together, i.e. within 35 A. The probability of transfer, and
therefore the chance of observing luminescence, decreases as the inverse of the sixth
or higher power of the separation distance.
In contrast semiconducting materials exhibit photoconductivity and the mechanism
for luminescence depends upon the ability of the photo excited electrons and holes
to become mobile. Emission occurs following the radiative recombination of either
an electron with an electron trap, a hole with a hole trap or an electron with a hole.
The activation spectrum (spectrum of that absorption which results in luminescence)
will therefore be characterized principally by the band gap of the semiconductor but
also by the ionization energies of the impurities. The emission spectrum, however,
will depend primarily on the nature of the impurity ions which act as the recombina-
tion centres. For example ZnS absorbs light of wavelengths shorter than 0·35 JIm but
emits in bands centred on 0·43 JIm (blue), 0·52 JIm (green) or 0·58 JIm (yellow)
depending on whether it is activated with Ag, Cu or Mn respectively.
Photon energy (eV)

3.0 2.5 2.0 1.5 1.0
I" " !" " I' "I '
'E
"'06
F centre
absorption
0.4 0.6 0.8 1.0 1.2 1.4

Wavelength ((J.m)
Fig.l0.26 Photoluminescence from F centres in KCl at 95 K [12).
The discussion has so far been directed solely to photoluminescence, the excitation
being produced by optical absorption. However, there are many other means which
can produce identical excited states in insulators or semiconductors and which can
subsequently give rise to luminescence. These are mentioned briefly.
Cathodoluminescence occurs when excitation arises from the impact of high energy
radiation or particles for example from 'Y-rays, X-rays, electrons, ions or nucleons.
Scintillation counters based on this effect are used for nuclear particle and radiation
detection and employ insulators such as NaI: T1 or perspex doped with anthracene.
The phosphorescent screen of a cathode ray tube might employ ZnS doped with Ag
or Cu.
Electroluminescence occurs when excitation is initiated by an electric field. The
forward bias voltage across a semiconductor P-N junction, for example, enables
minority carriers to be injected into the two sides of the junction. Some of these may
recombine radiatively and if the emission is in the visible region of the spectrum a
controllable light source is obtained. GaP emits red light and is commonly used as a
light emitting diode (LED) in visual displays.
Other types of luminescence are thermoluminescence produced as a result of heat-
ing, triboluminescence from mechanical strain, chemiluminescence from chemical
reactions and bioluminescence as a result of biological action.
10.9 Lasers
10.9.1 Principles of laser action

The basic principles upon which a laser works can be described by reference to the
energy states of an ion in dilute solid solution in a host medium (e.g. ruby, i.e. Cr3+
in Ah 0 3 ), The ion will be characterized by a ground state and a series of excited
states, the relative occupation of these states being determined by their energies, the
level of illumination and the temperature.
Consider two states Eland E 2, E 2 being the higher energy. E 1 can be the ground
state, but this is not essential. An ion can only be in one state at a given instant but
for a large number of ions there will always be a number in each state. The relative
numbers are decided by Maxwell-Boltzmann statistics such that if there are Nl in
stateE t andN2 inE2:
Nt exp(-EdkT)
N2 = exp(-E2/kT) = exp{(E2 - Ed/kT}. (10.39)
In thermal equilibrium there will always be more ions in the lower energy state, for
if E2 - El is 2 eV, then at 300 K,NdN2 is very large, being 1034 and virtually all
ions would be in the ground state.
Should the ions be illuminated by photons of energy (E2 - Ed, three processes
can arise, each of which is represented in Fig. 10.27. If ions are initially in state E 1,
optical absorption can follow and the ions are excited into state E2 • The number of
absorption processes will depend upon the number of incident photons and the
number of ions Nt in state El and it is likely to be large sinceNI is large.
£2 - - - - . . . - - - - £2------ £ 2 - -........- - -
hv
~
hv hv hv hv
~ '''\1'\1''_ ~
£,---+--- £,-----'--- £, _ _--L._ __
(a) Absorption (b) Spontaneous emission (e) Stimulated emission

Fig. 10.27 The various optical absorption and emission transitions possible between two
electronic energy levels.
Should ions be initially in the higher state E 2 , either by prior thermal or optical
excitation, they can return to the lower state by one of two possible processes. First
by spontaneous emission of a photon. In the absence of any external influence such as
the incidence of photons, this process is the only one that can occur, and the photons
are emitted randomly in direction and time. The rate at which spontaneous emission
can occur depends on the lifetime of the excited state, being slower the longer the
lifetime.
The second possible de-excitation process occurs as a result of the excited ion being
stimulated to emit, by a photon of just the same energy as that of the de-excitation.
As a result, a negative absorption or increase in the number of photons is produced,
since in each stimulated emission two photons emerge where there was initially one.
The important factor about this process is that the emitted photon possesses the same
direction and phase as the stimulating photon.
The transition probability for an ion absorbing in state EI can be shown to be
exactly the same as that for an ion in state E z being stimulated to emit. In normal
circumstances, however, NI is vastly in excess of N z and so absorption predominates
for a given incident light beam intensity. If, however, an artificial situation is produced
in which there are more ions in the higher energy state (i.e. population inversion) an
incident beam of photons of energy E z - E I would be more likely to cause stimulated
emission than absorption. An increase in the number of photons would therefore be
produced and such Light Amplification by the Stimulated Emission of Radiation is the
basis of LASER action. In order to build up an appreciable amplification it is neces-
sary to maintain the population inversion and to retain the gradually increasing number
of photons within the lasing medium. Photons will tend to escape from the system
but if the medium is placed between parallel mirrors, a highly directional beam will be
produced in which the light is continuously traversing the lasing medium. If light
losses due to poor reflections and scattering are minimized, and the mirror separation
d is such as to cause successive reflections to be in phase, i.e.
d = nA/2, (10.40)
thus giving a resonant cavity, amplification will result. The output from the laser can
be taken through one end mirror, by having it semi-silvered, and it will be a very
intense, monochromatic, coherent directional beam.
10.9.2 Solid state lasers

Many lasers utilize the energy states of an ion in dilute solid solution for example
ruby, Ah03, in which 0'01 per cent of the Al 3+ ions are replaced by Cr3+ ions. The
energy level structure of the Cr::l+ ion, upon which this system is based, is shown in
Fig. 10.28. Population inversion is achieved by intense excitation or optical pumping
of ground state ions into one of the two broad bands of excited states, 3 and 4, from
which the ions relax, non-radiatively, into state 2. The inversion occurs between 2 and
1 and a lasing wavelength of 0·6943 J,Lm is produced.
>-
at
~1..
c;
II
hv
.J\.IV\I\r
hv
o Pumping ~ 0
~
Emission 6943 A
Fig. 10.28 Schematic representation of the energy level structure of the Cr 3+ ion in Alz 0 3 and
its utilization in the ruby laser.
The ruby laser is used to provide either a pulsed or a continuous output but it
requires efficient cooling because of the energy released to the crystal by the non-
radiative relaxations to state 2. Table 10.10 gives a few of the many solid state lasing
systems that have been developed.
TABLE 10.10
Laser systems
(a) Solid state
Host Laser ion Emission Cum)
A1203 Cr 3 + 0·6943
CaF2 Nd 3+ 1·046
CaF2 Sm2+ 0·7085
CaF2 Ho 3+ 2·09
CaW04 Nd 3+ 1·06
Cawo 4 Ho 3+ 2·05
(b) Gas
Gas Lasing centre Emission (/olm)
He-Ne Ne 0·6328,1·15, 3·39

A A+ 0·4579,0·4764,0·4879,0·4965
Kr Kr+ 0·4619,0·4680,0·5681
Xe Xe+ 0·4603,0·5419, 0·5971
N2 N2 o· 334, 0·88, 1·04
C0 2- He CO 2 9·4, 10·4
(c) Semiconductor diode
Semiconductor Emission (/olm)
GaAs 0·84
GaP 0·72
GaAsxPl-x 0·64-0·86
InP 0·91
InAs HO
PbS 4·27
PbSe 8·53
SnxPbl_xTe 9·5-28
10. 9. 3 Gas lasers

The majority of the large number of gas lasers operate through excitation by collision
with electrons in a d.c. or rJ. excited discharge. One of the commonest is the helium-
neon laser, a mixture of He and Ne gases at partial pressures of 1 and 0·1 torr res-
pectively. Fig. 10.29 shows the energy level structure utilized. In this laser the energetic
electrons in the discharge excite the He atoms, which transfer their energy by collision
to the Ne atoms. The Ne atoms possess a variety of possible energy states, some of
which (4 and 5) are long lived (metastable), and some of which are short lived (2 and
3). As a result, population inversion can be achieved between states 2, 3 and states 4,
5 and a selection oflasing wavelengths obtained. A pulsed or continuous output can
be achieved.
10.9.4 Semiconductor diode lasers

Laser action can be produced in a number of heavily doped III-V semiconducting
P-N junctions. Fig. 10.30a shows the energy diagram for the junction in the absence
of a biasing field and it is noted that the Fermi levels on the Nand P sides are located
He Ne
20
17.5
:> _1
/
.!!.
I
>- I
~ 15
Q) I
c: I
w
I
I
: Collision with
I I walls of tube
I I
I
J
I
I
I
I I I
t
Fig. 10.29 Schematic representation of the energy level structure of He and Ne and its utilization
in the He-Ne gas laser.
N p
.;~
~:r:::;I~~mffff~ '.,m' level
(al
N P
Recombination
U~l
Bias
~ voltage
_Q) ...
W
0 c:
Q)
Q, Q)
WP;1$;1&;
(b)
junction
+
(c)
Fig. 10.30 The semiconductor diode laser. (a) The P-N junction without bias. (b) The P-N
junction with bias. (c) The physical construction of the laser diode.
within the conduction and valence bands respectively. This is because of the heavy
doping and the semiconductor, in this condition, is said to be degenerate. A very large
electron concentration exists in the conduction band and a very large deficiency of
electrons (Le. large concentration of holes) in the valence band. If a forward biasing
field is applied, of amplitude the order of the energy gap (1'5 eV in GaAs), the energy
diagram will be as shown in Fig. 10.30b. Because of the much reduced potential
barrier, a very large current flows, but more importantly there will exist in the thin
(~1 J.!m) junction region a population inversion between electron states in the con-
duction band and those in the top of the valence band. Providing the semiconductor is
of a direct band-gap type, so that the probability of radiative recombination is high,
there will be a very good chance of obtaining stimulated emission following an initial
recombination by spontaneous emission.
Amplification will only occur if the stimulated emission is retained within the junctio
region and this can be arranged by fabricating the device as shown in Fig. 1O.30c. The
light is contained in the plane of the junction by cleaving the opposite faces to be
near parallel. The high refractive index for the III-V compounds ensures a sufficient
reflection coefficient at the surface (~ 30 per cent in GaAs, since n =3'3) for lasing
action. Because of the large current and power dissipated in the device, it is operated
in a pulsed mode, the biasing field being applied as a pulse of the order of microseconds
in length. The output light pulse is obtained through the end faces of the crystal. The
most common material used is GaAs for which emission occurs at 0·838 J.!m. This and
others are shown in Table 10.10.
References
1. Bleaney, B. I. and Bleaney, B. Electricity and Magnetism, Oxford University Press (1968).
2. Fowles, G. R. Introduction to Modern Optics, Holt, Rinehart & Winston (1968).
3. Longhurst, R. S. Geometriazl and Physical Optics, Longmans (1975).
4. Wang, S. Solid State Electronics, McGraw-Hill (1966).
5. Dash, W. C. and Newman, R. Phys. Rev. 99,1151 (1955).
6. Spitzer, W. G. and Fan, H. Y. Phys. Rev. 106, 882 (1957).
7. Davis, E. A. and Mott, N. F. Phil. Mag. 22,903 (1970).
8. Goryunova, N. A., Gross, E. F., Zlatkin, 1. B. and Ivanov, E. K. J. Non-Cryst. Solids, 4,57
(1970).
9. Newman, R. and Taylor, W. W. Solid State Phys. 8,49 (1959).
10. Harvey, A. F. Coherent Light, Wiley-Interscience (1970).
11. Schulman, J. H. and Compton, W. D. Color Centers in Solids, Pergamon (1963).
12. Avery, A. J. Ph.D. Thesis, Southampton University (1967).
13. Dexter, D. 1. and Knox, R. S. Excitons, Interscience (1965).
14. Baumeister, P. W.Phys. Rev. 121,359 (1961)
15. Yariv, A. Introduction to Optiazl Electronics, Holt, Rinehart & Winston (1971).
16. Jenkins, F. A. and White, H. E. Fundamentals of Optics, McGraw-Hill (1957).
17. Karninow, I. P. and Turner, E. H. Appl. Optics 5,1612 (1966).
18. Spencer, E. G., Lenzo, P. V. and Ballman, A. A. Proc. IEEE 55,2074 (1967).
19. Hulme, K. F. Rep. Progr. Phys. 36,497 (1973).
20. E.M.I. Photomultiplier Tubes Selection Chart.
21. Hornbeck, J. A. and Haynes, J. R. Phys. Rev. 97, 311 (1955).
22. Curie, D. Luminescence in Crystals, Methuen (1963).
Questions
1. Simple dispersion theory shows that for an ionic material the refractive index due
to electronic polarization in the visible region of the spectrum can be represented
Ne 2 1
n 2 = 1 +-- 2 2'
Eorn CWo - W )
where Wo is the electronic resonance angular frequency, and N is the polarizable electron
concentration.
Show that for frequencies below resonance, the variation of n is according to eqn
(10.5).
2. Assuming the dispersion of fused silica varies according to eqn (10.5), use the data
in Fig. 10.3 to compute the values of A and B (assume B > C).
3. The F centre can be considered as an electron orbiting a centre of effective charge
+ e. Use the simple Bohr model of the atom to predict the energy of the F centre
absorption in KC1, assuming the absorption transition to be Is - 2p. The refractive
index for KCl is 1·49. How does the value compare with the observed value of2·20 eV?
4. A crystal of calcite is cut in the form of a rectangular slab, the slab being 1 cm
thick, and the slab face being parallel to the optic axis. A beam of light of wavelength
0·5 J,lm is at grazing incidence on the slab face so that its direction is perpendicular to
the optic axis. Given that no = 1·665, ne = 1·489, calculate the separation of the
points on the rear of the slab at which the E- and O-rays emerge.
5. Light of wavelength 0·5461 J,lm from a mercury lamp is incident normally on a
crystal of uniaxial quartz (no = 1·54, ne = 1·55). If the optic axis is parallel to the
crystal surface and the incident light is linearly polarized with its electric vector at
45° to the optic axis, calculate
(a) the phase difference between the E and 0 rays after 1 mm of quartz, and
(b) the thickness of quartz necessary to produce circularly polarized light (Le. to
produce a phase difference of rr/2.
6. In question 5 the crystal is replaced by one of KDP, with optic axis perpendicular
to the surface. If an electric field is now applied parallel to this axis and the direction
of polarization of the incident light is arranged to be at 45° to one of the new induced
principal axes, calculate the voltage necessary to produce circularly polarized light
(no = 1·511,r63 =9·5 x 10- 12 mV-I).
7. The temperature dependence of the energy gap of a semiconductor can be
expressed as
Eg(T) =Eg(O) + aT.
If for InSb,Eg(O) = 0·26 eV and a = -2·8 x 10- 4 eV K- I ,
(a) calculate the maximum wavelength able to be detected by intrinsic photo
conduction at 77 K;
(b) calculate the ionization energy of the donor impurities necessary to be intro-
duced to extend the ability of InSb to detect out to 10 J,lm; and
(c) discuss the usefulness oflnSb as a detector at temperatures greater than 77 K.
11 Superconductivity
11.1 Introduction
This chapter is about the properties of some materials at low temperatures. What is
meant by a low temperature? Normal room temperature is about 300 K and the
absolute zero of temperature at 0 K is infinitely far below that because it is unattain-
able. Between these limits there are a number of fairly easily attainable standard
temperatures, the boiling points of liquids (Table 11.1) which at normal temperatures
are encountered as gases.
TABLE 11.1
Boiling points of liquids spanning
a range of low temperatures
Liquid Boiling point (K)
Helium (He4 ) 4'2

