Subject: Solid State Physics – II

Topic: Defects in Crystals

Dr Khizar Hayat
Assistant Professor, Department of Physics

Abdul Wali Khan University Mardan

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 Defects in Crystals
1. Crystal imperfections
2. Thermodynamics of Point defects
3. Schottky and Frenkel defects
4. Color centres
5. Dislocations in Solids
6. Edge dislocation
7. Screw dislocation
8. Slip and plastic deformation
9. Stacking faults
10.Grain Boundaries
11.Strength of Crystals
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 Defects in Crystals
Questions?
• What types of defects exist/arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable / unwanted?

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 In a perfect crystal, all the atoms are at rest on their correct
lattice positions at absolute zero and such a perfect lattice
can be obtained hypothetically.

 If materials were perfect crystals then their properties would

be dictated by their composition and crystal structure alone.

 However, in actual crystals, imperfections or defects are

always present which effect the properties of crystals;
therefore, it is very important to understand the defects or
imperfections in these crystals.
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The concept of imperfections or defects in crystals is important to
understand because some properties of crystalline materials are
structure-insensitive (means the materials properties are not affected
by the presence of defects in the crystal) such as elastic constant,
melting point, density, specific heat, stiffness, coefficient of thermal
expansion, etc.

However, some properties of crystalline materials are structure-

sensitive (means the materials properties are greatly affected by
relative minor changes in crystal structure by the defects or
imperfections) such as all mechanical properties, ductility, crystal
growth, magnetic hysteresis, dielectric strength, conduction in
semiconductors,
5 etc. 11/17/2018
It is the possibility of making imperfectly crystalline materials
that permits material’s scientists to tailor material’s properties
into the diverse combinations that modern engineering
devices require.

In this course we will study to identify and describe

the various types of defects or imperfections in
crystalline solids.

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 Crystalline defects or imperfections
0-dimensional 1-dimensional 2-dimensional 3-dimensional
defects defects defects defects

The defects that They are lines The surfaces along The defects that
affect isolated sites along which the which distinct change the
in the crystal crystal pattern is crystallites are crystal pattern
structure are called broken are called joined together are over a finite
0-dimensional 1-dimensional called 2-dimensional volume are called
defects defects defects 3-dimensional
defects

Also called Also called

Point Defects Also called Surface or planer Also called
Dislocations or Defects macroscopic or Bulk
Line Defects or Volume Defects
• Vacancy atoms
• Interstitial atoms
•
• Free or external • Voids or pores
• Substitutional Edge dislocations
atoms, etc • Screw dislocations
surfaces • Inclusion
• Grain Boundaries • Second phase
• Mixed dislocations
• Internal defects
7 particles or
11/17/2018 dispersants, etc
NOTE: Thermal vibrations
As in a mathematically or hypothetically perfect lattice the
atoms should exactly occupy the sites to which they are
attached. However, in practice or in reality, no crystal is
perfect, as the atoms in crystals vibrate about their mean
position at lattice the sites.
The frequency of vibration is almost independent of
temperature, but the amplitude of vibration increases with
increasing temperature.

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 1. Point Defects (0-dimensional defects)

 The defects that affect isolated sites in the crystal structure

are called point defects

Point defects are structural imperfections resulting from

thermal agitation.

Classes of Point Defects

• Vacancy
• Interstitial defect
• Substitutional defect

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 Point Defects (0-dimensional defects)
Vacancy: A Vacancy refers to an atomic site from
where the atom is missing.
OR
An atom or an ion missing from its regular
crystallographic site

Vacancy

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 Point Defects (0-dimensional defects)
Vacancy:
Vacancy
distortion
of planes

 It is not possible to create a crystal free of vacancies.

