Crystal Defects

The ideal crystal has an infinite 3D repetition of identical units, which

may be atoms or molecules.
The missing and lacking of atoms or ions in an ideal or imaginary
crystal structure or lattice and the misalignment of unit cells in real
crystals are called crystal defects
The presence of a relatively small number of defects have a profound
impact on the macroscopic properties of materials, and the control
(and intentional introduction) of defects is important in many kinds
of material processing.
Example: Production of advanced semiconductor devices require not
only a rather perfect Si crystal as starting material, but also involve
introduction of specific defects in small areas of the sample.
Forging a metal tool introduces defects and increases strength and
elasticity of the tool.
2
These imperfections result from deformation of the solid, rapid cooling
from high temperature, or high-energy radiation (X-rays or neutrons)
striking the solid.
Crystal defects or imperfections have strong influence upon many
properties of crystals, such as strength, electrical conductivity and
hysteresis loss of ferromagnets.
Thus, some important properties of crystals are controlled by as much as
by imperfections and by the nature of the host crystals.
➢ The conductivity of some semiconductors is due entirely to trace
amount of chemical impurities.
➢ Color, luminescence of many crystals arise from impurities and
imperfections
➢ Atomic diffusion may be accelerated enormously by impurities or
imperfections
➢ Mechanical and plastic properties are usually controlled by
imperfections.
3
 (a) (b)
Figure: A two-dimensional representation of a perfect single
crystal with regular arrangement of atoms (a). But … nothing is
perfect, and structures of real materials can be better
represented by the schematic drawing (b).
4
 Classification of Defects

0D 1D 2D 3D
(Point defects) (Line defects) (Surface / Interface) (Volume defects)

Surface Twins
Vacancy Dislocation
Interphase Precipitate
Impurity Disclination
boundary
Dispiration Faulted
Frenkel Grain region
defect boundary
Schottky Voids /
Twin Cracks
defect
boundary
Thermal
Stacking vibration
faults
5
6
Point defects , as the name implies, are imperfect point-like regions
in the crystal (atoms missing or in irregular places in the lattice).
Point defects include intrinsic (vacancies, interstitial) and extrinsic
(dopants) defects .
Vacancy
Non-ionic Interstitial
Impurity
crystals Substitutional
0D
(Point defects) Frenkel defect
Ionic
Other ~
crystals
Schottky defect

Imperfect point-like regions in the crystal about the size of 1-2

atomic diameters.
7
Vacancy
Vacancies are empty spaces where an atom should be, but is
missing.
They are common, especially at high temperatures when atoms are
frequently and randomly change their positions leaving behind
empty lattice sites.
❑ Missing atom from an atomic site is called a vacancy.
❑ Atoms around the vacancy displaced from their equilibrium
positions.
❑ This gives rise to a stress field in the vicinity of the vacancy.
❑ Based on their origin vacancies can be:
➢ Random/Statistical (thermal vacancies) or
➢ Structural (due to off-stoichiometry in a compound).
8
❑ Based on their position vacancies can be random or ordered.
(Ordered defects become part of the crystal structure and are ‘no
longer defects’ in the usual sense).
❑ Vacancies play an important role in diffusion of substitutional
atoms and in many other processes/effects in materials science,
including climb of edge dislocations, some forms of creep and
increased resistivity.
❑ Non-equilibrium concentration of vacancies can be generated by:
➢ quenching from a higher temperature
➢ bombardment with high energy particles
➢ plastic deformation.
➢ off-stoichiometry in ordered compounds.
Neighbouring atoms are
displaced from their
equilibrium position in a
perfect crystal
9
 Impurity/Alloying Element/Dopant
❑ A ‘foreign’ element added (called as impurity/alloying
element/dopant based on the context) can go to an
interstitial site (between atoms) or may substitute for an
atom of the host.
❑ Interstitial atoms are squeezed in between regular lattice
sites.
❑ If the interstitial atom is of the same species as the lattice
atoms, it is called self-interstitial.
❑ Foreign, usually smaller atoms (carbon, nitrogen, hydrogen,
oxygen) are called interstitial impurities.
❑ If the foreign atom replaces or substitutes for a matrix atom,
it is called a substitutional impurity.
10
 Overlaid to illustrate the relative
size of atom and void (usually
the insterstitial atom is bigger
Interstitial than the void)

Compressive & Shear

Impurity Stress Fields
Or alloying element
Compressive stress fields

Substitutional

Substitutional Impurity
Foreign atom replacing the parent atom in the
crystal, e.g. Cu sitting in the lattice site of FCC-Ni
Tensile Stress
Interstitial Impurity Fields
Foreign atom sitting in the void of a crystal, e.g. C
sitting in the octahedral void in HT FCC-Fe

11
❑ In some (rare) situations the same element can occupy both a
lattice position and an interstitial position ► e.g. B in steel.
❑ By using ion irradiation or some other ‘strong forces’ an
substitutional atoms may be forced to occupy an interstitial
position.
❑ The diffusion mechanism of these two types of point defects
(interstitial vs substitutional) is different. This is because for the
diffusion of substitutional atom the neighbouring site has to be
vacant; while in the case of interstitial diffusion the neighbouring
site is usually vacant (as the solubility of interstitial atoms is
small).

