Crystal Defects Content Crystal Defect

The Structure of Matter 1.0 Perfect Crystal

2.0 Processing, Microstructure and
Properties
3.0 Crystal defect
By 3.1 Vacancies and Interstitials
Dr.Srimala 3.2 Impurity Atoms
3.3 Point Defects in Ionic Crystals
3.4 Defect Complexes
4.0 Vacancies formation
5.0 Divacancy
6.0 Defects in the ionic compounds
6.1 Kroger-Vink notation
6.2 Frenkel Defect
6.3 Schottky defects

Liquid Crystal Image

1.0 Perfect Crystal

2.0 Processing, Microstructure and Properties
A perfect crystal with every atom in the correct position does not exist.

Defect: imperfection or "mistake" in the regular periodic arrangement of

atoms in a crystal

Defects, even in very small concentrations, can have a dramatic impact on Processing is the manner in which the material is made.
the properties of a material.
The processing determines the defects that are present.
Most materials properties are determined by the crystal defects present

“Crystals are like people: it is the defects in them which tend to make them Since materials properties are determined by crystal
interesting!” - Colin Humphreys
defects there is a correlation between the processing of
. the materials and the materials properties.

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3.0 Crystal defect
3.1 Vacancies and Interstitials
Pure metal will contain numerous defects in its crystal
structure such as

1. A foreign atom substitutionally placed

2. A foreign atom interstitially placed Point defects
3. Parent atoms interstitially placed
4. Vacancies

5. Twins and stacking faults plane defects

6. Grain boundaries a. Schottky defect b. Interstitial (impurity) defect

7. Dislocations
8. Voids bulk defects
9. inclusions On the left are vacancies and on the right are interstitials

3.3 Point Defects in Ionic Crystals

3.2 Impurity Atoms

• Ionic crystals unlike other solids are

made up of charged ions.
• Point defects in ionic crystal are charged.
• Charge neutrality must always be
maintained.

Cotterill 1985
The colored atoms are impurity atoms. They are atoms of a different element.
On the left the impurity atom sits between the black atoms and is called an
interstitial impurity.
On the right the impurity atom replaces or substitutes for a black atom and is
called a substitutional impurity

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3.4 Defect Complexes Line Defects
Edge dislocation
To maintain charge neutrality several point defects are created
Migration aids ductile
FD - Frenkel defect - cation deformation
hops from lattice site to
interstitial

SD - Schottky defect - anion Fig 10-4 of

and cation vacancies. Bloss,
Crystallography
and Crystal
Chemistry.©
MSA

Cotterill 1985

Line Defects Plane Defects

Screw dislocation (aids mineral growth) Lineage structure or mosaic crystal
Boundary of slightly mis-oriented volumes within a single
crystal
Lattices are close enough to provide continuity (so not
separate crystals)

Fig 10-5 of
Bloss,
Crystallography
and Crystal
Chemistry. ©
MSA

Fig 10-1 of Bloss, Crystallography and Crystal Chemistry. © MSA

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 Crystal Defects
Plane Defects
Domain structure (antiphase domains) Plane Defects
Also has short-range but not long-range order
Stacking faults
Common in clays and low-T disequilibrium
A - B - C layers may be various clay types (illite, smectite,
etc.)

ABCABCABCABABCABC
AAAAAABAAAAAAA
ABABABABABCABABAB

Fig 10-2 of Bloss, Crystallography and Crystal Chemistry. © MSA

Why do defects form? 4.0 Vacancies formation

The introduction of defects increases entropy ΔS and decreases
free energy ΔG Perfect crystal-all lattice sites are occupied-no
G  H  T ( S ) vacancies are present
We introduce vacancies- by removing atom
A minimum value for ΔG is from the perfect lattice.
reached for an optimum
concentration of defects

The structure with defects is

more stable

• Will these vacancies remains in the lattice as

stable defect?
• Or will they migrate to the surface restoring the
perfection of the lattice?

