PHYS 7500

Condensed Matter
Physics
1
Professor Sen Cadogan
Room 311 Room 311
Allen Building
Notes #1
1
Course Information
A selection of good CMP books
Kittel, Hook & Hall, Ashcroft & Mermin,
Myers, Dekker, Rosenberg
Assessment:
Exam 60%
Assignments 40%
Web page available
Diagrams are taken from Hook & Hall
unless otherwise noted
Most problems will be taken from the
above books
2
Possible Topics
Crystal structures & dynamics (Ch 1-2 :
Hook & Hall)
Electrons in metals (Ch 3)
Energy bands (electrons in a periodic
potential) (Ch 4)
Semiconductors (Ch 5)
Superconductivity (Ch 10)
Brief Introduction to Mssbauer
Spectroscopy
Brief Introduction to Neutron Scattering
3
Crystals
Periodicity (regular arrangement of atoms)
Symmetry
Infinite 3D array
Lattice (mathematical array of identical
points)
+ Basis (1 or more atoms)
= Crystal
The lattice shows the crystal symmetry
(e.g. mirror planes, rotation axes 2/n-fold
rotation)
Lattice vectors a, b and c
Any point can be reached by a translation
vector (u,v & w are integers)
c b a r w v u + + =
4
Unit Cell
A generating cell, building block
Repetition of the cell in 3D builds up the
whole lattice
Infinite number of possible cells
Primitive cell has minimum volume Primitive cell has minimum volume
one lattice point
Bravais (1845) 14 lattice types in 7 crystal
classes
( ) c b a = V
5
7 crystal classes
Cubic, hexagonal,
tetragonal,
orthorhombic,
trigonal,
monoclinic,
triclinic
c

triclinic
Describe with 3
axes and 3 angles
e.g. cubic : a=b=c
and == = 90
o
a
b

6
Simple Cubic
Lattice points on the corners
8 points each point is shared between 8
neighbouring cubes
So, 1 point/cube (primitive)
e.g. CsCl
7
Body-Centred Cubic
Lattice points on the corners + 1 in the
centre of the cube
So, 2 points/cube e.g. Fe, Na, Cr
(8 x 1/8) + 1 = 2
8
Face-Centred Cubic
Lattice points on the corners + 1 in the
centre of each face
Face atoms are shared betrween 2 cubes
So, 4 points/cube e.g. Al, Ni, Cu
(8 x 1/8) + (6 x 1/2) = 4
9
Other important structures
Hexagonal Close Packed
Diamond (e.g. Si, Ge) 2 fcc
lattices with a relative
displacement of (a/4, a/4, a/4) displacement of (a/4, a/4, a/4)
Zincblende (ZnS) e.g. GaAs
10
Atomic Positions
e.g the body-centred position in
the bcc structure is (a/2, b/2,
c/2)
Notation is (0.5, 0.5, 0.5)
c
a
b
11
We can also draw this centred position as a
projection
e.g. project into the ab plane
The point is c/2 above the ab plane
b
a
(1/2)
12
Metal Structures
Generally simple
Dense packing + high symmetry
FCC 12 nn 74% packing fraction
BCC 8 nn 68% packing BCC 8 nn 68% packing
SC 6 nn 52%
HCP 12 nn 74%
13
Packing Fraction
% of available volume occupied by an
atom (considered as hard spheres)
( )
( )
52 . 0
2
3
4
. .
2
3
4
3
4
1
2
3
3
3
3
3
= =
=
= =
=
a
a
F P
a V
a
r V
a
r
cube

14
Crystal structure determination
Crystal class (cubic, tetragonal,
hexagonal )
Bravais Lattice (face-centred, body,
simple )
Lattice parameters (a, b, c, , , )
e.g. cubic, a=b=c and ===90
o
so
1 unknown (a)
e.g. tetragonal a=bc, ===90
o
so
2 unknowns (a and c)
Atomic positions
Overall symmetry of lattice ( Space
Group .. 230 groups)
15
X-ray diffraction
Roentgen (Nobel 1901)
von Laue (1914)
Bragg & Bragg (1915)
Atomic size ~ 1
Spacing between atomic planes ~
few
The (x-ray) ~
Atomic planes = diffraction grating
16
Braggs Law
Elastic scattering no energy loss so
k
in
= k
out
(
in
=
out
)
Path difference = 2 d sin
Constructive interference when path
difference = n