12
❑ Formation of a vacancy leads to ‘missing bonds’ and distortion of the
lattice.
❑ The potential energy (Internal energy & Enthalpy) of the system
increases.
❑ Work required for the formation of a point defect →Enthalpy of
formation (Hf) [kJ/mol or eV/defect].
❑ Though it costs energy to form a vacancy, its formation leads to increase
in configurational entropy (the crystal without vacancies represents just
one state, while the crystal with vacancies can exist in many
energetically equivalent states, corresponding to various positions of
the vacancies in the crystal → ‘the system becomes configurationally
rich’).
❑ These type of vacancies are called Thermal Vacancies .

13
In ionic crystals (e.g. table salt – NaCl) the bonding is provided by
coulombic forces between positively and negatively charged ions. Point
defects in ionic crystals are charged as well. The Coulombic forces are
very large and any charge imbalance has a very strong tendency to
balance itself. To maintain charge neutrality several point defects can be
created.
A Frenkel defect is a pair of cation (positive ion) vacancy and a cation
interstitial or it may also be an anion (negative ion) vacancy and anion
interstitial.
However anions are much larger than cations and it is not easy for an
anion interstitial to form.
A Schottky defect is a pair of anion and cation vacancies.
In both Frenkel and Schottky defects, the pair of point defects stay near
each other because of strong columbic attraction of their opposite
charges.
14
 Missing Anion

Missing Cation

Frenkel defect Schottky defect

Cation being smaller get displaced A Schottky defect consists of a pair of anion
to interstitial voids. e.g. AgI, CaF2 and cation vacancies→ this maintains charge
neutrality. e.g., Alkali halides

15
Concentration of Defects
Energy is required to form a defect: this means that the formation of
defects is always an endothermic process.
Let us consider the effect on the free energy of a perfect crystal of
creating a single defect, say a vacant cation site. This requires a
certain amount of energy, H, but causes a considerable increase in
entropy, S, because of the large number of positions which this
defect can occupy. Thus, if the crystal contains 1 mol of cations,
there are ∼1023 possible positions for the vacancy. The entropy
gained is called configurational entropy and is given by the
Boltzmann equation:
S = k ln W
where the probability, W, is proportional to 1023; other, smaller,
entropy changes are also present due to the disturbance of the
crystal structure in the neighborhood of the defect.
16
As a result of this increase in entropy, the enthalpy required to form
the defect initially is more than offset by the gain in entropy.
Consequently, the free energy, given by
G = H - TS decrease.

Figure: Energy changes on introducing defects into a perfect crystal.

17
 Calculation of equilibrium concentration of vacancies
Let nv be the number of vacancies, N the number of sites in the
lattice
Assume that concentration of vacancies is small i.e. nv<< N
H f
 the interaction between vacancies can be ignored ( nv
= 0 ) ()

 Hformation (nv vacancies) = nv . Hformation

Let Hf be the enthalpy of formation of one vacancy.
G = Hf − T S
For nv vacancies, G = nv. Hf − T S ---------------(1)

S = Sconfigurational = Sstate with vacancies – Sstate without vacancies = perfect crystal

G (putting n vacancies) = nv. Hf − T Sconfig Configurational

entropy

18
 Calculating Sconfig:
S = kln W
For the state without vacancies (perfect crystal), the number of
configurations is ‘1’  Sperfect crystal = k ln (1) = 0
Hence, Sconfigurational = Sstate with vacancies
In a lattice with N atoms there are nv vacancies and (N–nv) filled
sites. The possible number of configurations (W) is given by:
N
Cnv
(i.e. the possible number of ways one can chose nv vacant sites from a perfect
lattice containing N sites).