4

• We analyze this problem by
considering the effect of the
vacancies upon Gibbs free energy
of the lattice
• Let say we have N lattice sites, how does the free energy
change as a function of the n, no of vacancies?
• If G decrease, then the vacancies thermodynamically stable
Therefore, we use symbol Ω -is simply the number of
distinguishably different ways that n vacancies may be
arranged on N lattice sites.
To determine Ω lets consider an analogous problem:
Given 100 lattice sites and the three atoms Fe, Co, and Ni,
in how many ways can we put these atoms on the 100
lattice points?
Fe may go 100 different sites
For each of these, Co may go 99 ways
For each of these, Ni may go 98 ways
Answers = 1000 x 99 x 98
= 100!/(100-3)!=970200
Let the free energy change due to vacancies be
G  G  G ( perfect )  nH  T (nS )
G  nH  T ( nSv  Sc )
H = energy per vacancy
SV = vibrational entropy per vacancy
Sc = configurational entropy of the entire
crystal
There’s many different geometrical ways in which
the vacancies may arrange on the lattice (mixing,
randomizing of n vacancies in N aotms.
What is the answers to the same question if all three atoms are
Fe atoms?
For the previous sets, we know that
Fe may go 3 different ways
For each of these, Co may go 2 ways
For each of these, Ni may go 1 ways
Therefore, for the previous sets we have counted 3!
permutation of three atoms. If the three atoms are the same
these 3! permutation are indistinguishable and we must divide
the equation by 3!
Answers = 100!/[(100-3)!3!]=161700
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 For the configurationally entropy

Sc  k ln Ω
N!
Ω
Vacancies are indistinguishable from one ( N  n)!n!
another, so by analogy we have Since N and n are large apply Stirling’s approximation
N! ln X !  X ln X  X for large X
Ω
( N  n)!n! After some algebraic manipulation we obtain

Where N is the total number of lattice sites Sc  k[ N ln N  N  ( N  n) ln( N  n)  n ln n  n  ( N  n)]

n is the number of vacancies Sc  k[ N ln N  ( N  n) ln( N  n)  n ln n]

Vibrational entropy • Now we can evaluate each term in equation below

Is related to the ways in which the energy levels in the

G  nH  T (nSv  Sc)
solid are occupied. H is the energy required to remove the atom to the surface or interface

v • Figure 1 is a plot of the terms based on the equation

S v  3k ln
v' Energy terms raises the free
H energy but the total free energy
actually drops at first due to
ne G increase entropy upon introducing
Where v’ is the final frequency of the atoms around the vacancy and v vacancies
is their original frequency. n

The vacancy tends to increase the vibrational amplitude

So that v/v’ >1 and SV is positive. Therefore, the total entropy change
associated with introducing vacancies nSv  Sc must be positive
 T nSv  Sc
• A maximum decrease in free energy is obtained at this minimum, so
this point represent the equilibrium condition and the value of n at this
minimum is the equilibrium number of vacancies, ne

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Therefore at equilibrium, n
 H  T  S v   kT ln
N n
dG
0 n
 eksp  [
H

 Sv
]
dn N n kT k
No of vacancy
dG d n H  Sv
 ( nH  TnSv  TSc)  0  eksp  [ ]. eksp [ ]
No of atoms N n kT k
dn dn n H  Sv
k=1.38x10-23J/K

dSc For 1 mole vacancies  eksp  [ ]. eksp [ ]

H  TSv  T N n RT R R=8.314
dn n
 Vacancy fraction
d N n
H  TSv  kT {ln[ N ln N  ( N  n) ln( N  n)  n ln n]}  X v = Vacancy concentration
dn
( N  n) n
H  TSv  kT [  ( 1)  ln( N  n)   ln n]
( N  n) n

The value of H typically range from 80 to160kJ/mole and

ΔSV / k Sv
slope is proportional to k from 1.0 to 2.0.
the enthalpy of Intercept gives the
formation of vacancy vibrational entropy of
vacancies
S v
ln XV Example Cu: k = 1.5, H = 113kJ/mole, the number
Slope = ΔHV / k of atoms per volume from the density is 5x1022 sites/cm3.
Therefore the number of vacancies per cubic centimeter is
then found to be
0
- 1/T Temperature 1000oC, vacancies/cm3 =5x1018
Arrhenius plot of vacancies fraction versus temperature 200oC, = 2x103