 About 1 out of 10,000 sites are vacant near melting.
Thermodynamics (temperature and counting) provides an expression for

Vacancy Concentration: Nv  Q 
 exp   v 
N  kBT 

Qv=vacancy formation energy

kB= 1.38 x 10–23 J/atom-K = 8.62 x 10–5 eV/atom-K
kB/mole = R = 1.987 cal/mol-K
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 Point Defects (0-dimensional defects)
Vacancy:
Planes distortion as a result of vacancy

Anion
Cation

Cation
vacancy

11/17/2018 Anion vacancy 12

 Point Defects (0-dimensional defects)
Schottky imperfection:
A pair of cation and anion missing from an ionic crystal
resulting in a pair of vacant ion sites is called Schottky
imperfection

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 Point Defects (0-dimensional defects)

Interstitial defect:
A point defect produced when an atom is placed into the crystal at
a site that is normally not a lattice point.
 Self Interstitials defects
 Substitutional interstitials defects

 Self Interstitials: “Extra" atoms of the same material occupy

the interstitial sites in between atomic sites

self-
distortion interstitial
of planes

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 Point Defects (0-dimensional defects)
Frenkel imperfection:
An ion displaced from a regular site to an interstitial site is
called Frenkel imperfection.
OR
A combine vacancy-interstitial defect is called Frenkel
defect.

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 Point Defects (0-dimensional defects)

Interstitial defect:
 Substitutional Interstitials:
When foreign atoms occupy the interstitial sites in between
atomic sites of the parent material

Substitutional
Interstitials

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 Point Defects (0-dimensional defects)
Substitutional defect:
A point defect produced when an atom is removed from a regular
lattice point and replaced with a different atom, usually of a different size.
OR
A Substitutional impurity refers to a foreign atom that has replaced
a parent atom.

large substitutional atom small substitutional atom

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 Point Defects (0-dimensional defects)

Substitutional Interstitials
‘new element replaces host atoms’ ‘new element goes in holes’

e.g. Ni in Cu, steels e.g. semiconductor devices:

doped-Si

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 Can we roughly estimate what atoms will form solid solutions?

Yes
 When alcohol (C2H2OH) is mixed with water (H2O), the
mixing occurs at molecular scale and the resultant mixture is
called liquid solution.

 Similarly, a solid solution is

form when the elements of
two or more than two
different materials (e.g., Cu
& Ni) are mixed together
provided they obey the
Hume-Rothery Rule such a
solid solution is also called
Substitutional solid solution.

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 Hume Ruthery Rule

1. Less than 15% difference in atomic radii

2. The same crystal structure
3. Similar electronegativity (the ability of atom to attract an electron)
4. The same valance

 For example, Ni solubility is very high in Cu as they obey the Hume

Ruthery Rules

 If one or more of the above rules are violated, only partial solubility is
possible

 For example, the Al and Si violate Hume Ruthery rules 1, 2 and 4 and as
a result less than 2 atomic percent Si is soluble in Al

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 2. Dislocations or Line Defects (1-dimensional defects)
They are lines along which the crystal pattern is broken
are called Line Defects or 1-dimensional defects
DISLOCATIONS
 Edge dislocation
 Screw dislocation EDGE MIXED SCREW
 Mixed dislocation

 They play an important role in a variety of deformation processes like

creep, fatigue and fracture

 They can play a ‘constructive role’ in crystal growth

Material under constant load or stress it may undergo progressive plastic

deformation over a period of time. This time-dependent strain is called Creep.
Fatigue is the weakening of a material caused by repeatedly applied loads.
A fracture is the separation of an object or material into two or more pieces
under the action of stress. 11/17/2018 21
 Dislocations or Line Defects (1-dimensional defects)
Edge dislocation:
Edge dislocation is represented by the inverted T, i.e., “ ”
and it represents the edge of an extra half plane of atoms.

The line which

runs along the
edge of the
extra row of
atoms is called
the dislocation
line.

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Edge dislocation in CdTe
 Dislocations or Line Defects (1-dimensional defects)
Edge dislocation:
 As, in the perfect crystal, an m×n atomic step loop
closes at the starting point.