Hydrogen 20'3
Nitrogen 77'4
Argon 87'3
Oxygen 90'2
Methane 111'7
Uquid helium is of particular importance because under reduced pressure it boils

at 1 K. The much rarer liquid He 3 (an isotope of helium) normally boils at 3·2 K but
can be made to boil under reduced pressure at 0·5 K with fairly simple equipment. By
using more specialized techniques [1] these two liquids provide the gateway to even
lower temperatures perhaps a few millionths of a degree above the absolute zero but still,
incidentally, infinitely far above it.
The region of low temperatures of interest in this chapter lies roughly in the range
below 20 K. It is in this range that some materials enter an entirely new and different
state of matter, the superconducting state, where some properties are strangely different
from anything experienced at normal temperatures. The discovery of superconductivity
was one of the most exciting of the century. One particular aspect is that some metals
suddenly change from being normal electrical conductors (Le. possessing electrical
resistance) to a state in which they have no measurable electrical resistance whatever
and so dissipate no power when carrying an electric current. The practical implications
for electrical engineers appear obvious but the necessity for the use oflow temperature
coolants and expensive and complex equipment usually outweigh practical advantages
SUPERCONDUcrIVITY 257
of using superconductors outside of the laboratory. If superconductivity could be

achieved at room temperature the situation would be transformed but this seems a
forlorn hope at present and the phenomenon is frrmly confmed to the realm of low
temperatures. The highest temperature to date at which superconductivity has been
shown to exist is 22·3 K. The purpose of the present chapter will be to outline and
explain the main properties of superconducting materials and give an insight into the
materials which exhibit these phenomena.
11.2 Resistanceless and superconducting states
Attention has been drawn above to one feature of a superconducting material, that is,
of having immeasurably small electrical resistance. A point of great importance is that
there is more to the super conducting state than being just resistanceless. To make this
clear some features of the resistanceless state are first considered and then contrasted
with the behaviour of a material in a truly superconducting state.
Consider then a material which has zero electrical resistance. According to the
predictions of classical electromagnetic theory its state can be characterized by saying
that its electrical field vector I is zero. There is, in addition, a direct relation between
an electric field and the rate of change of a magnetic flux density B producing it. This
Maxwell law is written in vectorial form as
curl I = -(dB/dt). (11.1)
Eqn (11.1) merely expresses Faraday's law for the relation between e.m.f. and rate of
change of flux through an area. Hence for the resistanceless state since I = 0
dB/dt = 0; whence B = constant. (11.2)
Oassical theory, then, predicts that the magnetic flux density threading the resistance-
less state will always be constant while that state exists. If this is so, the simple experi-
ment illustrated in Fig. 11.1 can be conducted to show this. Fig. 11.la shows a material
in the form of a cylinder in a resistanceless state A in the absence of a magnetic field.
A magnetic field is then applied transversely and the material is in state B because eqn
(11.2) states that since B = 0 initially in the sample it must remain so, even in the
presence of a magnetic field. The magnetic lines of induction avoid the specimen to ensure
that this happens. But suppose the starting point is as in Fig. 11.1 b where a magnetic
field is applied when the sample is in its normal state (Le. with resistance) say at room
temperature (C). If the temperature is now lowered sufficiently the sample is assumed
at some point to become resistanceless (D). Again the rule that B is constant means
that the flux of B through the sample is unchanged in the transition from the normal
to the resistanceless state. If now the applied magnetic field is switched off the flux
still threads the sample to keep B constant (E).
Suppose now that the experiment is repeated for a sample which displays super-
conductivity. The result is different and forces us to draw a clear distinction between
the hypothetical resistanceless state and the real superconducting state. Referring to
Fig. l1.la again the sample is now in the superconducting state (B = 0) and as before
a magnetic field is switched on. The transition to state B occurs. The result is the same
as for the resistanceless sample. Fig. 11.lc shows however what happens in the second
part of the experiment. In C the material in its normal state (at room temperature
again) is threaded by magnetic flux in the presence of an applied magnetic field. The
temperature is lowered until the material becomes super conducting. Immediately the
magnetic flux is expelled from the specimen (D). B is no longer constant but instead
(a)
o B
A
(b)
c D E
(c)
c D
o E
Fig. 11.1 Resistanceless cylinder in a transverse magnetic field. (a) Field applied in resistanceless
state B. (b) Field applied in normal state C, temperature lowered until resistance disappearsD, field
removedE.
Superconducting cylinder in a transverse magnetic field. (a) Field applied in resistanceless state
B.(c) Field applied in normal state C, temperature lowered until superconducting state reached D,
field removed E.
B = 0 characterizes the state of the sample. When the magnetic field is switched off
with the sample in the superconducting state, B stays zero (E). The expulsion of
magnetic flux on entry into the superconducting state is known as the Meissner effect.
It will be necessary later to make some reservations about the size of magnetic field
and the type of material but this experiment shows that the fundamental characteristic
of one type of superconductivity is B = 0 and not resistance R = O. Such a material is
a perfect diamagnet whose magnetic susceptibility X =-1 corresponds to B =0 since B =
J.LoH(1 + X). Materials showing this behaviour are known as Type I superconductors.
For the moment discussion is confmed to this type.
11.3 Superconductivity
Metals which display superconductivity differ from other metals in that at temperatures
below a critical temperature Tc the electrical resistivity is immeasurably small and the
SUPERCOND UCTIVITY 259
material is then in the superconducting state. This effect is shown in Fig. 11.2 which
also contrasts the behaviour of a normal metal for which at very low temperatures the
remanent resistivity is characteristic of residual impurities. The resistance of a super-
conductor is believed to be zero rather than just very small. It is possible to initiate a
current in a closed superconducting loop and apparently it will flow indefinitely, un-
diminished, without a source of e.m.f. Such a current is termed persistent.
f-I~
Q: 0
M
Q:
CD
U
Normal metal
...co
C
IJ)
"iii
~
CD
>
".;:;
co
Qj
a:
o 10 20
Temperature T (K)
Fig. 11.2 Temperature dependence of the resistance of a normal and superconducting metal.
TABLE 11.2
Data on some superconductors
Material Critical Ho (Am-I) Type

temperature T c (K)
Zn 0'88 4 x 10 3 I soft
Ga 1'09 4 x 10 3 I soft
Al 1'20 8 x 10 3 I soft
Th 1'37 1'3 x 10 4 I soft
In 3-40 2'3 x 104 I soft
Sn 3'72 2'5 x 104 I soft
Hg(P) 3'95 2'7 x 104 I soft
Hg(a) 4'15 3'3 x 104 I soft
Ta 4"48 6'7 'x 104 II soft
V 5'30 1'05 x 105 II soft
Pb 7"19 6'5 x 10 4 I soft
Nb 44% Ti 10'5 9"6 x 10 6 II hard
Nb 9'5 l'56x10 s II soft
Nb 25% Zr 10'8 5'6 x 106 II hard
NbN 16 8 x 106 II hard
V3 Ga 16'5 2"8 x 10 7 II hard
V 3Si 17 1'3 x 10 7 II hard
Nb3A1 18 II hard
Nb3Sn 18'5 1'6 x 10 7 II hard
Nb 3Alo·s Ge O·2 20'9 II hard
Nb3Ge 22'3 II hard
The normal to superconducting state transition is an extremely sharp one, the drop
from finite to zero resistance occurring over a temperature range of 0·05 K for a pure
material. Superconductors are characterized by Te and values of Te for some are given
in Table 11.2. Important as Te is, cooling below it will not necessarily create a super-
conducting state. As has been observed, magnetic induction is probably more funda-
mental than temperature. It is found in fact that the presence of a magnetic field can
prevent the formation of the superconducting state even below Te. Above Te a given
material can never be superconducting but below it there is, for every temperature, a
critical value of magnetic field He which, if exceeded, will destroy the superconducting
state. This magnetic field tends to a maximum value (H 0) at the absolute zero of tem-
perature. The general behaviour can be represented as a plot of the critical field He
versus temperature and is shown for lead in Fig. 11.3. The region enclosed by the
coordinate axes and the curve is the superconducting region and that outside is
the normal region.
-
0;- 7
E
.,<t.
0
';(
J: " 5
"0
..
~
o
~
Cl
4
3-
IV
E 2 Superconducting
lead
o 5 10
Temperature (K)
Fig. 11.3 Temperature dependence of critical magnetic field He for lead.
All superconductors show a similar dependence of He on T and it is found empirically

that it can be represented by the parabolic equation (I 1.3):
He=Ho (1_~22) (11.3)
The specification of Ho for a superconductor is important in relation to possible practical

applications and values for this parameter are included in Table 11.2. In addition to He
and Te a third critical parameter is often specified. A given superconductor cannot
support an electric current density greater than a critical value J c which is temperature
dependent and reaches a maximum at T = 0 K. Critical current density and critical
magnetic field are closely related since the passage of current necessarily produces a
magnetic field. Further discussion of J e will follow later.
11.4 Penetration depth
The Meissner effect has shown that in the presence of a magnetic field less than He,
B = 0 within a superconductor. An explanation of how this comes about is required.
Closely linked with the problem is the behaviour of a superconductor which carries a
SUPERCONDUCTIVITY 261
current supplied from an external source such as a battery connected across it. This
resistanceless current is 'Called a supercurrent. Since B = 0 in this case too, it implies
current density J = 0 inside the superconductor. Since the current cannot flow inside
it must flow as a surface current. One view of the Meissner effect then could be that
a surface current flows in this case also to make B =0 inside by opposing any magnetic
field which would produce a fmite B in the bulk. An alternative and equally valid view
is to treat the material as having zero relative magnetic permeability, i.e. tJr = O.
Surface supercurrents can flow then either as a screening current to make B = 0 or
as a transport cu"ent driven by an external source. It is reasonable to suppose that to
avoid an infmite current density these supercurrents will flow in a region of finite
thickness near the surface. This is found to be so and the magnitude of the current and
of the magnetic field associated with it falloff exponentially with distance from the
surface. B is not zero in this region and the magnetic field decreases with distance x
into the superconductor according to
H=Ho e- xl\ (11.4)
where H 0 is the value of magnetic field at the surface and A is a characteristic length
known as the penetration depth; A is the distance for H to fall from Ho to Hole
(Fig. 11.4).
Hs - Surface value
2>. 3>' 4>. 5>'

Depth of penetration x
Fig. 11.4 Magnetic field penetration at the surface of a superconductor.
The presence of surface currents and associated magnetic fields will obviously have a
profound effect on the properties of thin fllm superconductors, or indeed of any super-
conductors whose dimensions are comparable to the penetration depth. Some values
of A are given in Table 11.3. The small values of A show why these bulk Type I
superconductors exhibit ideal diamagnetism.
Equations to describe the superconducting state were developed by F. and H. London
by modifying Maxwell's electrodynamic equations. The London equations successfully
predict the distribution of current and magnetic field and A occurs as a characteristic
parameter in them [2].
TABLE 11.3
Penetration depths
Superconductor A(O K)
Hg 7 x W- 8 m
In 6'4 x 10-8 m
Ph 3'9 x 10-8 m
Sn 5'0 x 10-8 m
II.S The two-fluid model
One of the most fruitful qualitative models of a Type I superconductor is the two-
fluid model. In this model, the superconductivity of a region of superconductor at a
temperature T < Tc arises from an electron fluid which comprises two distinct types
of electron. There are those which have superconducting properties, and move without
resistance, the superelectrons and those with normal properties, normal electrons. This
fluid representing all the conduction electrons in a solid contains both types in a relative
proportion which is temperature dependent. At Tc all the electrons are normal and as
the temperature decreases an increasing proportion become superelectrons until at
T = 0 all are superelectrons. The transition from one type to the other is to be regarded
as a thermal excitation, from a super or perfectly ordered state (of zero entropy) to the
normal condition. The proportion in the super state is known as the order parameter W
which depends on temperature below Tc as follows:
(11.5)
Although this model proves extremely useful in thinking about superconducting
behaviour it must not be taken too literally.
11.6 The intermediate state
The influence of a magnetic field on a superconductor and the existence of a critical

field for restoration of the normal state have already been discussed. An interesting
variation on this theme is provided by the effect of a magnetic field on a superconduct-
ing sphere Fig. 11.5. At temperatures below Tc the sphere will be perfectly diamagnetic.
In an applied field Ha the fields at the equatorial positions such as A will be different
from Ha. The reason for this is that the tangential field just outside the sphere at A
-----~----~:
H=Ha
-=------
H='Jv2 Ha
Fig. 11.5 Superconducting sphere in applied field Ha showing enhanced field at equatorial
positionsAB.
SUPERCONDUCTnnTY 263
must be the same as that just inside. Now within any material there will be an intrinsic
demagnetizing effect which either adds to or subtracts from the applied field. For the
(diamagnetic) superconductor this internal field is additive so that the total internal
field Hi is given by
(11.6)
where n is a demagnetizing factor which takes different values for differently shaped
specimens. For a sphere it has the value 1/3. Thus from eqn (11.6) the internal field at
A is (3/2)H•. As a result the external field at A must also have this value.
Now suppose that H. is increased until the field at A reaches the critical value Hc.
The material of the sphere near A will want to become normal and so flux will pene-
trate at the equator. As an immediate consequence this material, now paramagnetic,
will be subject to an internal field which has reverted to a value H. less than the
critical field H c. Clearly this is a paradoxical situation. It is resolved by the specimen
adopting a completely different pattern of flux within it, as shown in Fig. 11.6. In this
Normal state
Superconducting state
Fig. 11.6 The intermediate state.
state the equatorial situation is once more stabilized, the flux having penetrated in the
form of laminae leaving superconducting material at A. Moreover, the magnetic energy
of the specimen is lowered by allowing flux to penetrate. It costs more energy to keep
it out than to let it in. If the applied field is further increased more laminae will develop.
This state of a Type I superconductor in which flux has partially penetrated is called
the intermediate state. There are a number of experimental techniques by which the
intermediate state may be directly observed. Examples are mapping with tin powder [3]
or using magneto-optics [4] .It is found that the size of the laminae is of the order of
a millimetre.
11. 7 Coherence length
In general the intermediate state consists of regions of normal material interwoven with
superconducting regions. According to the two-fluid model, there will be a high pro-
portion of superconducting electrons in the superconducting regions, the proportion
depending on the temperature. In the normal regions there are none. At the boundary
between a normal and superconducting region it is unreasonable to suppose that this
transition occurs abruptly. The proportion of superelectrons is measured by the order
parameter Wand Pippard [5] was the first to recognize the idea of a transition length
associated with W, a length in which W changed from its value in the super conducting
region to zero in the normal region. This distance is known as the coherence length (~)
and is about 10-6 m.
11. 7.1 Coherence length and surface energy