19
 ---(2)

From equations (1), (2)

Δ𝐺 = 𝑛𝑣 . Δ𝐻𝑓 − 𝑇Δ𝑆𝑐𝑜𝑛𝑓𝑖𝑔 = 𝑛𝑣 Δ𝐻𝑓 − 𝑘𝑇 ln( 𝑁!) − ln( 𝑛𝑣 !) − ln{ 𝑁 − 𝑛𝑣 !}

Using Sterling’s approximation: ln(N!) = [N ln(N) – N]

G = nv .H f − kT {N ln( N ) − N } − {nv ln(nv ) − nv } − {( N − nv ) ln ( N − nv ) − ( N − nv )}

G = nv .H f − kT  N ln( N ) − nv ln(nv ) − ( N − nv ) ln ( N − nv ) 

At equilibrium, at constant T, the Gibbs free energy of the system

must be a minimum with respect to changes in the number of
defects nv; thus,
G
For energy minimum =0
nv

20
 zero from ()

G H f Sconfig

= H f + nv −T =0
nv T nv nv

N ln N is a constant and hence its differential is zero; the differential of ln x is 1/x

and of (x ln x) is (1 + ln x). On differentiating, we get
G ( N − nv ) 1
= H f − kT [0 − {(−1) ln( N − nv )} + { (−1)} − {ln nv + nv . }] = 0
nv T ( N − nv ) nv
G  N − nv 
= H f − kT [ln( N − nv )} − ln nv ] = H f − kT ln  =0
nv T  nv 
H f  N − nv  ∆𝐻𝑓
 = ln   Assuming N  nv  = ln
𝑁
𝑘𝑇 𝑛𝑣
kT  n v 
∆𝑯𝒇 k = kB = Boltzmann constant
nv  N exp (− ) = 1.38  10–23 J/K
𝒌𝑻
= 8.62  10–5 eV/K
Use R instead of k if Hf is in J/mole (instead of J/atom)
21
 Variation of G with vacancy concentration at a fixed temperature

T (oC) n/N
500 1 x 10−10
1000 1 x 10−5
1500 5 x 10−4
2000 3 x 10−3
Hf = 1 eV/vacancy
= 0.16 x 10−18 J/vacancy

❑ Close to the melting point in FCC metals Au, Ag, Cu the fraction of vacancies is
about 10−4 (i.e. one in 10,000 lattice sites are vacant).
❖ Show that the number of Schottky defects in a 1 : 1 crystal of composition MX
is given by
∆𝑯𝒔
ns = N exp (− )
𝟐𝒌𝑻
Book: Solid State Chemistry: An Introduction, page-204
22
 Typical enthalpies of formation of Schottky and Frenkel defects
Schottky Defects Frenkel Defects
Hs (J) HF (J)
Compound Hs (eV) Compound HF (eV)
 10 –23  10 –23

LiI 2.08 1.30 -AgI 1.12 0.70

LiBr 2.88 1.80 AgBr 1.92 1.20
NaCl 3.69 2.30 AgCl 2.56 1.60
CaO 9.77 6.10 CaF2 4.49 2.80
MgO 10.57 6.60 ZrO2 6.57 4.10

➢ Even in solids like LiI with low Hs (enthalpy of formation of Schottky defects)
(1.30 eV) the fraction of defects at RT (300K) is small (1.210–11). At 1000K the
fraction is 5.310–4.
➢ This implies there are very few Schottky defects at RT.
➢ Depending on the values of Hs & HF both these defects may be present in a
crystal (though one of them dominates in most systems).
23
Problem : At what temperature does the first vacancy become
stable in a Cu crystal?
Data:
▪No. of atoms in the crystal = NAvagadro
▪ Hf (Cu) = 1.24 eV/vacancy
▪ kB = 8.62  10–5 eV/K
▪ nv = 1
𝒏𝒗 𝜟𝑯𝒇
= 𝐞𝐱𝐩 −
𝑵 𝒌𝑻
𝒏𝒗 𝜟𝑯𝒇
 𝐥𝐧 =−
𝑵 𝒌𝑻
𝜟𝑯𝒇 𝟏. 𝟐𝟒
𝑻ቚ = = −𝟓
= 𝟐𝟔𝟐. 𝟕𝟐𝑲
𝒇𝒊𝒓𝒔𝒕𝒗𝒂𝒄𝒂𝒏𝒄𝒚 𝒌 𝐥𝐧 𝑵 (𝟖. 𝟔𝟐 × 𝟏𝟎 )(𝟓𝟒. 𝟕𝟓𝟓)

24
 Line imperfections/defects
The defects, which take place due to dislocation or distortion of
atoms along a line, in some direction are called as ‘line defects’.
Line defects are also called dislocations. In the geometric sense,
they may be called as ‘one dimensional defects’.
A dislocation may be defined as a disturbed region between two
substantially perfect parts of a crystal (A Dislocation is a line
discontinuity in the regular crystal structure).