 However, in the region of a dislocation, the same

loop fails to close.

 Here, we define a vector called the Burgers vector b:

(Johannes Martinus Burgers, 1895)

 The displacement vector to close a stepwise loop

around the dislocation (edge or screw) region is
called Burgers vector.

 The magnitude of the Burgers vector (b) represents

the magnitude of the crystal defect.
 For edge dislocation, the Burger vector b is
perpendicular to the dislocation line
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 Edge dislocation
Interaction between dislocations
 An elastic interactions occur between edge dislocations on the same slip plane.
 Such interaction is of two types i.e., Attractive interaction and Repulsive interaction.
 To understand these interaction we need to consider Positive and Negative edge
dislocations.
 If a single edge dislocation is present in a material it can be called either positive or
negative edge dislocation.
 If two (or more) dislocations are present on the same slip plane, with the extra half-plane on
two different sides of the slip plane, then one of them is positive and the other negative.

Positive edge dislocation Negative edge dislocation

Can come together

ATTRACTION and
cancel one another

They will move away from one another

REPULSION to
the surface of the material
 Dislocations or Line Defects (1-dimensional defects)
Screw dislocation:

The dislocation produced as a result of spiral stacking of

crystal planes around the dislocation line is called the screw
dislocation.

 For screw dislocation, the

Burger vector b is parallel to
the dislocation line

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 Dislocations or Line Defects (1-dimensional defects)
Mixed dislocation:

The mixed dislocation has both edge and screw character.

Burgers vector for the mixed

dislocation is neither
perpendicular nor parallel to
the dislocation line but
retains a fixed orientation in
space.

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 3. Surface or planer Defects (2-dimensional defects)

The surfaces along which distinct crystallites are joined

together are called 2-dimensional defects

 Free surfaces

 Grain Boundaries or inter-crystalline Boundaries

 Internal defects or Interfaces within crystals

(such as stacking faults)

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 Surface or planer Defects (2-dimensional defects)
Free surfaces:
Free surfaces are the external surfaces at which the solid
terminates

Adsorbed atom

Adsorbed molecule

Solutes segregated
to interface

The dangling bonds at the

interface provide favorable
sites for the adsorption of
atoms that do not fit well into
the bulk lattice
 Surface or planer Defects (2-dimensional defects)
Free surfaces:

 Vapor or liquid molecules do the interaction with the solid

at free surfaces and influences the behavior of the solid in
many important ways

 Oxygen, sulfur and phosphorous are common surfactants

in engineering solids

 It also affects the shape of the solid

 Surface or planer Defects (2-dimensional defects)

Grain Boundaries or Inter-crystalline Boundaries

The boundaries which separate grains or distinct phases
within the solids are called grain boundaries or inter-crystalline
boundaries OR

The interfaces that separate grains are called grain

boundaries

Grain
boundaries
in
SrTiO3

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 Surface or planer Defects (2-dimensional defects)
Grain Boundaries or Inter-crystalline Boundaries
Low angle grain boundaries (misorientation < 10º)

Two extremes

TILT TWIST
An array of edge dislocations An array of screw dislocations
Low angle grain
boundaries in
Cubic Zirconia
seen using by
TEM

Dickey et. al., Microscopy

and Microanalysis (2000) pg.
120
 Surface or planer Defects (2-dimensional defects)
About 8º TILT BOUNDARY IN SrTiO3 POLYCRYSTAL
2.761 Å

No visible
Grain
Boundary

Fourier filtered image

Dislocation
structures at
the Grain
boundary
 Surface or planer Defects (2-dimensional defects)
Twin Boundary
When the atomic arrangement on one side of the surface or boundary in a crystallite is
related to the other side by a symmetry operation (usually a mirror) such type of boundary
is called the twin boundary.
High-resolution micrograph

Mirror
related
variants
Twin plane

Annealing twin boundaries (formed during re-crystallization)

Twin boundary
Deformation twin boundaries (formed during plastic deformation)
 Surface or planer Defects (2-dimensional defects)

Grain Boundary

 The grain boundary region may be distorted with atoms

 The thickness may be of the order of few atomic diameters

 The crystal orientation changes abruptly at the grain boundary

 Grain boundary energy is responsible for grain growth on

heating

 Large grains grow at the expense of smaller ones

 Surface or planer Defects (2-dimensional defects)
Internal defects:
The defects that disrupt the crystalline pattern over a surface within a crystal are
called the internal defects.
For example, Stacking Fault
Stacking faults are found in close-packed structures.