In certain circumstances the intermediate state is energetically favoured for a Type I
superconductor. To understand this consider the situation at a normal-superconducting
boundary for this state.
The normal region is normal because H has reached He, while the superconducting
region is superconducting because H has not exceeded He. These two regions are in
eqUilibrium and the situation is analogous to an equilibrium between two phases to
which simple thermodynamic arguments can be applied. The material some distance
from the boundary in both the normal and superconducting regions is also in phase
equilibrium. The appropriate thermodynamic requirement is that the Gibbs free
energy G is the same for both:
(11.7)
In the presence of a field H, G is increased by a magnetic contribution to the energy
given by
f M dH,
H
tlE= -/.Lo (11.8)
o
where M is the magnetization.
For the normal material the magnetization is negligible since the material is para-
magnetic with a small susceptibility. The superconductor, however, is diamagnetic
with M = -H and so tlE is large and positive. Since this contribution to the energy
of the superconducting region has been taken account of in eqn (11.7), in the absence
of the magnetic contribution to the energy, Gs < Gn. For H = He
tlE = /.LoHe 2 /2. (11.9)
The relative energies in each region some distance from the boundary have now been
established (Fig. 11.7a). The negative contribution to the free energy in the super-
conducting region comes from the ordering of the superelectrons and its magnitude
is given by eqn (11.9). Thus, in the presence of the magnetic field He the two contribu-
tions exactly balance to make Gs = Gn (Fig. 11. 7b).
I
I
I
G"----------i--------I;~~
I S
Normal Boundary Superconducting

(a)
I: '-J~;"
__ c (Po,;';"
magnetic
Gn _ _ _ _ _ _ _ .'.. _ _ _ _ _ _ 2 contribution)
I lJ.oHc2 (Negative
I - - ordering
I
I
_ _ 1- contribution)
(b)
Fig. 11.7 (a) Free energies in normal and supereondueting states. (b) Equilibrium of normal and
supereonducting states in presence of a critical field He.
The situation near the boundary is more complicated because both the magnetic and
electron ordering contributions vary with distance and the algebraic sum is not
necessarily zero. The characteristic length which governs how quickly the magnetic
contribution to G rises from the value Gn to Gn + !lloHc 2 is the penetration depth A
while for the order parameter it is the coherence length ~. Thus two distinct cases
arise: (a) when ~ > A and (b) when A <~. These are illustrated in Fig. 11.8(a) and (b)
G ______________
G
~
Normal \super~ondueting
(a) (b)
G G
G. Gn G.
-----+~------------~--- ~---+~------------~~
(e) (d)
Fig. 11.8 Magnetic and ordering contributions to Gibbs free energy near a normal-superconducting
boundary in equilibrium for (a) ~ > Aand (b) ~ < A, and their resultant for (c) ~ > A, (d) ~ < A.
while the variation of total free energy as a function of distance from the boundary is
shown in Fig. 11.8(c) and (d). For ~ > A the surface energy is positive while for ~ < A
it is negative. Fig. 11.8a describes the situation for Type I superconductors and so it
costs energy to form normal-superconducting boundaries. This factor determines the
pattern of boundaries in the intermediate state. Case (b) will be discussed in the next
section.
11.8 Type II superconductors
An important feature of Type I superconductors is the existence of an intermediate

state when the applied field reaches a critical value dependent on specimen geometry.
This is shown in Fig. 11.9 where the magnetization of the superconductor is plotted
as a function of applied field for (1) a sphere, (2) a cylinder subjected to a transverse
magnetic field and (3) a cylinder subjected to a longitudinal field. The curves show that
the intermediate state begins at various values of H which are geometry dependent but
for case (3) there is no such state because the demagnetization factor is zero.
A quite different class of superconducting material is also found to exist and this is
known as Type II. The most important difference from Type I is that although field
penetration occurs for applied fields lower than a critical field, this penetration is not
geometry dependent and can occur even where the demagnetization factor is zero. The
field penetration is also different in scale; it is microscopic in size and filamentary in
nature with dimensions about 10- 7 m.
To appreciate further differences between Type I and Type II consider the following
situation. Pure lead is a Type I superconductor exhibiting the magnetization curve (1)
-M
...
"
c
o
III
N
II
C
III
III
:E
~~ j~ ~
Applied magnetic field H
Fig. 11.9 Magnetization of a superconductor as a function of applied field for different specimen
geometries: (1) a sphere, (2) cylinder in transverse field, and (3) cylinder in longitudinal field.
of Fig. 11.10, assuming zero demagnetization factor. When about 10 per cent indium
is added to give a lead-indium alloy the behaviour is no longer characteristic of Type I.
The magnetization curve (2) is completely different and characteristic of Type II
materials.
-M
..
c
o
III
N
ic
III
III
:E
Hel He He2
Applied magnetic field H
Fig. 11.10 Effect of impurity on magnetization curve of a superconductor: (1) pure lead, and (2)
lead-indium alloy.
Above a critical field called Hcl penetration occurs in ftlamentary form so that the
material remains superconducting. Increase of field causes further penetration until
H =H c2, an upper critical field at which complete penetration occurs and the super-
conductor becomes normal. The condition of the specimen between Hcl and HC2 is
called the mixed state. HC2 is generally much higher than Hc for a Type I superconductor
(Table 11.2).
11.8.1 The mixed state

The intermediate state was explained in terms of a positive surface energy associated
with the formation of laminae. These are relatively large because it is energetically
favourable to make the ratio of surface to volume as small as possible. A small number
of large laminae are preferable to a large number of small ones.
The condition for a negative surface energy has been considered in subsection 11.7.1,
that is when ~ < A and is that appropriate to Type II material. Thus when a Type II
material is subjected to an external magnetic field which is slowly increased from zero,
the negative contribution to the free energy from the ordering of superelectrons makes
the superconducting state the preferred one until H =H c !' Because of the negative
surface energy associated with filament formation in Type II materials, when Hc! is
exceeded it is energetically favourable for small filaments to form with a large surface
to volume ratio. The number of these increases gradually with the field until HC2 is
reached when complete penetration is achieved and the material becomes normal.
From a practical viewpoint the importance of Type II superconductors lies in the
fact that Hc2 is much higher than critical fields for Type I materials. The concept of
coherence length provides the basis of the explanation for this phenomenon. The fila-
ments of the mixed state, which incidentally are sometimes called vortices because of
the circulating shielding currents associated with them, have a radius which is essentially
equal to the coherence length ~. The smaller ~ associated with Type II materials there-
fore allows more filaments to be packed in per unit volume before overlap takes place
and the material goes normal. This produces a much higher critical field H c2 .
It should be noted that hard drawn wires which have many metallurgical faults have
higher critical fields Hc2 than softer materials. This is because the coherence length is
closely related to the mean free path of the normal electrons and both involve inter-
action with lattice ions (subsection 11.9.2). Since the mean free path is much lower for
a hard drawn material with many dislocations ~ is lower and Hc2 is bigger.
The filaments of the mixed state may readily be observed by electron microscopy
when they are decorated with tiny iron particles deposited by special techniques [61.
11.8.2 Critical currents

A superconductor is characterized not only by Tc and Hc but also by a critical value
of current density lc. This is of considerable practical importance since, for the pro-
duction of high magnetic fields, it is necessary to be able to pass large currents through
a superconducting solenoid in the presence of the transverse magnetic field produced
by these currents. If a wire of a Type I superconductor carries a current I, there is a
surface magnetic field HI associated with that current of value I/21Tr, r being the radius
of the wire. If this field exceeds the critical magnetic field the material will go normal.
If in addition a transverse magnetic field is applied to the wire the condition for the
transition to the normal state at the surface is that the sum of the applied field and the
field due to the current should equal the critical field (Fig. 11.11a). Thus, as seen from
Fig. 11.11 b,
i.e.
hence
(11.10)
The critical current Ic will decrease linearly with increase of the applied field until it
reaches zero at Ha = Hc /2. Similar considerations apply to pure Type II superconductors
_H_8 -~-~-
*"""""
--------~~~~-------
fi----=---:
~1 ~ :
Section "x-x"
(b)
Fig. 11.11 (a) Wire carrying current I subjected to transverse field Ha' (b) Cross section of wire
showing fields at equatorial positions on the surface.
for Ha <Hcl ' that is when the superconductor is not in the mixed state. The current
carrying capability is little different from the Type I case. For Ha > Hc!> pure materials
have a small critical current which decreases to zero near Hc2 ' This is not the case for
impure Type II materials in the mixed state. The behaviour of the critical current in a
wire as a function of a magnetic field applied transversely is shown in Fig. 11.12 for
both pure and impure Type II material.
The latter is able to carry a much higher critical current, typically 108 Am- 2 flowing
through the bulk of the solid. The relative values of the currents in the mixed state shown
in the figure differ by several orders of magnitude. What is the reason for this remarkable
difference in current carrying ability? The important features are the presence of the mixed
state and the requirement for an impure material, impure in the sense of possessing
metallurgical faults (dislocations) and/or chemical impurity. The explanation lies in
the interaction of the current along the wire with the fllaments of the mixed state
aligned transversely to the current direction as illustrated in Fig. 11.13.
The filaments and their associated magnetic flux experience a Lorentz force F of
the form I x B acting in the plane of the paper. In pure Type II materials this force can
cause the fllaments to move against the viscous drag of their surroundings. This requires
work to be done, the energy coming from the currents, and is a manifestation of
electrical resistance. The material is then no longer superconducting. When the material
is very impure the resistance to fllament motion is strong because the impurities pin
/ Applied transverse magnetic field H. "'-

He, He,
T
~ig. 11.12 ~ritical current density in a wire as a function of transverse applied field for pure and
Impure matenal.
Force
Fig. 11.13 The mixed state. Normal filaments threading a current carrying wire subjected to a
transverse field.
the fIlaments. A much larger current is now required to provide the Lorentz force for
migration and the critical current is correspondingly greater. Type II materials which
are deliberately heat treated and cold worked to introduce dislocations so as to improve
Je are known as hard superconductors. In contrast, materials which are relatively dis-
location free are called soft and include Type I and some Type II.
11.9 Theory of superconductivity
Previous sections have given an outline of some important properties of superconductors.

Now consideration is given to the nature of the superconducting state and to the
understanding of that state from a microscopic viewpoint. The difficulty of the problem
may be appreciated from the fact that from the time of the discovery of supercon-
ductivity in 1911, almost forty years elapsed before any hope of a solution appeared.
A satisfactory theory was formulated in the 1950s based on the ideas of Frohlich,
Cooper, Bardeen and Schrieffer [7].
11. 9.1 The energy gap in superconductors

The distribution of electronic states in metals has been discussed in Chapter 7 and also
the arrangement of electrons in these states in their lowest energy configuration. The
density of free electron states varies continuously with energy as shown in Fig. 11.14a
and at 0 K every state is occupied up to the Fermi level E F.
(a)
EF E
L--
I
I
I
I
I
:.-- 21:
I
(b) I
I
I
I
I
I
I
I
I
EF E
Fig.l1.14 Density of states as a function of energy (a) normal metal and (b) a superconductor.
For superconductors, however, those electrons which give rise to supercurrents are
in an even lower energy state. An energy gap appears to exist in the density of states
distribution when the temperature is below the critical temperature Tc (Fig. 11.14b).
The steep rise in the density of states shown in the diagram is a consequence of the
appearance of the superconducting energy gap and has been confirmed experimentally
[8] .
The gap of width 2€ is positioned at the Fermi level and the density of states is
exceptionally large immediately above and below it. Experimental evidence for this
energy gap has come from specific heat measurements [9] and from optical data,
particularly infra-red absorption spectra [10]. The latter have shown a sharp absorption
edge. Above the frequency corresponding to this edge photons are strongly
absorbed. Such measurements are consistent with the excitation of electrons
by photons across a gap just as in a semiconductor photo detector, but here the gap
width is very small, about 10-4 eV. The effect of the gap, then, can only be observed
at low temperatures. The width of the gap is also found to be temperature dependent
decreasing to zero at Te and remaining zero for T> Te (Fig. 11.15).
1.0r--_ ___
o 1.0
Reduced temperature
Fig. 11.15 Temperature dependence of the energy gap for a superconductor.
The evidence for a gap in the energy spectrum also suggests the possibility that
electrons in the energy states below the gap may have different properties from those
above and perhaps be responsible for superconductivity. If thermal excitation across
the gap is to be small, kT must be less than 2€ (-10- 4 eV) indicating that temperatures
of about 1 K are required. Also the specific heat measurements indicate that the super-
conducting state has a lower entropy than the normal state and so is in some way
more ordered. Since the superconducting-normal transition only involves changes in
electronic properties, other properties being little affected, it is reasonable to suppose
that the greater degree of order is associated with the electrons. A picture emerges
therefore in which ordered electrons below the energy gap are in some way responsible
for superconductivity while those above the gap possess normal properties.
11.9.2 Electron interactions

For an energy gap to occur there must be a mechanism whereby electrons in super-
conductors can lower their energy and one which does not appear in normal metals or
in superconductors above Te. Since the gap is very small (-10- 4 eV) such a mechanism
is a weak attractive interaction which operates as long as the interaction energy is
greater than kT. Two interactions which certainly occur and which should be con-
sidered as possibilities are: (a) electron-electron interactions through Coulomb forces;
and (b) interactions between electrons and lattice. Interactions of type (a) are repulsive
and raise the energy of the participating electrons. If (b) is to be involved this interaction
must be strong enough to overcome the Coulomb force. The participation of the lattice
in superconductivity was shown by an important experimental result known as the
Isotope effect [11]; the critical temperature Te for a particular superconductpr was
found to depend on the isotopic massM of the particular element and given by
constant
{l 1.1 I)
.../M .
This result suggests that lattice vibrations play an important role and that indeed inter-
actions of type (b) are significant. It was the nature of this Frohlich interaction that
took so long to elucidate. It is represented schematically in Fig. 11.16.
Fig.l1.16 The Frohlich interaction.
Suppose an electron travelling with momentum kl encounters a lattice ion. Because