n = 2 d sin
d

17
Notation
1. Directions e.g. [231]
2. Planes: axial intercepts, then reciprocals, then
integers.
c b a T + + = 3 2
integers.
= Miller indices e.g. (463)
3. Index = 0 if the plane does not cut a particular
axis
Q. Why reciprocals ?
A. All planes are describable within the unit cell
18
Interplanar spacing
d(a, b, c, , , , h, k, l)
e.g. cubic
Miller Indices of the plane
2 2 2
l k h
a
d
+ +
=
X-rays scatter from the electrons
Scattering power is element-specific (# of
electrons)
e.g. Fe (Z=26) & Co (Z=27) hard to
distinguish
e.g. Fe (Z=26) & Pt (Z=78) easy to
distinguish
Hard to see light elements.
19
Scattering Amplitude Scattering Amplitude
Sum the scattering over all atoms in the
structure
is the atomic-specific form factor
i
f
( )

+ +

i
lz ky hx i
i
i i i
e f
2
Indexing an XRD pattern
(hkl) Line positions () crystal class &
lattice parameters
Relative peak intensities atomic
positions within cell
i
f
[ ] 0 = Z f
i
20
Systematic absences Systematic absences
Simple Cubic: atom position (0,0,0)
So, all (hkl) peaks appear in the XRD pattern
Body-Centred Cubic: atoms at (0,0,0) and
(, , )
( )
1
0 0 0 0 2
= =
+ +
e e
l k h i
( )
( )
+
+ +
+ +
e e
l k h i
l k h i
2
0 0 0 2
2
1
2
1
2
1

So, peaks with h+k+l=odd e.g (120), (111) are

absent
( )
( )
( )
)
`

= + +
= + +
=
+ =
+
+ +
+ +
+ +
odd l k h
even l k h
e e
e e
l k h i
l k h i
l k h i
0
2
0
2
0 0 0 2
2 2 2

21
Neutron Diffraction Neutron Diffraction
Neutrons can also be used to solve crystal
structures
De Broglie
~ 1.5 at RT
Neutrons have no electric charge so minimal
p
h
=
absorption
Neutrons scatter mainly from nuclei so can
see light elements well (unlike X-rays)
Can also distinguish neighbouring elements
(e.g. Fe and Co)
Neutrons have a magnetic moment so you can
also determine magnetic structures.
22
Wigner Wigner--Seitz cell Seitz cell
Another way of constructing a unit cell
Draw a line from the central point to each
surrounding point
Draw the perpendicular bisectors to each line
The enclosed volume is the Wigner-Seitz cell
(a unit cell).
23
Reciprocal Lattice Reciprocal Lattice
A family of crystal planes can be
represented by (i) the normal vector + (ii)
the interplanar spacing
n
hkl
Define a new lattice in Reciprocal Space
d
hkl
hkl
hkl
hkl
d
n
G 2 =
24
Each family of planes in REAL space one
lattice point in RECIPROCAL space
Define lattice vectors in RECIPROCAL
space
Relate to the REAL space lattice vectors
a*, b* and c*
* * *
c b a G l k h
hkl
+ + =
c b
0
2
*
*
=
=
b a
a a
( ) c b a
c b
a

= 2
*
25
Crystal Binding Crystal Binding
Cohesive Energy: separate a crystal into its
components
NaCl + 8.18 eV Na
+
+ Cl

Long-range attractive Coulomb forces

Short-range repulsive forces prevent overlap of
electron shells (Pauli)
Repulsion Repulsion
empirical repulsive potential (Lennard-Jones)
Quantum Mechanics (Born-Mayer)
B, and are parameters to be determined
experimentally
( )

r
e r U
R

=
( )
12
r
B
r U
R
=
26
Attraction
Coulomb (valence electrons, ions )
5 distinct categories
1 van der Waals
the inert gases e.g. Ar in their solid state
Closed electron shells neutral, spherical on
average
Fluctuations instantaneous electric dipole
moments
Weak attraction between dipoles (E fields)
Attractive potential energy:
Total pair-potential energy is
Total potential energy of solid is
( )
6
r
A
r U
A
=
( )
6 12
ij ij
ij
r
A
r
B
r U =

|
|

\
|
=
j i
ij ij
r
A
r
B
U
6 12
2
1
27
Lennard-Jones (van der Waals)
28
2 Ionic
e.g. NaCl Na 11 e