Stacking Fault
 Error in the sequence of stacking atomic planes → Stacking fault

FCC stacking …ABC ABC ABC ABC…

FCC stacking
with a stacking fault …ABC AB AB ABC…

Thin region of HCP type of stacking

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 Surface or planer Defects (2-dimensional defects)
Stacking Fault

In the sequence ..…....ABC||BCABC……. the defect marked ||

corresponds to a missing A-plane, and hence is an intrinsic

stacking fault. An intrinsic stacking fault is created by

the condensation of vacancies onto a close-packed plane.

Extrinsic stacking faults appear, for example, after an

irradiation treatment creates many interstitials that
subsequently gather together on close-packed planes.
4. Volumetric or bulk Defects (3-dimensional defects)
The defects that change the crystal pattern over a finite volume are
called 3-dimensional defects
OR

The three-dimensional defects are the aggregates of atoms or

vacancies

 Voids or pores
 Inclusions
 Dispersants or Second phase particles

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 Volumetric or bulk Defects (3-dimensional defects)
Voids or pores:

Voids (or pores) are holes in the solid formed by trapped gases or
by the accumulation of vacancies
OR
Voids (or pores) are caused by gases that are trapped during
solidification or by vacancy condensation in the solid state

 They are almost always undesirable defects.

 Their major effect is to decrease mechanical strength
and promote fracture at small loads.

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 Volumetric or bulk Defects (3-dimensional defects)
Inclusions:
Inclusions are foreign particles or large precipitate
particles.

 Inclusions vary in size from a few microns to macroscopic

dimensions, and are relatively large, undesirable particles
that entered the system as dirt or formed by precipitation

 They are usually undesirable constituents in the

microstructure. For example, inclusions have a
deleterious/harmful effect on the useful strength of
structural alloys since they are preferential sites for failure.
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 Volumetric or bulk Defects (3-dimensional defects)
Inclusions:

Inclusions are also often harmful in microelectronic devices

since they disturb the geometry of the device by interfering in
manufacturing, or alter its electrical properties by introducing
undesirable properties of their own.

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 Volumetric or bulk Defects (3-dimensional defects)
Dispersants or Second phase particles:
Second phase particles or dispersants vary in size from a
fraction of a micron to the normal grain size (10-100µm), but
are intentionally introduced into the microstructure

 Dispersants influence the behavior of the primary phase

 They may be large precipitates, grains, or polygranular
particles distributed through the microstructure

 When a microstructure contains dispersants the

properties such as mechanical strength and electrical
conductivity are some average of the properties of the
dispersant phase and the parent
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 Volumetric or bulk Defects (3-dimensional defects)

BaTiO3
Grains

Grain
boundary

Dispersant or
Voids or pores
Secondary phase
11/17/2018 particle BaWO4 43
 Color Centers
 Color centers are imperfections in crystals that cause color (defects
that cause color by absorption of light). Electrons in the defect region
only absorb light at certain range of wavelength.

 This phenomenon is common in many transparent insulators

(example: diamond). Many metal oxides fall in this category.

 Examples of color centers:

i. A diamond with C vacancies (missing carbon atoms) absorbs light, and these
centers give green color

ii. Replacement of Al3+ for Si4+ in quartz gives rise to the color of smoky quartz

iii. A ruby (Al2O3) may contain < 1% Cr and it will look pink or red, but the same
material without Cr will be completely colorless
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