of the Coulomb interaction the momentum of the electron will be reduced to kl - q
and a local lattice vibration will be set up, characterized by the remainder of the
momentum q. Should a second electron of momentum k2 enter the locality of this
lattice vibration then this electron may be influenced by it. The precise effect will
depend very much on the phase of the vibration at that time but it is possible that the
whole of the momentum could be transferred to this second electron giving it a
momentum k2 + q. The process as a whole leaves the lattice completely unchanged
and yet momentum has been transferred between electrons. Detailed analysis of this
interaction has shown that it can be both attractive or repulsive depending on the
relative momenta of the two electrons. It is most strongly attractive when the momenta
are equal and opposite (k2 =-kd and when their energies (proportional to k 2)are the
same. The result of the attractive interaction is to cause the total energy of the two
electrons to drop from a value of 2E(k 1) to 2E(k 1) - 2€, where € represents the
binding energy per electron. This binding energy represents an energy gap since the
electrons are either bound or not and there is no intermediate stable state.
This attractive Frohlich interaction is thought to be responsible for the electron
ordering in superconductors. In the ordered state the electrons exist in pairs called
Cooper pairs moving within about 10-6 m of each other. Because of limitations on the
response time of the lattice to the motion of an electron, and the requirement of
momentum conservation in electron-phonon interactions, only a proportion of the
conduction electrons can take part in this pairing process. These lie within k0Debye of
the Fermi level. The importance of the lattice implies the existence of strong electron-
phonon interactions. This suggests why metals with many crystalline defects or im-
purities can become superconductors since in these, normal electrons encounter the
lattice ions more frequently.
11.9.3 Zero resistance
The final step in the argument is to show why the existence of an energy gap leads to
superconductivity. Fig. 11.17 shows energy (E) versus momentum (k) curves for two
metals at 0 K; (a) a normal metal which is not a superconductor and (b) a supercon-
ductor. These curves appear similar but in fact are quite different. For the normal
metal all electron states below EF are occupied and represent individual electrons. For
the superconductor every electron just below the energy gap is one of a Cooper pair,
the 'bond' between each member being represented by a horizontal line.
E E
+k
E
- Electric field E
- Electric field
s'
Fig. 11.17 E-k diagrams for electrons in: (a) normal metal with zero electric field; (b) supercon-
ductor with zero electric field; (c) normal metal in applied electric field; and (d) superconductor in
applied electric field.
At temperatures above 0 K some electrons will exist in energy states above the
Fermi level, distributed according to Fermi-Dirac statistics. For the normal metal
successive states near the Fermi level are only about 10-7 eV apart and so even at
low temperatures some of the higher states will be occupied. In a superconductor
an energy gap of 10-4 eV has to be surmounted and very few electrons will exist in
states above the gap near 0 K. Those that do will be single unpaired electrons possessing
normal properties. As the temperature increases the number of paired electrons de-
creases and the thermal effect on the lattice will cause the attractive interaction to be
less favourable and hence the energy gap to become smaller. The disappearance of the
energy gap coincides with the critical temperature Te. This so-called BCS theory closely
predicts the temperature dependence of the energy gap shown in Fig. 11.15.
The effect of an electric field applied to a normal metal is to impose a general drift
motion on the free electrons. This drift, which is opposite to the field direction be-
cause of the negative charge of the electrons, is illustrated by the E-k diagram of
Fig. 11.17c. This results in an increase in the total energy of the electrons resulting
from the kinetic energy associated with the drift velocity. If the electric field is
removed the state represented by Fig. 11.17 c will not perSist as the drifting electrons
will exchange momentum with the lattice ions. The total energy decrease and the
general state of motion will rapidly return to the equilibrium state represented by
Fig. 11.17a.
If a field is applied to a superconductor the effect on the paired electrons must
be considered. In zero field each electron in a pair will have equal and opposite mo-
mentum and an applied field will increase the momentum of one of a pair by the same
amount as the momentum of the other is decreased. Each pair will therefore drift as a
unit as shown in Fig. 11.17d. When the field is removed the state of motion of the
electrons will only return to the symmetrical E-k distribution of Fig. 11.17b if it is
energetically favourable to do so. To lower the energy of a particular pair (say aa' in
Fig. 11.17 d), the scission of the pair bond would be necessary and this would require
the energy of interaction to be supplied equal to the energy gap. In a superconductor
below Tc the kinetic energy of drift saved by splitting up a pair is insufficient to offset
the energy required to break the bond. The asymmetric E-k distribution of Fig. 11.17d
persists therefore and the current still flows after the electric field is switched off.
The specimen exhibits superconductivity as a persistent current. There is zero resistance
because the electrons cannot be scattered by the lattice below Tc owing to the need to
break a pair bond and this is not energetically favourable for the reasons described.
11.10 Superconducting materials and their applications
11.10.1 Superconducting magnets

At the present time the principal application of superconductors is to the production
of high magnetic fields (H> lOS Am-I) [12,13]. Their ability to pass large currents
without Joule heating means that only small power supplies are needed. The disadvant-
age of having to cool to liquid helium temperatures is small compared with the require-
ment for heat dissipation in conventional solenoids. A good example of such a solenoid
is a Bitter magnet [14]. The cooling is obtained through a stack of copper discs inter-
leaved with mica to form a conducting copper helix. The entire stack is perforated
with small holes through which water is pumped. For a magnetic field of 107 Am-I in
a 0·025 m bore solenoid the total power requirement is 1.7 MW and cooling water is
pumped through at a rate of 5 m 3 S-I.
The properties required of a superconductor for this application are that it should
remain superconducting at high currents and in high magnetic fields. The high field
which its transport current is producing does not then drive it into the normal state.
Type II materials are therefore required.
The three most important materials are all alloys of niobium and their principal
properties are given in Table 11.4. Nb (25 per cent Zr) has been widely used in the past
but is now largely replaced by the other niobium alloys. Nb (44 per cent Ti) has a
lower critical magnetic field (Hc2 ) than Nb 3 Sn but because it is easier to work, being
TABLE 11.4
Properties 0/ superconducting magnet materials
Material Critical Upper critical Critical current J c (AIIf"2)

temperature Tc field Hel (4·2 K)(Am- 1 ) (at specified field)
Nb(25% Zr) 10·8 K 5·6 x 106 109 at 3·2 x 106 Am- 1

Nb(44% Ti) 10·5K 8·8 x 106 6 x 10 8 at 7 x 106 Am-1
Nb3Sn 18·5 K 2·3 x 10 7 109 at 1·5 x 10 7 Am- 1
much less brittle it is used for fields up to 7 x lOs Am-I. Above this Nb 3 Sn must be
used. Even though their critical temperatures are well above the boiling point of
helium (4·2 K) the magnets are operated at this temperature because helium is the only
coolant available.
Materials for superconducting magnet coils must be in the form of easily wound
wire or ribbon but the precise form of the material is also governed by another require-
ment. Occasionally there is a movement of flux in a sample because filaments have tem-
porarily broken free of the pinning forces. During their movement heat is generated
which further reduces pinning forces and enhances flux movement. These flux jumps can
soon lead to a catastrophic return to the normal state resulting in the sudden release
of large quantities of stored magnetic energy. This may lead to the boiling off of
helium and melting of the coil. To prevent this sequence of events an alternative low
resistance path is provided for the sudden heat generated by embedding the super-
conducting wires in a copper matrix. This is achieved by packing a large number of
rods of the superconducting matrix into a copper tube (about 0·1 m diameter) which
is then drawn into a very fme wire and finally heat treated. Nb (44 per cent Ti) is made in
this way for solenoids. Nb 3 Sn cannot be satisfactorily drawn into a wire as it is too
hard and brittle. Instead, it is made as a thin ribbon either by vapour deposition of
Nb 3 Sn onto stainless steel or by passing a niobium tape through molten tin to form
a diffused layer ofNb 3 Sn. In both cases the ribbon is soldered to copper strip to give
thermal stability. Nb (25 per cent Zr) cannot be co-drawn with copper but can be
drawn into a wire without the copper and subsequently electroplated. In this form it
does not prove as satisfactory as co-drawn wire and has generally been superseded.
The uses of superconducting magnets for static magnetic fields have been mainly
for research purposes and occasionally for motors and generators.
11.10.2 A.c. applications

So far only direct current in superconductors has been considered. The behaviour of a
superconductor under a.c. conditions is quite different and the zero resistance state
may be lost. A brief consideration is given to a.c. behaviour, Type I and Type II
materials being treated separately. A.c. operation implies that the current direction
is changing continuously and this can only occur if the electrons are experiencing a
varying electric field. For d.c. operation the electric field in a superconductor was
zero, but for a.c. this cannot be so. Both normal and superelectrons then experience
a field, the former interaction being a dissipative process. In Type I materials any
normal resistance is effectively shorted by the zero resistance of the superelectrons
but there is also a dissipative process associated with these due to their inertial response
to the field. A continuous lag between field and current represents an inductive
reactance in the circuit which can be appreciable at high frequencies. However, for
frequencies less than 109 Hz, Type I superconductors can be considered lossless under
a.c. conditions but are not of practical importance since the critical magnetic fields
and currents are low. Type II materials below Bel behave in the same way but
fortunately the material niobium possesses high values for both Be I (1·6 x lOs Am-I)
and J e (79 X 103 Am-I of circumference). Niobium therefore has found use in the
development of superconducting cables for the low loss transmission of mains fre-
quency a.c. power [15]. Such cables are thought commercially viable where high
current densities are required and where, for environmental reasons, the cables should
be underground.
Type II materials are quite different since if the superconductor experiences a field
in excess of Bel the current no longer flows as a surface current but flows in the bulk.
If the current is alternating or if there is an alternating applied magnetic field then
there will be a changing magnetization within the superconductor. Because of pinning
by dislocations there will be resistance to flux movement and a consequent hysteresis
effect and power loss. This loss is unavoidable in Type II materials but can be minimized
by operation at low frequencies (e.g. mains frequency) and by making the material in
the form of very thin wire or tape in which the pinning forces are large enough to
prevent flux motion. The materials in Table 11.4 fall into this category and have been
used in the development of windings for altemators [12,13].
11.10.3 Other applications

Because of the problems and expense of providing cryogenic equipment and coolants
many possible uses of superconductors have not proved commercially viable. This
situation may change with the advent of new materials and techniques and so other
possible applications are mentioned here.
The diamagnetic property of a superconductor leads to repulsion of any magnetic
field to which it is subjected, provided the field does not exceed He. A force then
exists between the superconductor and the field and a classic laboratory demonstra-
tion shows a bar magnet floating above a superconducting lead dish. This demonstration
suggests the possibility of a frictionless bearing by magnetic levitation although the
technology may be complex. This idea has also been applied to the development of a
superconducting gyroscope in which a niobium rotor is levitated in the field of a
su perconducting magnet [16].
A superconductor possesses two states, the superconducting and normal and the
application of a magnetic field greater than He can initiate a change from the former
state to the latter. Removal of the field reverses the process. Such a two state device
can be used as the basis of a logic system and various superconducting computer
memory elements have been developed [17]. They have not proved competitive with
magnetic memory stores. The principle is illustrated by reference to the first such
element, the cryotron [18]. This consists of a tantalum wire around which is wound a
niobium wire. Tantalum (Te == 4·5 K) is the gate and niobium (Te == 9·5 K) the control.
The current in the control winding can produce a magnetic field sufficient to drive the
tantalum normal, closing the gate. Removal of the control current reopens the gate. The
switching time between states (10-4 s) is too long for high frequency applications.
Modifications have improved upon this time and in the later developments, the Crowe
cell [19], and the continuous film memory [20], it is 10-7 s.
11.10.4 The future

To find a material which has all the useful properties of a superconductor at room
temperature is a current dream of scientists and engineers. There seems little hope
that the conventional superconductors described above will be able to fulfIl this role
and the main hope is for a different mechanism to manifest these properties.
Currently interest centres on solids which are essentially one dimensional (long
chain) or two dimensional (layered) in structure. Under certain conditions these
can show new properties not present in three-dimensional structures. Layered structures
have weak van der Waals forces between the layers and foreign molecules can be
intercalated to form new compounds. Examples of layer materials are graphite, MoS z ,
GaS, HfS z , SnSz and transition metal di-chalcogenides MX z (X == S or Se or Te).
Experiments have been done on such compounds intercalated with both inorganic
(potassium and transition metals) and organic (aniline and pyridine) molecules [21].
As well as having other interesting properties TaSz(CsHsN)vz is a conventional
superconductor with Tc == 3·5 K.
One-dimensional solids which have been studied are mixed valency platinum salts
particularly K2 (Pt(CN)4)BrO'30 3H 20 known as KCP and some organic compounds
such as TCNQ. Both these classes of materials display one-dimensional effects. These
studies are very much on the frontiers of solid state physics at the moment and it
remains to be seen where they will lead.
References
1. Kittd, C. Introduction to Solid State Physics, Wiley (1971).
2. London, F. and London, H. Proc. Roy. Soc. A149, 71 (1935).
3. Faber, T. E. Proc. Roy. Soc. A248, 460 (1958).
4. de Sorbo, W. and Healy, W. A. Cryogenics 4,257 (1964).
5. Pippard, B.Physica 19,765 (1953).
6. Trauble, H. and Essmann, U. J. Appl. Phys. 39,4052 (1968).
7. Saunders, G. A. Con temp. Phys. 7,192 (1965).
8. Hebel, L. C. and Slichter, C. P. Phys. Rev. 113, 1504 (1959).
9. Phillips, N. E. Phys. Rev. 134, A385 (1964).
10. Richards, P. L. and Tinkham, M. Phys. Rev. 119,575 (1960).
11. Reynolds, C. A. Serin, B. and Nesbitt, L. B. Phys. Rev. 84,691 (1951).
12. Williams, J. E. C. Superconductivity and its Applications, Pion (1970).
13. Catterall, 1. A. Con temp. Phys. 12,495 (1971).
14. Bitter, F. Rev. Sci. Instr. 10,373 (1939).
15. Snowdon, D. P. Sci. Am. April 84 (1972).
16. Harding, J. T. Jet Propulsion, Lab. Tech. Rept. No. 32-897.
17. Ittner, W. B. and Kraus, C. J. Sci. Am. July, 124 (1961).
18. Buck. D. A. Proc. IRE 44. 482 (1956).
19. Crowe, J. W. IBM J. 1,295 (1957).
20. Burns, L. 1., Alphonse, G. A. and Leek, G. W. IRE Trans. Electron Comput. EC-I0, 438 (1961).
21. Geballe, T. H. Sci. Am. November, 22 (1971).
Questions
1. Given the data of Table 10.1 calculate the critical current density for a 1 mm dia-
meter wire of lead at (a) 4·2 K and (b) 7 K. A parabolic dependence of He upon T may
be assumed.
2. A superconducting Nb solenoid requires a current of 20 A in order to produce a
magnetic field of 6 x 104 Am-I. If the solenoid is immersed in liquid helium (4'2 K)
and H 0 for Nb is 1'56 x 105 Am-I, estimate the minimum diameter wire that may be
used.
3. The BCS theory of superconductivity shows that the super conducting energy gap
at 0 K is given by 3·5 kTe • Calculate the maximum wavelength of microwave radiation
that will be absorbed at 0 K in (a) lead and (b) aluminium.
4. Aluminium is characterized by the following properties: Tc = 1·20 K; H 0 =
8 X 103 Am-I; atomic wt = 26·98 kg; density = 2698 kg m- 3 and it is monovalent.
A cylindrical sample of diameter 5 mm is subjected to a magnetic field parallel to
its axis, at 0 K.
(a) Calculate the energy of magnetization in a 2 cm length when the magnetic field
is almost sufficient to bring the return of the normal state.
(b) What is this energy expressed per atom?
(c) The BCS theory states that the superconducting energy gap at 0 K is given by
3·5 kTc. Compute the proportion of conduction electrons in aluminium which
take part in the pairing interaction at 0 K.
S. Survey the values of Tc for the elemental superconductors and see if there exists
any well defmed pattern in its variation with the number of valence electrons per atom.
Appendix I Electrons in Solids
AI.I The free electron model
One fruitful model of a solid, particularly a metal, is that the electrons inside it are
confined by a potential well of the same volume as the solid, the potential being
supposed constant. The potential well is the three-dimensional analogue of the one-
dimensional well shown in Fig. AI. The problem is then to fmd the permitted states
v=o
v=-vo
x=o x= L
Fig. At One-dimensional potential well of depth Vo.
of a single electron in this well. These states are then assumed to be filled by all the
electrons treated as non-interacting particles except for the effect of the Pauli
Exclusion Principle. The quantum states of a single electron in the well are found by
solving the Schrodinger equation (AU) with appropriate boundary conditions.
(ALl)
The boundary conditions are 'IT =0 at x =0 and x =L (and similar conditions for the
y and z directions). These conditions are not strictly true unless the well is infinitely
deep but are a good approximation. The electron may be regarded as a wave character-
ized by a wave function l/I (xyz) and a wave number k (k = 27T/wavelength (A)). Since
the de Broglie relation gives the momentum of the electron as p = tzk, the kinetic energy
of the electron =p2/2m = 1i 2k 2 /2m =E - (- Vol, i.e.
h2 k 2
E+ Vo = 2m ' (AI.2)
APPENDIX I 279
so that the SchrOdinger equation becomes
li 2 1i 2 k 2
-11 2 1/1+-1/1=0. (AI.3)
2m 2m
With the specified boundary conditions the solution has the form
Irrx mrry nrrz
./, = A sin - sin - - sin- (AI.4)
'I' L L L '
where I, m and n are integers.
This solution arises by fitting into the box a three-dimensional sine wave satisfying
the boundary conditions. The latter require the rejection of otherwise possible
solutions and lead to a set of quantized states of differing wave number k. The argu-
ments of the sine function makes 1/1 = 0 at x = 0 and L, y = 0 and Land z = 0 and L if
I, m and n are integers. The set of possible states for the electron in the box then have
k values given by kx = Irr/L, ky = mrr/L, k z = nrr/L with
(AI.5)
The group of quantum numbers I, m, n takes successively higher values, the lowest
state having 1 = 0, m = 0, n = O.
The energy spacing between successive levels is clearly of the order of (112 12m) . rr2/L 2
(eqn (Al.2». For a crystal of volume 10- 6 m 3 this spacing is about 10- 15 eV near the
bottom of the well.
Information about the number of states in a given range of wave number k or energy
E may be obtained as follows. Consider a three-dimensional k space in which the co-
ordinate axes are kx, ky and k z (Fig. A2a). A point in this space represents the
dk
(a) (b)
Fig. A2 (a) Spherical shell embracing momenta between k and k + dk in the positive octant of
three-dimensional k space. (b) Cube of k space occupied by the lowest state of volume (rr/L)3.
momentum components of an electron apart from a factorll. Suppose the number of

states having wave vector between k and k + dk is required. In this coordinate space
one state is represented by the corner of a box of sides
n n n
k =1- k =1- k =1-
x L Y L Z L'
and this occupies a volume (nIL)3 in k space. Since these states are very numerous,
dividing the volume of the spherical shell between the vectors k and k + dk by the
volume occupied by one state gives us the result. But only the states in the positive
octant need be considered since the k's in all other octants merely introduce a change
of phase of the wave function and produce no new states. Therefore, the number of
states having wave number between k and k + dk is
1 4nk2 dk Vk 2 dk
dN(k) = 8"
(nIL)3 =~, (A 1.6)
where V is the volume of the crystal.