1s
2
2s
2
2p
6
3s
1
= [Ne] 3s
1
Cl 17 e

[Ne] 3s
2
3p
5
Ionization Energy:
Na + 5.14 eV Na
+
+ e

Electron Affinity:
Cl + e

Cl

+3.61 eV
Na + Cl + 1.53 eV Na
+
+ Cl

+ electrostatic attraction between Na

+
and Cl

+ electrostatic attraction between Na

+
and Cl

ions
Coulomb potential energy
( )
ij o
ij
r
Q
r U
4
2
=
+
2.82
U = 5.11 eV
29
Total electrostatic energy = ?
ATTRACTION
+ + +
+ + +
+ + +
REPULSION REPULSION
+ + +
+ + +
+ + +
30
NaCl
Na
+
has 6 Cl

nn at distance R
o
+ 12 Na
+
nnn at distance R
o
2
+ 8 Cl

nnnn at distance R
o
3
etc
Electrostatic energy per ion pair is

o o
R
e
U
4
2
=
is the Madelung constant depends on
structure
Convergence is a problem
L + + =
3
8
2
12
6

31
Madelung Constant Madelung Constant
Structure
CsCl (sc) 1.76268
NaCl (fcc) 1.74757
ZnO (hexag) 1.63870
ZnS (diamond) 1.63806
Simple cubic has the largest so why arent
all compounds simple cubic ?
Electrostatic energy varies as 1/R
o
so why
doesnt the crystal structure collapse ?
Quantum , Pauli, repulsion etc
32
3 Covalent
Sharing of valence electrons
e.g. H
2
, C, Si, Ge
(Hook & Hall)
Symmetric (+)
( )
( )
2 1
2 1



+

+
Anti-Symmetric (-)
33 34
Symmetric: electrons provide an electrostatic
attraction between the + ions
So, U is lower
2 2
middle middle
+
>>
2
K
Also, K is lower
2
K
35
4 Metallic
Not as identifiable as the others
Atom (e.g. Na) donates 1 or more electrons
to the entire crystal
Approx. uniform electron gas
High electrical & thermal conductivity
Delocalization of the electron reduces the
kinetic energy
Particle in a box problem
( )
2
2
8ma
nh
K
n
=
36
5 Hydrogen-bonding
H atom forms link between 2 other atoms (F,
O, N )
Partially covalent and partially ionic
Electric dipole moments
e.g. ice, glue, DNA
O
H
H
H
H
O
37
Lattice Vibrations Lattice Vibrations
Atoms in a crystal are never stationary even
at T=0 (Heisenberg, zero-point motion)
Assume small amplitude Harmonic Limit
Basically, Hookes Law
Atoms connected by springs (spring constant
)
2
2
1
x U x F = =
Levy
2
x U x F = =
38
1D chain lattice of identical masses (spacing a)
Only nearest-neighbour forces
Displacements from equilibrium positions =
n-1 n n+1 n+2
n
u
( ) ( ) u u u u F =
Travelling-wave solution
( ) ( )
( )
n n n n
n n n n n
u u u u m
ma
u u u u F
2
1 1
1 1
+ =
=
=
+
+

& &
Equation of Motion
( )
( ) t kna i
n
e A t u

=
39
Substitute back into Equation of Motion
k
v
na x
t kx
k

=
=
+
=
2
Wavevector
Speed
( )
( ) t kna i
n
e A t u

=
Substitute back into Equation of Motion
Solution is a Standing wave !
|

\
|
=
2
sin
2 2
max
2
ka

m

4
max
=
40
w
Dispersion relation Dispersion relation
Plot
k vs
k
3/ 3/ 2/ / 2/ /
Note: ALL possible values of are
contained in the range
1
st
Brillouin Zone
a
k
a

+
41
Low frequencies:
phase group
o
v v
k v
x x
k
=
=

sin
0
Homogeneous line
Many atoms participate in all displacements
Long- waves insensitive to the structural
details
Levy
42
Higher frequencies
k
v
dk
d
v
v v
a
a
k
phase group
phase group

= =

2
At the edge of the 1
st
Brillouin Zone
is the physical quantity
No energy transfer (propagation)
0 =
=
group
v
a
k

group
v
43
w
k
3/ 3/ 2/ / 2/ /
44