25
 BURGERS VECTOR
➢ The magnitude and the direction of the displacement are
defined by a vector, called the Burgers Vector.
➢ In figure (a), starting from the point P, we go up by 6 steps, then
move towards right by 5 steps, move down by 6 steps and
finally move towards left by 5 steps to reach the starting point
P. Now the Burgers circuit gets closed.
➢ When the same operation is performed on the defect crystal
(figure (b)) we end up at Q instead of the starting point.

Rule: RH/SF

(a) (b)

26
➢ So, we have to move an extra step to return to P, in order to
close the Burgers circuit.
➢ The magnitude and the direction of the step defines the
Burgers Vector (BV).
BV = 𝑸𝑷 = b
The two basic types of dislocations are (i) Edge dislocation and (ii)
Screw dislocation.
(i) Edge dislocations:
In this type of dislocations, the Burger vector is perpendicular to the
dislocation line and the distortion produces an extra half-plane
above the slip plane.
Edge dislocations are represented by ‘⊥’ or ‘T‘ depending on
whether the incomplete plane starts from the top or from the
bottom of the crystal.
27
28
 Dislocation movement
Dislocations move in steps. The edge dislocation at P moves to Q in
steps as depicted by the red (extra half-plane) and blue atoms.
Motion of dislocations allows slip – plastic deformation when
interatomic bonds are fractured and reformed. Actually, slip always
occurs through dislocations motion.
This movement is analogous to movement of a caterpillar.

Figure: Why do dislocations allow slip at much lower stress than in a perfect
crystal?
29
Screw dislocation
➢ In this dislocation, the atoms are displaced in two separate planes
perpendicular to each other.
➢ It forms a spiral ramp around the dislocation.
➢ The Burgers Vector is parallel to the screw dislocation line.

30
31
 Surface imperfections
They are the imperfections represented by a boundary. At the
boundary the atomic bonds are terminated. The atoms on the
surface cannot be compared with the atoms within the crystal. The
reason is that the surface atoms have neighbors on one side only.
Where as the atoms inside the crystal have neighbors on either
sides. Since these surface atoms are not surrounded by others,
they possess higher energy than that of internal atoms.
For most metals, the energy of the surface atoms is of the order of
1J/m2.

32
 Grain boundaries
Most crystalline solids are an aggregate of several crystals. Such
materials are called polycrystalline.
Each crystal is known as a grain. The boundary between the grains is the
grain boundary.

33
❖ It is a two dimensional imperfection. During crystallization, new
crystals form in different parts and they are randomly oriented with
respect to one another.
❖ The thickness of this region is 2 to 10 or more atomic diameters. The
boundary region is called a crystal boundary or a grain boundary.
❖ The boundary between two crystals which have different crystalline
arrangements or different compositions, is called as interphase
boundary or commonly an interface.
❖ Grain boundaries are important in several ways. They present paths
for atoms to diffuse into the material and scatter light passing
through transparent materials to make them opaque. They also affect
mechanical properties. The boundaries limit the lengths and motions
of dislocations that can move. This means that smaller grains (more
grain boundary surface area) strengthens materials.

34
 Tilt boundaries
This is called low-angle boundary as the
orientation difference between two
neighboring crystals is less than 10°.
The disruption in the boundary is not so
severe as in the high-angle boundary. In
general low-angle boundaries can be
described by suitable arrays of dislocation.
Actually a low-angle tilt boundary is
composed of edge dislocation lying one above
the other
𝒃
The angle or tilt will be 𝜽 =
𝑫
where b = Burgers vector and D = the
average vertical distance between
dislocations.
35
 Twin boundaries
If the atomic arrangement on one side of a boundary is a mirror reflection
of the arrangement on the other side, then it is called as twin boundary.
As they occur in pair, they are called twin boundaries. At one boundary,
orientation of atomic arrangement changes. At another boundary, it is
restored back. The region between the pair of boundaries is called the
twinned region.
These boundaries are easily identified under an optical microscope.

36
 Stacking Faults
Whenever the stacking of atomic planes is not in a proper
sequence throughout the crystal, the fault caused is known as
stacking fault.
For example, the stacking sequence in an ideal FCC crystal may be
described as A-B-C-A-B-C- A-B-C-……. But the stacking fault may
change the sequence to A-B-C-A-B-A-B-A-B-C. The region in which
the stacking fault occurs (A-B-A-B) forms a thin region and it
becomes HCP.
This thin region is a surface imperfection and is called a stacking
fault.

37