The total number of states up to an arbitrary level of wave number k is then
N(k) = - V
2n2
f k
k 2 dk =Vk- .
6n 2
3
(Al.7)
o
This number should be multiplied by 2 to take account of spin by the Pauli Exclusion
Principle. Eqns (Al.6) and (Al.7) can easily be expressed in terms of kinetic energy by
using eqn (Al.2). Then from eqn (Al.6), the number of states per unit wave number
range per unit volume of crystal
where n =N(k)
V
In terms of kinetic energy, the number of states per unit energy interval per unit
volume of crystal
dn dn dk k2 m
dE =dk . dE =2n 2 • fz2 k (Al.8)
=_1_ (2m)3/2 (E + Vo)1/2

4n 2 122 .
This is an important result, the density of states (per unit energy interval) is pro-
portional to (E + Vo)1/2.
If there are N electrons and the solid is at T = 0 K the lowest possible states are full
to a level of kinetic energy E F given by
~=~ (2m)3/2 JEF(E+ Vo)1/2 dE

2 4n 2 tl 2 '
o
i.e.
EF =4n 2 (::) (;f/3 2/3, ne (Al.9)
where ne is the electron density.

This level has a special significance and is called the Fermi level. It represents the
APPENDIX I 281
top of the electron distribution at T = O. Below this level all states are fllied with two
electrons each, allowing for spin, and above it all states are empty (Fig. A3). The Pauli
principle has forced the filling of higher levels thus pushing up the electron kinetic
energy. The energy EF can be interpreted as a temperature by using the classical
relationEF "" kTF , where k is Boltzmann's constant. Sodium, for example, has
Fermi E,F
laval
Fig. A3 Schematic description of filling of levels of the potential well by electrons at T = 0

showing effect of the Pauli principle.
EF =3·12 eV and so TF =37 000 K. This extremely high effective temperature at the
top of the electron distribution can never be utilized for obtaining heat energy because
the lattice of ions which forms the backbone structure of the solid can never become
so hot. The reason is that the lattice ions can only exchange energy with the electrons
by causing some of them to be excited to higher energy levels. The only energy avail-
able is that of the lattice itself which is at room temperature, say, and this energy is
about 0·025 eV per ion. Only electrons near the top of the distribution will be affected
and the energy they receive will be very small and so in turn will be the energy they
can return to the lattice when they drop back to their ground state levels. A similar
argument shows that only a small proportion of the electrons present will contribute
to the specific heat of the solid. This prediction contrasts with the classical kinetic
theory picture where all the electrons in the solid contribute thermal energy of about
(3/2) kT. The classical result is not in accord with the experimental results whereas the
quantum result is.
When energy is supplied to the electron distribution at T = 0 K electrons near the
top of the distribution are excited to nearby empty levels (Fig. A4). The probability
fiE) T=Q
04-------------y.-=-=~~~~----
E
Fig. A4 Probability!(E) of occupancy, by an electron, of a level of energy E at various tempera-
tures according to Fermi statistics.
that a state at a level of energy E is occupied by an electron at T = 0 K is constant and

equal to unity up to the Fermi level E F and zero above it. When the temperature of
the distribution is raised some electrons near the top are excited leaving vacant levels
or 'holes' in the electron distribution. This higher temperature distribution is also

shown in Fig. A4. It is important to know exactly how this distribution changes with
temperature and this effect is described by the following expression:
f(E) = I/{l +exp(E-EF)/kT},
where feE) represents the probability that a state of energy E is occupied at tempera-
ture T Thus at T =0 K when E < E F the exponential term becomes zero and feE) = 1.
When E > E F the exponential term becomes infinite and feE) =O. By putting feE) =!
it can readily be seen that E =E F so that at any temperature we can define the Fermi
level as that level for which the occupation probability is!. The function feE) is
called the Fermi distribution function.
Calculated values of the Fermi level energy EF are given in Table Al.I for some
alkali metals.
TABLE A1.1
Metal Li Na K
4·72 3·12 2-14
Al.2 The band model
The above model is able to explain satisfactorily some features of metallic behaviour
but the assumptions on which it is based, particularly the neglect of Coulomb inter-
action between electrons, means it is not very realistic. Moreover, one of the major
features of a real crystal is the presence of a spatially varying and periodic electric
potential arising from the presence of lattice ions. The next step must be to consider
how this potential can be included in the model. One way is to extend the previous
treatment by considering a periodic series of cubical potential boxes through which
the electron is free to move as an independent particle. The wave function 1/1 of an
electron will then be determined by a set of periodic boundary conditions which again
lead to a set of quantized states.
A one-dimensional representation of the actual potential in which a 'free' electron
moves in the crystal is shown in Fig. AS. The deep attractive wells mark the positions
.. x
V(x)
+ + + +
Fig. AS Potential experienced by an electron in traversing a line of regularly spaced ions.
of the positive ions which are made up of a nucleus plus tightly bound inner shell
electrons. These ions are regularly spaced a few Angstroms apart, the lattice spacing.
It turns out that the electron moving in such a potential can be described by a plane
wave modulated by a factor depending on the potential but essentially the state of the
APPENDIX I 283
electron is again characterized by its wave number k. The momentum of the electron
in these circumstances is called the crystal momentum. The possible values of k are
quantized by the periodic boundary conditions. Each component of k has the form
kx = mrlL, where n is an integer and 1/L is the reciprocal of the crystal dimension in
the appropriate direction. These states are so densely packed in k space as to be quasi-
continuous. When the wavelength of an electron travelling through the crystal is such
that it will be diffracted by a particular set of atomic planes, the Bragg diffraction
condition is satisfied:
n"A. = 2d sin 8,
where n is an integer, "A. the electron wavelength, d the lattice spacing and 8 the angle
of incidence. This condition implies that k = mr/(d sin 8). At this k value the travelling
wave representing the electron can be considered as having been converted to a stand-
ing wave. The solution of the SchrOdinger equation shows that at this particular k
value, there is a gap in the energy spectrum where no real solutions exist, in fact
where k is imaginary.
In one dimension the situation is as shown in Fig. A6. Here the energy of an
electron moving in the x direction is plotted as a function of its wave number. Between
k =0 and k =rrld there is a quasi-continuous set of states (drawn as a continuous
E I
~ -------------------~ I
E2 - - - - - - - - - - - - - - - - - - IP
Fig. A6 One-dimensional E-k diagram for an electron in a periodic potential of spatial period
d. (Region kx = 0 to kx = Trld is the first Brillouin zone.)
line) for the electron. When kx = rrld it encounters an energy barrier of height (El - E 2 )
preventing further increase of wave number unless this amount of energy is available to
excite the electron over the barrier. There are no permitted states for the electron
between P and Qat kx = rrld.
The region OP is said to constitute the first Brillouin zone and by extending the
principle through higher k values and to three dimensions, the states of an electron in
a crystal may be grouped into a series of such zones separated by energy gaps. When
an electron meets such a gap it needs additional energy to move into the next zone.
Within a zone an electron can only move if there are empty states which it can occupy
on gaining energy. Just as in the potential well model the lower states will be filled.
Only the occupied zones of highest energy and the empty zones immediately above
them are usually of interest. The electrons near the top of the Fermi distribution will
be of greatest interest. Another way of representing the distribution is to draw a series
of energy bands instead of Brillouin zones without specifying k. Fig. A7 shows a set of
such bands. This band picture is that arrived at in Chapter I, from a different starting
point.
Fig. A7 Energy band diagram.
The shaded bands are supposed full of electrons and the upper one empty. The
highest fully occupied band is the valence band and the next empty (or partially
occupied) band the conduction band. Each band contains many quantum states closely
spaced in energy. The gaps between bands will vary widely for different materials and
for different directions in a crystal of a given material, and they may disappear
altogether so that bands completely overlap. Depending on the material considered
and therefore on the state of occupancy of the levels in these bands the Fermi level
may be found in the conduction band, in the gap, or in the valence band.
At.3 Electrons and holes-effective mass
The anomalous behaviour of an electron near a zone boundary, that is near the top of
an energy band is very different from free electron behaviour. These unusual properties
can be deduced from the E-k diagram using some simple classical ideas. From the
de Broglie relation the wave number of an electron of velocity u may be written
hk = mu, whence
u =hk/m (AI.9)
hlkl
If E = - - , it follows that
2m
(A 1.1 0)
Comparison of eqns (AI.9) and (AI.l 0) show that the slope of an E-k curve is a
measure of the electron velocity.
Newton's laws applied to the motion of the electron give
force F =-d dk
(mu) =Ii - . (Al.l1)
dt dt
Also using eqn (Al.9)
F du hdk
-=-=--
m dt mdt
APPENDIX I 285
Using eqn (AI.l 0)
F It d(mdE) =m1'1 dkd dk(mdE)

m =m dt Ii 2 dk dt 1'12 dk '
1 dk d2 E
=r; dt dk 2•
Hence from eqn (Al.ll):

F F
(A1.l2)
m =1i 2 /(d 2 E/dk 2 )
The mass of the electron can therefore be formally identified with the expression
1i 2 (d 2 E/dk 2 )-1.
In this light, consideration of the E-k curve of Fig. A6 shows that near the edge
of the zone the electron mass is negative. Fig. A8 illustrates the variation of dE/dk
1t
dI
I
I
I
L -_ _ _ _ _ _ +-__ kx I
I
1t I
d
(a) (b)
Fig. AS (a) Variation of dE/dkx(o: velocity) with kx (0: momentum) for an electron in the first
Brillouin zone. (b) Variation of d 2 Eldkx 2 (0: l/mass) with kx for an electron in the rust Brillouin
zone. (One-dimensional 'crystal'.)
and d 2 E/dk 2 within a zone. Since the electron mass can change depending on the
curvature of the E-k curve, the mass of an electron in a crystal is called its effective
mass. It arises because of the influence of the crystal potential on the motion of the
electron. The appearance of a negative effective mass is another way of interpreting
Bragg diffraction of the electron wave. When an electron near the top of a full band
having a negative effective mass is excited to a partially empty band the vacancy it
leaves behind 'the absence of an electron of negative effective mass', may be treated
as a particle of positive charge and positive mass. This entity is called a hole. The
motion of a hole is an alternative and convenient way to describe the motion of all
the remaining electrons in the band.
APPENDIX II
Periodic chart of the elements
II III IV V VI VII VIII
r--
1 1 2
H H He
1·00797 1·00797 4·0026
2
3 4 5 6 7 8 9 10 8
Li Be B C N 0 F Ne
6·939 9·0122 10·811 12·01115 14·0067 15·9994 19·9984 20·179
2
11 12 13 14 15 16 17 18 8
8
Na Mg AI Si P S CI Ar
22·9898 24·305 TRANSITION ELEMENTS 26·9815 28·096 30·9738 32·064 35·453 39·948
,/ \
19 20 21 24 25 26 27 28 29 30 31 33 34 35 36 2
22 23 32 8
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 18
8
39·102 40·08 44·956 47·90 50·942 51·996 54·9380 55·847 58·9332 58·71 63·54 65·37 69·72 72·59 74·9216 78·96 79·909 83·80
2
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 8
18
Rb Sr V Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 18
85·47 87·62 88·905 91·22 92·906 95·94 101·07 102·905 106·4 107·870 112-40 114·82 118·69 121· 75 127·60 126·9044 131·30 8
(99)
2
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 8
18
Cs Ba *La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn 32
132·905 137·34 138·91 178·49 180·948 183·85 186·2 190·2 192-2 195·09 196·967 200·59 204·37 207·19 208·980 18
(210) (210) (222) 8
87 88 89
tAc *Lanthanum Series
Fr Ra 2
58 59 60 61 62 63 64 65 66 67 68 69 70 71 8
(223) (226) (227) 18
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Vb Lu 32
140,12 140·907 144·24 150·35 151·96 157·25 158·924 162·50 164·930 167·26 168·934 173·04 174·97 9
(147) 2
I \ .. ____ __ ! _______
'"
______
t Actinium Series
, 2
90 91 92 93 94 95 96 97 98 99 100 101 102 103 8
18
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 32
32
232·038 (231) 238·03 (237) (244) (243) (247) (247) (252) (254) (257) (257) (255) (256) 9
--- 2
APPENDIX III LIST OF THE ELEMENTS
DISTRIBUTION OF ELECTRONS WITHIN THE SHELLS

Atomic Name Symbol Atomic Group Number Atomic
Number Weight K L M N 0 P Q of Number
pdf Neutrons
s s p s p d s s pdf s p d s
1 HYDROGEN H 1·008 1 I - 1
2 HELIUM He 4·003 2 - 2 2
3 LITHIUM Li 6·939 2 1 I 4 3
4 BERYLLIUM Be 9·012 2 2 II 5 4
5 BORON B 10·81 2 2 1 III 6 5
6 CARBON C 12·01 2 2 2 IV 6 6
7 NITROGEN N 14·01 2 2 3 V 7 7
8 OXYGEN 0 16·00 224 VI 8 8
9 FLUORINE F 19·00 2 2 5 VII 10 9
10 NEON Ne 20·18 2 2 6 - 10 10
11 SODIUM Na 22·99 2 2 6 1 I 12 11
12 MAGNESIUM Mg 24·31 2 2 6 2 II 12 12
13 ALUMINIUM AI 26·98 2 2 6 2 1 III 14 13
14 SILICON Si 28·09 2 2 6 2 2 IV 14 14
15 PHOSPHORUS P 30·99 226 2 3 V 16 15
16 SULPHUR S 32·06 2 2 6 2 4 VI 16 16
17 CHLORINE CI 35·45 2 2 6 2 5 VII 18 17
18 ARGON Ar 39·95 2 2 6 2 6 - 22 18
19 POTASSIUM K 39·10 2 2 6 2 6 - 1 I 20 19
20 CALCIUM Ca 40·08 2 2 6 2 6 - 2 II 20 20
21 SCANDIUM Sc 44·96 2 2 6 2 6 1 2 Ilia 24 21

22 TITANIUM Ti 47·90 2 2 6 2 6 2 2 IVa 26 22
23 VANADIUM V 50·94 2 2 6 2 6 3 2 Va 28 23
24 CHROMIUM Cr 52·00 2 2 6 2 6 5 1 Via 28 24
25 MANGANESE Mn 54·94 2 2 6 2 6 5 2 Vila 30 25
DISTRIBUTION OF ELECTRONS WITH IN TH E SHELLS
Atomic Name Symbol Atomic Group Number Atomic
Weight K L M N 0 P Q of Number
Number
s s p s p d s pdf s pdf s p d s Neutrons
26 IRON Fe 55·85 2 2 6 2 6 6 2 VIII 30 26

27 COBALT Co 58·93 2 2 6 2 6 7 2 VIII 32 27
28 NICKEL Ni 58·71 2 2 6 2 6 8 2 VIII 30 28
29 COPPER Cu 63·54 226 2 6 10 1 la 34 29
30 ZINC Zn 65·37 226 2 6 10 2 lIa 34 30
31 GALLIUM Ga 69·72 226 2 6 10 2 1 III 38 31

32 GERMANIUM Ge 72·59 2 2 6 2 6 10 2 2 IV 42 32
33 ARSENIC As 74·92 226 2 6 10 2 3 V 42 33
34 SELENIUM Se 78·96 226 2 6 10 2 4 VI 46 34
35 BROMINE Br 79·91 226 2 6 10 2 5 VII 44 35
36 KRYPTON Kr 83·80 2 2 6 2 6 10 2 6 48 36
37 RUBIDIUM Rb 85·47 226 2 6 10 2 6 - - 1 I 48 37
38 STRONTIUM Sr 87·62 2 2 6 2 6 10 2 6 - - 2 II 50 38
39 YTTRIUM Y 88·91 2 2 6 2 6 10 2 6 1 - 2 lila 50 39
40 ZIRCONIUM Zr 91·22 226 2 6 10 2 6 2 - 2 IVa 50 40
41 NIOBIUM Nb 92·91 226 2 6 10 2 6 4 - 1 Va 52 41

42 MOLYBDENUM Mo 95·94 226 2 6 10 2 6 5 - 1 Via 56 42
43 TECHNETIUM* Tc (97) 226 2 6 10 2 6 6 - 1 Vila (54) 43
44 RUTHENIUM Ru 101-1 2 2 6 2 6 10 2 6 7 - 1 VIII 58 44
45 RHODIUM Rh 102·9 226 2 6 10 2 6 8 - 1 VIII 58 45
46 PALLADIUM Pd 106·4 2 2 6 2 6 10 2 6 10 - - VIII 60 46

47 SILVER Ag 107·9 2 2 6 2 6 10 2 6 10 - 1 la 60 47
48 CADMIUM Cd 112·4 2 2 6 2 6 10 2 6 10 - 2 lIa 66 48
49 INDIUM In 114·8 2 2 6 2 6 10 2 6 10 - 2 1 III 64 49
50 TIN Sn 118·7 2 2 6 2 6 10 2 6 10 - 2 2 IV 70 50
51 ANTIMONY Sb 121·8 2 2 6 2 6 10 2 6 10 - 2 3 V 70 51
52 TELLURIUM Te 127·6 226 2 6 10 2 6 10 - 2 4 VI 78 52
53 IODINE I 126·9 2 2 6 2 6 10 2 6 10 - 2 5 VII 74 53 I
54 XENON Xe 131·3 2 2 6 2 6 10 2 6 10 - 2 6 - 78 54
55 CAESIUM Cs 132·9 2 2 6 2 6 10 2 6 10 - 2 6 - - 1 I 78 55
56 BARIUM Ba 137·3 2 2 6 2 6 10 2 6 10 - 2 6 - - 2 II 82 56
57 LANTHANUM La 138·9 2 2 6 2 6 10 2 6 10 - 2 6 1 - 2 Ilia 82 57
58 CERIUM Ce 140·1 2 2 6 2 6 10 2 6 10 2 2 6 - - 2 Ilia 82 58
59 Pr 140·9 2 2 6 2 6 10 2 6 10 3 2 6 - - 2 Ilia 82 59
PRASEODYM I UM
NEODYMIUM Nd 144·2 2 2 6 2 6 10 2 6 10 4 2 6 - - 2 Ilia 82 60
60
61 PROMETHIUM- Pm (145) 2 2 6 2 6 10 2 6 10 5 2 6 - - 2 lila (84) 61

62 SAMARIUM Sm 150·4 2 2 6 2 6 10 2 6 10 6 2 6 - - 2 Ilia 90 62
63 EUROPIUM Eu 152·0 2 2 6 2 6 10 2 6 10 7 2 6 - - 2 lila 90 63
64 GADOLINIUM Gd 157·3 2 2 6 2 6 10 2 6 10 7 2 6 1 - 2 Ilia 94 64
65 TERBIUM Tb 158·9 2 2 6 2 6 10 2 6 10 9 2 6 - - 2 Ilia 94 65
66 DYSPROSIUM Dy 162·5 226 2 6 10 2 6 10 10 2 6 - - 2 Ilia 98 66

67 HOLMIUM Ho 164·9 226 2 6 10 2 6 10 11 2 6 - - 2 ilia 98 67
68 ERBIUM Er 167·3 2 2 6 2 6 10 2 6 10 12 2 6 - - 2 Ilia 98 68
69 THULIUM Tm 168·9 2 2 6 2 6 10 2 6 1013 2 6 - - 2 Ilia 100 69
70 YTTERBIUM Yb 173·0 2 2 6 2 6 10 2 6 1014 2 6 - - 2 Ilia 104 70
71 LUTETIUM Lu 175·0 2 2 6 2 6 10 2 6 1014 2 6 1 - '2 Ilia 104 71

72 HAFNIUM Hf 178·5 226 2 6 10 2 6 10 14 2 6 2 -- 2 IVa 108 72
73 TANTALUM Ta 180·9 226 2 6 10 2 6 1014 2 6 3 - 2 Va 108 73
74 TUNGSTEN W 183·9 2 2 6 2 6 10 2 6 1014 2 6 4 -- 2 Via 110 74
75 RHENIUM Re 186·2 2 2 6 2 6 10 2 6 10 14 2 6 5 - 2 Vila 110 75
DISTRIBUTION OF ELECTRONS WITHIN THE SHELLS
Atomic Name Symbol Atomic Atomic
Group Number
Number Weight P Q of Number
K L M N 0
p d s Neutrons
s s p s p d s pdf s pdf s
76 OSMIUM Os 190·2 226 2 6 10 2 6 1014 2 6 6 - 2 VIII 116 76

77 IRIDIUM Ir 192·2 226 2 6 10 2 6 1014 2 6 9 - - VIII 116 77
78 PLATINUM Pt 195·1 226 2 6 10 2 6 1014 2 6 9 - 1 VIII 116 78
79 GOLD Au 197·0 2 2 6 2 6 10 2 6 1014 2 6 10 - 1 la 118 79
80 MERCURY Hg 200·6 226 2 6 10 2 6 1014 2 6 10 - 2 lIa 122 80
81 THALLIUM TI 204·4 226 2 6 10 2 6 1014 2 6 10 - 2 1 III 124 81

82 LEAD Pb 207·2 226 2 6 10 2 6 1014 2 6 10 - 2 2 IV 126 82
83 BISMUTH Bi 209·0 226 2 6 10 2 6 1014 2 6 10 - 2 3 V 126 83
84 POLONIUM* Po (209) 226 2 6 10 2 6 1014 2 6 10 - 2 4 VI (125) 84
85 ASTATINE* At (210) 226 2 6 10 2 6 1014 2 6 10 - 2 5 VII (125) 85
86 RADON* Rn (222) 2 2 6 2 6 10 2 6 1014 2 6 10 - 2 6 - (136) 86

87 FRANCIUM* Fr (223) 226 2 6 10 2 6 1014 2 6 10 - 26- 1 I (136) 87
88 RADIUM· Ra (226) 226 2 6 10 2 6 1014 2 6 10 - 2 6 - 2 II (138) 88
89 ACTINIUM* Ac (227) 226 2 6 10 2 6 1014 2 6 10 - 2 6 1 2 lila (138) 89
90 THORIUM* Th 232·0 2 2 6 2 6 10 2 6 1014 2 6 10 - 262 2 lila 142 90
91 PROTACTINIUM Pa (231) 2 2 6 2 6 10 2 6 1014 2 6 10 2 2 6 1 2 ilia (140) 91

92 URANIUM* U 233 2 2 6 2 6 10 2 6 1014 2 6 10 3 2 6 1 2 lila 146 92
93 NEPTUNIUM* Np (237) 2 2 6 2 6 10 2 6 1014 2 6 10 4 2 6 1 2 ilia (144) 93

94 PLUTONIUM* Pu (244) 2 2 6 2 6 10 2 6 1014 2 6 10 6 2 6 - 2 lila (150) 94
95 AMERICIUM· Am (243) 2 2 6 2 6 10 2 6 1014 2 6 10 7 2 6 - 2 lila (148) 95
.---- -
96 CURIUM* Cm (247) 2 2 6 2 6 10 2 6 1014 2 6 10 7 2 6 1 2 Ilia (151) 96
97 BERKELlUM* Bk (247) 2 2 6 2 6 10 2 6 1014 2 6 10 8 2 6 1 2 lila (150) 97
98 CALIFORNIUM* Cf (251) 226 2 6 10 2 6 10 14 2 6 10 10 2 6 - 2 lila (153) 98
99 EINSTEINIUM* Es (254) 226 2 6 10 2 6 1014 2 6 10 11 2 6 - 2 Ilia (155) 99
100 FERMIUM* Fm (253) 226 2 6 10 2 6 1014 2 6 1012 2 6 - 2 lila (153) 100
101 MENDELEVIUM* Mv (256) 226 2 6 10 2 6 1014 2 6 1013 2 6 - 2 lila (155) 101

102 NOBELlUM* No (253) 2 2 6 2 6 10 2 6 1014 2 6 10 14 2 6 - 2 lila (151) 102
103 LAWRENTIUM* Lw (257) 226 2 6 10 2 6 1014 2 6 1014 2 6 1 2 lila (154) 103
104 2 2 6 2 6 10 2 6 1014 2 6 1014 2 6 2 104
105 226 2 6 10 2 6 1014 2 6 1014 2 6 2 105
106 2 2 6 2 6 10 2 6 1014 2 6 1014 2 6 2 106

107 2 2 6 2 6 10 2 6 1014 2 6 1014 2 6 2 107
108 226 2 6 10 2 6 1014 2 6 10 14 2 6 2 108
109 226 2 6 10 2 6 1014 2 6 1014 2 6 2 109
110 2 2 6 2 6 10 2 6 1014 2 6 1014 2 6 2 110
Notes: 1. Elements merked * are unstable.

2. In all cases, the atomic weight is shown to four significant figures where these are available.
3. The number of neutrons in the nucleus is calculated for the most commonly found isotope.
4. Room has been left at the bottom of the table for newly discovered elements to be inserted.
Bibliography
Chapter 1
Sproull, R. L. Modern Physics, Wiley (1964).
Chapter 2
Barrett, C. S. and Massalski, T. B. Structure 0/ Metals, McGraw-Hill (1966).
Stille, J. K. Introduction to Polymer Chemistry, Wiley (1962).
Chapter 3
Gilman, J. J. (Editor). The Art and Science o/Growing Crystals, Wiley (1963).
Chapter 4
James, R. W. X-Ray Crystallography, Methuen (1928).
Phillips, F. C. Introduction to Crystallography, 3rd edn, Longmans (1963).
Kelly, A. and Groves, G. W. Crystallography and Crystal De/ects, Longmans (1973).
Chapter 5
Smallman, R. E. Modern Physical Metallurgy, Butterworths (1970).
Nielsen, L. E. Mechanical Properties 0/ Polymers, Van Nostrand (1962).
Brydson, J. E. Plastics Materials, Iliffe (1969).
Chapter 6
King, A. L. Thermophysics, Freeman (1962).
Goldsmid, H. J. The Thermal Properties 0/ Solids, Routledge & Kegan Paul (1965).
Morse, P. M. Thermal PhYSics, Benjamin (1964).
Reif, F. Fundamentals 0/ Statistical and Thermal Physics, McGraw-Hill (1965).
Chapter 7
Mott, N. F. and Jones, H. Theory o/the Properties 0/ Metals and Alloys, Dover (1958).
Bulman, P. J. Trans/e"ed Electron Devices, Academic Press (1972).
Mott, N. F. and Davis, E. A. Electronic Processes in Non Crystalline Materials, Oxford
University Press (1971).
Mott, N. F. Metal-Insulator Transitions, Taylor & Francis (197 4).
Chapter 8
Zaky, A. A. and Hawley, R. Dielectric Solids, Routledge & Kegan Paul (1970).
Cady, W. G. Piezoelectricity, McGraw-Hill (1946).
Nye, J. F. Physical Properties o/Crystals, Clarendon Press (1957).
Burfoot, J. C. Ferroelectrics, Van Nostrand (1967).
Fatuzzo, E. and Merz, W. J.Fe"oelectricity, North-Holland (1967).
BIBLIOGRAPHY 293
Chapter 9
Tebble, R. S. and Craik, D. J. Magnetic Materials, Wiley (1969).
Morrish, Physical Principles of Magnetism, Wiley (1965).
Soohoo, R. F. Theory and Applications of Ferrites, Prentice-Hall (1960).
Thourel, L. The Use of Ferrites at Microwave Frequencies, Pergamon (1964).
Chapter 10
Garbuny, M. Optical Physics, Academic Press (1965).
Jenkins, F. A. and White, H. E. Fundamentals of Physics Optics, McGraw-Hill.
Fowles, G. R. Introduction to Modern Optics, Holt, Rinehart and Winston (1968).
Kruse, P. W., McGlauchlin, L. D. and McQuistan, R. B. Elements of Infra Red
Technology, Wiley (1961).
Moss, T. S. Optical Properties of Semiconductors, Butterworths (1959).
Yariv, A. Introduction to Optical Electronics, Holt, Rinehart and Winston (1971).
Baldwin, G. C. An Introduction to Non Linear Optics, Plenum Press (1969).
Lasers and Light, Readings from Scientific American, Freeman (1969).
Chapter 11
Parks, R. D. Superconductivity, Dekker (1969).
Lynton, E. A. Superconductivity, Methuen (1969).
Rose-Innes, A. C. and Rhoderick, E. H. Introduction to Superconductivity, Pergamon
(1969).
Williams, J. E. C. Superconductivity and its Applications, Pion (1970).
General
Materials-Readings from Scientific American, Freeman (1967).
Hutchinson, T. S. and Baird, D. C. The Physics of Engineering Solids, 2nd edn, Wiley
(1968).
Kittel, C. Introduction to Solid State Physics, 4th edn, Wiley (1971).
Elliott, R. J. and Gibson A. F. An Introduction to Solid State Physics, Macmillan
(1974).
Azaroff, L. V. and Brophy, J. J. Electronic Processes in Materials, McGraw-Hill (1963).
Table of Physical Constants
Avogadro's number =6·025 X 1016 (kg mol)-1

Bohr magneton /J.B =9·273 x 10-:14 A m2
Bohr radius aH = 5·292 x 10- 11 m
Boltzmann's constant k = 1·380 x 10- 23 J deg- 1 K
=8·614 X 10- 5 eV deg- 1 K
Electron charge e = 1·602 x 10- 19 Coulomb
Free electron rest mass m = 9·108 x 10- 31 kg
Gas constant R = 8·317 X 103 J (kg mol)-1 deg- 1 K
=
Permeability of vacuum /J.o 41T X 10- 7 henry m- 1
Permittivity of vacuum Eo = 8·854 X 10-12 farad m- 1
Planck's constant h = 6·625 X 10-34 Js
Ii= h/21T = 1·054 X 10-34 Js
Velocity of light c = 2·998 X 10 8 ms- 1
Units
1 Debye = 3·33 X 10- 29 Coulomb m
leV =1·602 x 10-19 J
1 Angstrom A = 1 X 10-10 m
1 micron/J.m = 1 x 10- 6 m
Answers to Questions
Chapter 2
1. Covalent; Van der Waals; metallic; ionic
3. 4; 2; 74 per cent; 68 per cent
4. ./ 8/3
s. 1: 0·414
8. 3·92 x 10- 10 m
9. About 10- 7 m; 1 in 103
10. 1·33 X 10- 4 rad
Chapter 4
1. 9°9'; 13°1'; No
2. 3·15 X 10- 10 m(b.c.c.)
3. 2·50 x 10- 5 K- 1
4. 19°49'
s. 252 K
6. 10·7 mm
Chapter 5
1. 10·7 mm
2. K =EG/3(3G-E)
3. 0·43
4. (111) [10f]; (111) [011]; (111) [101]; (111) [011]; 2·45 x 106 Nm- 2
5. 1·49 x lOs Nm- 2
7. Yes; {100}
Chapter 6
1. e- S •7
3. Electrons 6·83 x 10- 3 J mol- 1 deg- 1 K
Lattice 0·058 J mol- 1 deg- 1 K
Chapter 7
1. (a) 8·37 x 102s m- 3
(b) 7·47 x 10- 4 ms- 1
Chapter 8
2. 5·06 x 10- 9 W
4. 5·23 X 10- 30 Cm
s. 1·48; 9·6 x 10- 5 s
7. (a) i = dq/dt a: dlt../dt = constant
(b) No response
(c) Current pulse
Chapter 9
1. 3·71p.B
2. 0·61p.B
3. 9·12 X 108 Am- 1
S. (a) 5P.B (b) 5P.B
Chapter 10
2. A = 2·097; B = 1·03 X 10- 14 m2
3. 2·07 eV
4. 1·55 x 10- 3 m
S. (a) 115 rad (b) 0·014 x 10- 3 m
6. 4·17 kV
7. (a) 5·21p.m (b) 0·12 eV
Chapter 11
1. (a) 1·7 x 108 Am- 2 (b) 1·36 x 107 Am- 2
2. 1·16mm
3. (a) 0·57 mm (b) 3·43 mm
4. (a) 1·58 x 10- 5 J (b) 4·2 x 10- 9 eVatom- 1 (c) 2·3 x 10- 3 per cent
Index
Absorption, optical-see Optical absorption molecular, 23, 34

Acceptor, 132 unsaturated covalent, 19, 22
Acoustic surface waves, 172 Van der Waals, 19,23,28,30,34
Acousto-electric amplification, 136-137 Boron nitride structure, 134
Activator ion, 247 Boundary
Addition polymerization, 61 grain,39
Age hardening, 101 tilt, 39
Alkaline earth mixed oxides, 143 Bragg law, 66,283
Alloys, electrical properties, 129-130 Bravais lattice, 25
Amorphous materials, 40, 80, 146, 150 Bridgeman method for crystal growing, 46-48
Amorphous semiconductors, 59,83 Brillouin function, 190
Anisotropy, Brillouin zone, 130,283
constant, 190 Brittle fracture, 96
energy in a ferroelectric, 179 Brittle material, 89
energy in a ferromagnet, 193 Brownian motion, 149
field, 191 Bulk elastic modulus, 89
magnetic, 190 Burgers circuit, 38
Annealing, 100 Burgers vector, 38,93-95
Antiferromagnetic materials, 143, 186,197-201
compounds, 199 Capacitor, 153-154
domains in, 200 Cathodoluminescence, 249
observation of domains in, 201 Cell, primitive unit, 25
Atomic magnetism, 10-16 unit, 24
Atomic packing, 28-30 Ceramics
Atomic polarizability, 156 ferroelectric, 177
Atomic scattering factor, 67 magnetic, 206
piezoelectric, 172
Band theory of solids, 16-18, 282 Chalcogenides, 143
BCS theory of superconductivity, 273 Chalcogenide glasses, 149
B-H product, 196 Chemical transport method of crystal growth,
Biaxial crystal, 234 53-54
Bioluminescence, 249 Chemiluminescence, 249
Birefringence, 220, 233-240 Clausius-Mosotti equation, 161
natural, 233 Climb,95
induced, 237 Oose packing of atoms, 28-30
Bitter pattern, 195 Coercive field, electric, 175
Body centred cubic structure, 30 Coercive force, magnetic, 189
Bohr magneton, 11 Coherence length in a superconductor, 263-267
Boltzmann distribution, 107 Colour centres, 230
Bonding, 19-23 Compensation point, 204
energy of, 33 Compounds
covalent, 19,21,34 II-VI,134
hydrogen, 23 III-V, 134-136
in amorphous materials, 149 IV-IV, 134
ionic, 19,20,31-34 IV-VI, 134, 139
metallic, 19,22,28-30,34 V-VI,139
298 INDEX
Compounds-continued Defects
ionic, 20 dislocations, 36, 37
mixed valence, 140 Frenkel,35
transition metal, 139-141, 197-216 mterstitial, 35
Compression testing, 89 line,34,36
Condensation polymerization, 62 plane, 34, 39,40
Conduction band, 18, 130-134,284 pomt, 34, 35
Conductivity, electrical-see Electrical Schottky, 35, 36
properties vacancy, 35
ConfIgUrational coordinate diagram, 229, 248 Deformation, plastic, 90, 91
Cooper pair, 272 Degree of freedom, 106
Coordination, number, 29 Dendritic growth, 45, 57
octahedral, 202 Density of states
tetrahedral, 202 m amorphous materials, 148, 151
Correlation, 140 m metals, 112,280
Coupling coefficient, electro mechanical, m superconductors, 270
170-172 Diamagnetism, 12, 186
Covalentbondmg,19,21,34 Diamond structure, 31
unsaturated,19, 22, 34 Dielectric constant, 155
Covalent solid, 30, 34 loss, 162-164
Crack,97-98 properties of materials, 153-183
Creep, 102 relaxation, 161-165
Critical current m a superconductor, 260, Diffraction electron, 78-80
267-269 neutron, 76-78
Critical magnetic field m a superconductor, X-ray, 65-76
259-260 Dipole domam, 138
Critical temperature m a superconductor, mduced electric, 153, 156
258-260 magnetic, 11, 13
Cross Imkmg, 64 electric, 153-166
Cross slip, 95 moment electric, 153
Crowe cell, 276 permanent electric, 157
Cryotron, 276 Direct band gap semiconductor, 226
Crystal field, 12 Direct optical transition, 226
Crystallography Dislocations, 36, 56
crystal directions, 26 climb of, 95
crystal growth-see Growth cross slip of, 95
crystal morphology, 27 edge, 37, 38,93
crystal planes, 26 Frank-Read source, 94-95
crystal structure, 23 jog, 95-96
crystal symmetry, 23-26,167 loops, 93
crystal systems, 24 multiplication of, 94
X-ray, 23, 24, 65-69 observation of, 85
Crystal momentum, 283 screw, 37-38, 93
Cubic system, 26, 27 slip, 90-92
Curie Law, 158, 187 stackIDg fault, 39
Curie Temperature, 114, 143, 174, 188, 190, Disordered structures, 146,148
203 Dispersion hardenmg, 102
Curie-Weiss Law, 175, 188 Dispersion of e.m. radiation normal, 221
Curmg,64 anomalous, 222
Czochralski method for crystal growing, 46, Distribution function, radial, 80-81
48 Domams antiferromagnetic, 200
dipole, 138
ferrimagnetic, 205
Davisson-Germer experiment, 79 ferroelectric, 175, 179
De Broglie relationship, 1 ferromagnetic, 192-195
Debye magnetic bubble, 205-206
characteristic temperature, 111 observation in ferroelectric materials, 180
dielectric relaxation equations, 162 observation m ferromagnetic materials,
rmgs m electron diffraction, 79 195
-Scherrer method of X-ray diffraction, 73 Domam walls m ferroelectric materials, 179
theory of specific heat, 109, 110 m ferromagnetic materials, 194
unit of electric dipole moment, 153 Donor impurity, 132
INDEX 299
Double refraction, 235-237 valence, 18
Drift velocity of an electron, 124 Energy gap in a superconductor, 270
Drude theory of metallic conduction, 124-125, Epitaxial growth, 55-56
127 Epitaxy, 55
Ductile fracture, 98 Etching, chemical, 85
Ductile material, 89 Etch pit, 85
Exchange interaction, 13, 14, 179, 194
Edge dislocation, 37, 38, 93 Exchange constant, 14, 15
Effective mass of charge carriers, 131, 142, Exciton, 231
284 Exclusion Principle, 6, 7,19,21, 117
in III-V compounds, 136 Expansion coefficient, 115
Einstein theory of specific heats, 109, 110 thermal,114
Elastic modulus, Bulk, 89 Extended states, 148, 149
Shear, 89, 92 Extraordinary ray, 236
Young's, 89, 90 Extrinsic semiconductor, 131
Elastomer, 103
Elasto-<>ptic effect, 240 Face centred cubic, structure, 28, 30
Electric dipole, 153-166 Faraday effect, 195,216
displacement, 154 Faradays law, 257
moment, 153 Fatigue, 99
susceptibility, 155 Fault, stacking, 39
Electrical conductivity, 124 Fermi level, 17, 18, 117,128,131,132,151,
polarization, 140, 153-164, 241 242,270,272,273,280-281
properties of, Fermi statistics, 281-282
alloys, 129, 130 Ferrimagnetic materials, 198, 201-216
amorphous materials, 146, 150 applications of, 206-216
magnetic semiconductors, 143 domains in, 205
materials, 124-152 hysteresis in, 208-212
metals, 125-130 Ferrites, 143, 186,201-216
metals under pressure, 130 applications of, 206-216
semiconductors, 130-139 hexagonal,206
transition metal compounds, 141 microwave, 212-216
Electrical resistance, 124 rectangular loop, 208
resistivity, 124 soft, 207
Electro luminescence, 249 Ferroelectric materials, 166-167,175-180
Electro mechanical coupling coefficient, anisotropy energy in, 179
170-172 ceramic, 177-179
Electron band, 16-18,282-284 domains in, 175, 179-180
diffraction, 78 domain walls in, 179
drift, velocity, 124 observation of domains in, 180
cloud,2,5,6,14 phase transitions in, 175
magnetic moment of, 10 Ferromagnetic materials, 16, 186, 188-197
mobility, 125 applications of, 196-197
pairing in a superconductor, 272-274 B-H product for, 196-197
scattering, 128, 131 domains in, 192-195
spin,5 domain walls in, 194-195
Electronic polarizability, 156, 158 hard,196
Electronic polarization, 156, 158 observation of domains in, 195
Electronic structure of the elements, 8 soft, 197
Electro optical coefficient, 237 Ferromagnetism, weak, 205
Electro-<>ptic effect, linear, 237-240 Field critical magnetic, 259-267
non-linear, 241 Field ion microscopy, 84
quadratic, 240 Figure of merit for a pyroelectric material, 183
Electro-<>ptic modulation, Floating zone method of crystal growth, 49
longitudinal, 237-239 Fluorescence, 247
transverse, 240 Flux density, magnetic, 185
Electro-<>ptic properties of materials, 237-241 Fluxed melt method of crystal growth, 53
Electro-<>ptic tensor, 238 Fracture, 96-99
Electrostriction, 166 brittle, 96-98
Elements, list of, 287-291 ductile, 98
Energy bands, conduction, 17 fatigue, 99
theory of, 16-18,282-284 Frank-Read source, 94-95
300 INDEX
Free carrier optical absorption, 224, 227 Induced polarization, 156

Free electron theory of metals, 124-125, Infra red spectroscopy for structure deter-
278-281 mination, 84-86
Frenkel defect, 35 Insulator
Frohlich interaction in a superconductor, 272 electrical properties of, 18, 125, 144
Fundamental optical absorption, 223 dielectric properties. See dielectric
-metal transition, 144-146
Garnet, 143, 203 optical properties of, 218-224, 229-232
Gas laser, 252 Intensity modulation, 237-240
Gel method of crystal growth, 54 Intercalated compounds, 276
Glasses, chalcogenide, 149 Intermediate state of a superconductor, 262
transition metal oxide, 59 Inter planar spacing, 67
Glass transition temperature, 104 Intrinsic semiconductor, 130
Grain boundary, 39 Ionic bond, 19-21, 31-34
Graphite structure, 31 bond energy, 32-34
Griffith crack model, 97 materials, optical absorption in, 224,
Growth of crystals, 42-57 228-232
dendritic, 57 structure of, 31-34
epitaxial,55-56 polarization, 156, 158, 165, 222
from the melt, 42-52 Isotope effect in superconductors, 271
from the vapour, 43, 53
gel,54 Jog, 95-96
hydrothermal,53
spiral,44 Kerr effect, 195,240
Gunn diode, 137-139
Lande splitting factor, 10
Half wave voltage, 239 Langevin equation of paramagnetism, 187
Hardening, 99-102 Langevin-Debye equation for a dielectric, 157
age, 101 Larmor frequency, 13
dispersion, 102 Lasers, 250-254
precipitation, 101 Gas, 252
solution, 101 Principles of action, 250-251
strain, 99 Semiconductor, 252-254
work,99 Solid state, 251-252
Harmonic oscillator, 11 0 Lattice
Heat capacity of solids, 108-114 Bravais, 25
Hexagonal directions, 26
close packed structure, 29-30 hexagonal,27-29
crystal structure, 27 -30 imperfections, 34-40
Hole conduction, 18, 130-132, 285 interplanar spacing, 67
Hooke's law, 87,89 planes, 26
Hopping of electrons between states, 142 scattering of electrons, 131, 13 3
Hund's rules, 11, 16 structures, 23-34
Huyghen's construction, 235 vibrations, 34, 111
Hybridization, 21 Laue method of X-ray diffraction, 69-71
Hydrogen atom, 3-6 Layer line, 72
Hydrogen bond, 23 Light emitting diode, 249
Hysteresis Linear electro-optic effect, 237-240
ferrimagnetic, 208-212 Line defect, 34, 36
ferroelectric, 174, 178 Local field in a dielectric, 158-161
ferromagnetic,189 Localized state, 147-149
London equation, 261
Imperfections, see defects Lorentz force in a superconductor, 268
Impurities Lorentz local field, 158-161
effect on electrical conduction, 128-134 Lorenz number, 127-128
effect on photo conduction, 244-247 Loss tangent, 164
optical absorption due to, 22~230
Impurity scattering, 133 Madelung constant, 33
Index of refraction, 219-223,233-241 Magnetic
Indirect band gap semiconductor, 226 anisotropy, 190-192
Indirect optical transition, 227 bubbles, 205-206
Induced birefringence, 237 ceramics, 206
INDEX 301
exchange interaction, 13-16, 194 Miller indices, 26-28

field, critical, in a superconductor, 259-267 Mixed state of a superconductor, 266-267
flux density, 185 Mixed valence compounds, 140
hysteresis, 189, 208-212 Mobility of charge carriers, 124-127, 130-131,
induction, 185 135-140,148
materials, antiferromagnetic, 143, 186, in II-VI compounds, 135
197-201 in III-V compounds, 136
diamagnetic, 185-186 in IV-VI compounds, 139
ferrimagnetic, 198, 201-216 in V-VI compounds, 139
ferromagnetic, 16, 186, 188-197 in transition metal oxides, 140
paramagnetic, 13, 187-188 Mobility gap, 148-149
moment, orbital, 10 Modulation, light intensity, 237-240
spin, 10 Modulus, elastic
in transition metals, 12 Bulk,89
polaron, 143 Shear, 89,92
semiconductor, 142-144 Youngs, 89, 90
susceptibility, 185, 188 Molecular bond, 23, 34
Magnetization, 185-192 Molten zone, 51
sub-lattice, 204 Mott transition, 144-146
Magneton, Bohr, 11
Magnetostatic energy, 193
Magnetostriction, 192 Natural birefringence, 233-237
Mass, effective, of charge carriers, 131, 142, Neel temperature, 198-199
284 Negative resistance, 138
in III-V compounds, 136 Neumann's principle, 167
Materials, Neutron diffraction, 76-78
amorphous, 40, 59-60, 80-84 Nicol prism, 236
brittle, 89 Nominal strain, 87
determination of structure of, 65-86 Nominal stress, 87
dielectric properties of, 153-183 Non crystalline materials, 57-59
ductile, 89 Non direct optical transition, 228
electrical properties of, 124-151 Non linear optics, 241
magnetic properties of, 185-216 Nordheim's rule, 129
mechanical properties of, 87 -104 N-type semiconductor, 132
non-crystalline, 57 -59
optical properties of, 218-254
plastic, 60-64 Octahedral coordination, 202
preparation of, 42-64 Optical absorption, 223-232
structure of, 19-40 coeffiCient, 224
thermal properties of, 106-123 free carrier, 224, 227
Matthiessen's rule, 127-130 fundamental, 223, 225
Maxwell-Boltzmann statistics, 108-111,250 impurity, 228-230
Maxwell distribution of kinetic energies, 107 ionic materials, 224,230-232
Maxwell equations, 261 metals, 228
Mean free path of charge carriers, 127-128, semiconductors, 224-228
267 Optical
Mechanical properties of materials, 87-104 anisotropy, 233
Mechanical testing, 87-89 dispersion, 221-223
Meissner effect, 258 indicatrix, 234-237
Melt, fluxed, 53 mode scattering, 135
Melt growth of crystals, 42-52 polarization, 219
Melting, zone, 50 properties of, amorphous semiconductors,
Memory switch, 150-151 228
Metal ionic materials, 224, 228-232, 247-249
electrical properties of, 18, 34, 124-130, impurities, 228-230
278-281 metals, 228, 232-233
-insulator transition, 138, 144-146 semiconductors, 224-228, 241-247
optical properties of, 228, 232-233 pumping, 251
poly crystalline, 75 reflection, 218, 232-233
Metallic bond, 22, 28-30, 34 transitions, 226-228, 250
Microscopy, Field ion, 84 transmission, 218, 225
Microwave ferrites, 212-216 Optic axis, 234
302 INDEX
Order parameter in a superconductor, 262-263, Plastics, 60-64,103-104

265 mechanical properties of, 103-104
Ordinary ray, 235 structure of, 60-64
Orientational polarization, 157-158,222 Pnictide, 143
Orthoferrite, 143 Pockel's effect, 237
Ovonic switch, 150 Point defect, 34, 35
Oxides Poisson's ratio, 89
alkaline earth mixed, 143 Polarizability
rare earth mixed, 143 electronic, 156, 158
transition metal, 139 ionic, 156, 158
orientational, 157-158
Packing fraction, 30 Polarization
Packing of atoms, 28-30 electric, 140, 154-164,241
Paramagnetic materials, 13,187-188 electronic, 156, 222
Pauli exclusion principle, 6, 7,11,19,21, induced, 156
117,281 ionic, 156, 158,165,222
Pauli paramagnetism, 186, 188 mechanisms, 156-158
Peltier coefficient, 120 molar, 156
Peltier effect, 120-122 optical, dependence of refractive index on,
Penetration depth, 260-262, 265 220-221,233-241
Periodic potential, 282 orientational, 157-158, 222
Periodic table of the elements, 9-10,286 spontaneous, 174-175
Permeability, Polaron, 140, 142
relative, 185 magnetic, 143
frequency dependence in ferrites, 208-209, Poly crystalline materials, 96
213-216 Polymer
Permittivity, 153 mechanical properties of, 103-104
complex, 161-165 structure of, 60-62, 76
principal, 233 thermal expansion of, 115
relative, 155 Polymerization, 61-62
Perovskite structure, 143, 176-177 addition, 61
Persistent current, 259 condensation, 62
Phonon, 34-35, 111,116 P-Njunction,121,249,252-254
assisted optical transition, 227 Poling, 172
cloud, 142 Population inversion, 251
-electron interaction in a superconductor, Powder
272 metallurgy, 57-58
velocity, 11 7 diffraction, X-ray, 73-75
Phosphorescence, 247 Precession, magnetic, 212
Photo cathode, 242, 244 Precipitation hardening, 101-102
Photo conductivity, 230, 244-247 Preferred orientation, 75
Photo electric emission, 242-244 Preparation of materials, 42-64
Photo ionization of impurities, 230 Pressure, effect on electrical properties, 130
Photo luminescence, 247-249 Principal axis, 233
Piezoelectricity, 168-173 Principal permittivity, 233
anti resonance due to, 171 Proof stress, 87
applications of, 172-173 P type semiconductor, 132
ceramics, 172 Pyroelectricity, 166-167, 180-183
crystal structure, 167-168 applications of, 183
direct effect, 168 coefficient of, 180-182
electro-mechanical coupling coefficient, and crystal structure, 166-167
170-172 figure of merit in, 182-183
inverse effect, 168 materials for, 181-183
resonance, 171
scattering, 135 Quadratic electro-optic effect, 239-240
strain constant, 168-170 Quantum efficiency, 242-244
transducers, 172-173 Quantum numbers, 3-12
Pinning of filaments in a superconductor,
268-269,276 Radial distribution function, 80-81
Plane defect, 35, 39,40 Raman effect, 85
twin, 40 Random network model, 80-84
Plastic deformation, 90-91 Rare earth mixed oxides, 143
INDEX 303
Recombination, 246 structure of, 19-40

Recrystallization, 100-101 Solid state lasers, 251-252
Refining, zone, 50-52 Solution hardening, 101
Reflection, 218, 232-233 Sommerfeld model of a metal, 127-128, 278
coefficient, 233 Specific heat of solids, 108-114
Refraction, double, 235-237 Specific heat anomaly, 112-114
Refractive index, 219-223, 233-241 Spectroscopy
birefringence, 220, 233-241 infra red, 84-86
dispersion, 221-223 Raman, 85
ellipsoid, 234-237 Sphalerite structure, 134
Relative permittivity, 155 Spin
Relaxation, dielectric, 161-165 electron, 5
time, 125 magnetic moment, 10-13
Remanence, 189 quantum number, 5-9
Resistance, electrical, 124 Spinel structure
negative, 138 inverse, 201
Resistance-less state, 257 normal, 201-202
Resistivity, 124 Splat cooling, 59
Restrahlen absorption, 223, 227 Spontaneous emission, 250
Row line, 72 Spontaneous polarization, 174-175
Squareness ratio, 211
Sawyer-Tower circuit, 176 Stacking fault, 39
Scattering Statistics, thermal
electron, 128, 131 Boltzmann distribution, 107-108
impurity, 13 3 Fermi distribution, 281-282
lattice, 131,133 Maxwell distribution, 107
optical mode, 135 Maxwell-Boltzmann, 107-108
piezoelectric, 135 Stimulated emission, 250
Scattering factor, atomic, 67 Stockbarger method of crystal growth, 46-48
Schottky defect, 35-36 Stoichiometry, 143
Schrodinger equation, 1-2,4,278 Strain hardening, 99
Screw dislocation, 37-38, 93 Strain, nominal, 87
Second harmonic generation, 241 true, 88
Seebeck effect, 119 Stress, nominal, 87
Segregation coefficient, 50 proof, 87
Semiconductor, tensile, 88
amorphous, 59, 83 true, 88
diode laser, 252-254 yield, 87
direct gap, 226 Structure
electrical properties of, 130-139 body centred cubic, 30
extrinsic, 131 diamond, 30-31
impurities in, 228-230 face centred cubic, 28
indirect gap, 226 graphite, 30-31
intrinsic, 130 hexagonal close packed, 29-30
magnetic, 142-144 of amorphous materials, 40, 80-84
N-type,132 of covalent solids, 30-31
optical absorption in, 224-228 of ionic solids, 31-33
optical transitions in, 226-228 of polymers, 60-62, 76
photo conduction in, 244-247 perovskite,176-177
photo electric emission from, 242-244 practical determination of, 65-86
P-N junction, 121, 249, 252-254 sphalerite, 134
P-type,132 spinel, 201-202
thermoelectric effects in, 117-122 wurtzite, 134
Sensitizer, 248 Sub lattice, magnetic, 198, 202
Shear modulus, 89, 92 magnetization, 204
Slip, 90 Superconductor, 256-277
cross, 95 applications of, 274-277
Solid BCS theory of, 269-274
covalent, 30-31, 34 coherence length in, 263-267
ionic, 31-34 critical current in, 260, 267 -269
metallic, 22, 28-30, 34 critical magnetic field in, 259-260
molecular, 23, 34 critical temperature in, 258-260
304 INDEX
Superconductor-continued Transition metal compounds

energy gap in, 270-272 electrical properties, 139-141
hard, 269 magnetic properties, 197-216
intermediate state in, 262-263 Transition, optical, 226-228, 250
magnetic field penetration of, 257-269 Transmission, optical, 218,225
Meissner effect in, 258 Triboluminescence, 249
mixed state in, 266-267 True stress, 88
penetration depth in, 260-262 True strain, 88
soft, 269 T wall, 200
surface energy in, 264-267 Twin, 39,94
Two fluid model of, 262 Twin plane, 40
Type I, 257-265 Two fluid model of superconductivity, 262
Type II, 265-269 Type I superconductivity, 257-265
zero resistance of, 257-258, 273-274 Type II superconductivity, 265-269
Super electron, 262
Super exchange interaction, 198 Uniaxial crystal, 234
Surface energy in a superconductor, 264-267 Unit cell, 24-28
negative, 265-267 Unit cell vector, 26-27
positive, 265 Unsaturated covalent bond, 22
Surface acoustic wave, 172
Susceptibility Vacancy disc, 56
electric, 155 Valence band, 18, 130-134, 284
magnetic, 185, 188 Van der Waals bond, 23, 28-30, 34,63, 276
Switching in a dielectric, 149-151 Van der Waals force, 23, 30
memory switch, 150-151 Vapour growth, 43, 44, 53
threshold switch, 150 V centre, 231
Symmetry, 23-26,167-168 Vector
centre of, 25, 167 Burgers, 38, 93-95
effect on dielectric properties, 167-168 unit cell, 26-27
Verneuil method of crystal growth, 48-50
Vitrification, 104
tan Ii, 164-166 Vortices in a superconductor, 267
Temperature, critical in a super conductor,
258-260 Wave function, 1-6,278-279
Curie, 114, 143, 174, 188, 190,203 Wave mechanics, 1-6
Neel,198-199 Weiss field, 195
Tensile stress, 87 Whisker, 93
Tetrahedral coordination, 202 Wiedemann-Franz Law, 127
Thermal Work hardening, 99
conductivity, 115-117 Wurtzitestructure, 134
expansion, 114-115
properties of materials, 106-123 X-ray crystallography, 23-24, 65-76
statistics, 106-112 X-ray diffraction
Thermo-electric e.m.f., 117-119 Laue technique of, 70-71
Thermo-electricity, 117-123 layer line in, 72
figure of merit, 121-122 powder technique of, 73-75
generator, 121-123 rotating crystal technique of, 71-73
Peltier effect, 120-123 row line in, 72
refrigerator, 121-123 theory of, 65-69
Seebeck effect, 119 topography, 75, 201
Thomson effect, 119-120
Thermo-electric power, 117-118 Yield stress, 87
Thermo-luminescence, 249 Young's modulus, 89-90
Thermoplastic, 64
Thermosetting plastic, 64, 104 Zero resistance state of a superconductor,
Thomson effect, 119-120 257-258,273-274
Threshold switch, 150 Zinc blende structure, 134
Tilt boundary, 39 Zone,
Topography, X-ray, 75 noating, method of crystal growth, 48-50
Transition metal, 9-10, 12 refining, 50-52

Physical Properties of Materials

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Physical Properties of Materials

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PHYSICAL PROPERTIES OF MATERIALS

THE MODERN UNIVERSITY PHYSICS SERIES

Clark: A First Course in Quantum Mechanics (Revised Edn.)

M. C. LOVELL, A. 1. A VERY, M. W. VERNON

VAN NOSTRAND REINHOLD COMPANY

New York - Cincinnati - Toronto - London - Melbourne

Reprinted with corrections 1977

All rights reserved. No part of this work covered by

Published by Van Nostrand Reinhold Company Ltd.

Van Nostrand Reinhold Company

Van Nostrand Reinhold Limited

Van Nostrand Reinhold Australia Pty. Limited

Library of Congress Cataloging in Publication Data

ISBN-l3: 978-0-442-30097-5 e-ISBN-13: 978-94-011-6065-0

University Press, Cambridge

CHAPTER 2 STRUCTURE OF SOLIDS

CHAPTER 3 PREPARATION OF MATERIALS Page

CHAPTER 4 PRACTICAL DETERMINATION OF STRUCTURE

CHAPTERS MECHANICAL PROPERTIES OF MATERIALS

CHAPTER 6 THERMAL PROPERTIES

CHAPTER 7 ELECTRICAL PROPERTIES

CHAPTER 9 MAGNETIC PROPERTIES

APPENDIX I ELECTRONS IN SOUDS

APPENDIX II PERIODIC CHART OF THE ELEMENTS 286

APPENDIX III UST OF THE ELEMENTS 287

Table of Physical Constants 294

Answers to Questions 295

1. 2 Wave mechanics [1]

A =h/mu =h/p, (Ll)

-h2- (a a -1/1 +a -1/1) =--+V1/I

Fig. 1.1 Wave function IJi as a function of distance x.

Fig. 1.2 Standing waves on a string of length L fixed at both ends.

1.2.1 The hydrogen atom

and eqn (1.4) becomes

'i/21/1(r, 0, l/J) + h2 e2 ) 1/I(r, 0, l/J) =0,

1 a (r2 -a1/1 ) + -1- - a

1/I(r, 0, l/J) = R(r)F(O)4J(l/J) , (1.8)

4J(l/J)=Ae imlfP , (1.9)

Fig. 1.5 Typical electron cloud patterns.

1.3 Many-electron atoms and the Pauli Principle

1. 3.1 Electron states in multi-electron atoms

----- --- ---- ------- ----,i=1

Hydrogen I n=1 n=2 n=3 n=4

Atomic number Element K L M

1.4 Transition elements

Atomic number Element Electron configuration

1.S Atomic magnetism

these two electron contributions, i.e.

Il orb = IlB + 21lB = 31lB (1.12)

Fig. 1.8 Typical d wave functions.

Fig. 1.9 Overlap of charge clouds of d electrons on adjacent atoms.

Fig. 1.10 Lining up of successive spins by pair interaction (J> 0).

Fig. 1.11 Antiparallel arrangement of spins (J < 0).

Fig. 1.12 Variation of exchange constant J with interatomic distance.

1.6 Electrons in solids

Fig. 1.13 Energy level splitting as a function of atomic spacing.

Fig. 1.14 Energy bands in a solid.

(I) Conductor (II) Conductor (III) Semiconductor (IV) Insulator

1. Mott, N. F. Elements of Wave Mechanics, Cambridge University Press (1952).

2.1 Introduction-atomic bonding

(i) ionic bonding,

V ={decrease in potential energy} + ( increase in potential energy}

nA/r~+1 = mB/r[['+l. (2.4)

X .... ----- Resultant energy