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 Exercise 1.1
This results illustrates two interesting things

Take the energy to form a mole

of vacancies in Cu as 20,000
1. A perfect metal is not thermodynamically stable. The free calories and the vibrational
energy is lowered when vacancies are added and the entropy as 1.0k per vacancy,
equilibrium number of vacancies quiet large although it is where k is Boltzman’s constant.
still a small fraction of the total number of lattice sites Compute the number of
vacancies per cubic centimeter
of Cu at 20oC and at its melting
2. The number of vacancies is temperature dependent. point (1083oC). Take the
density of Cu as 8.94 g/cm3.
JMR for Cu= 64

H v  2000 cal/mole
5.0 Divacancy
H v  2000 x4.184 J/mole  83.6kJ/mole
Sv  1.0k / vacancy Defects may occur in combinations in an elemental crystal.
8.94
For Cu, N  x 6.02 x10 23 The most common of these is the divacancy, which is a pair
64
N  8.4122 x10 22 atom/cm3 of adjacent vacant lattice sites
n H Sv
 eksp  [  ]
N n kT k
How to visualize
n 83.6 x103 1.0 k
 eksp  [ ]. eksp[ ]
Answer 1 .1 8.4122 x10 22
n 8.314T k the formation of a
divacancy?
For T  20 o C  293K
n 83.6 x10 3
 eksp  [ ]. eksp[1.0]
8.4122 x10 22  n 8.314( 293)
n
 3.38 x10 15 by two steps
8.4122 x10 22  n
1. The separate formation of two vacancies from a perfect
 
n  8.4122 x10 22 3.38 x10 15  3.38 x10 15 n
crystal
n  2.84 x108 vacancy/cm3
2. The formation of the divacancy configuration from two
separated single vacancies
For 1356K, n  1.38 x10 20 vacancy/cm3

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The enthalpy change associated with the first process is Divacancy (cont….)
simply 2Hv
The enthalpy change associated with second process is
Hint (interaction enthalpy)
X vv  exp[ 1 / k ][ 2 Δ S v  Δ S int ]
Thus the enthalpy of formation of a divacancy can be . exp  [1 / kT ][ 2 Δ H v  Δ H int ]
written 2
Hvv  2ΔHv  ΔH int Xvv  {exp[ 1 / k ][ Δ S v ] exp  [1 / kT ][ Δ H v ]}
. exp[ Δ S int / k ] exp  [ Δ H int / kT ]
The same argument can be used to express 2

excess entropy X vv  { X v} exp[ Δ S int / k ] exp  [ Δ H int / kT ]

Svv  2ΔSv  ΔS int
Therefore for divacancy  Svv   Hvv 
Xvv  eksp   eksp  
 k   kT 

Exercise 1.2 Hvv  2ΔHv  ΔH int

Hvv  2ΔHv  0.1ΔHv
Hvv  29.58  0.19.58 kJ  182.02 kJ

Suppose the interaction parameters for Svv  2ΔSv  ΔS int

divacancies are about 10 percent of the values of Svv  2ΔSv  0.1ΔSv 
corresponding single defect parameters; Svv  28.85  0.18.85  16.815 J/mole.K
  S vv    Hvv 
Δ H int  0.1Δ Hv
ΔS int  0.1ΔSv
Answer 1 .2 X vv  eksp 
 k
 eksp  
  k T 
At 600K,
Δ Hv  95800 J / mole and Δ Sv  8.85J / mole.K  16 . 815   182020 
X vv  eksp   eksp   8 .314 600  
 8 . 314   
Calculate the equilibrium concentration of X vv  eksp 2 . 022  eksp  36 . 489 
divacancies at 600K and at 1300K X vv  eksp  34 . 467   1 . 0744 x10  15

At 1300K,
X vv  eksp  14 . 819   3 . 666 x10  7

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6.0 Defects in the ionic compounds 6.1 Kroger
Kroger--Vink notation

The anion (more electronegative) component in a ionic

compound is typically a nonmetallic element and designated Kroger-Vink notation X YZ
as X
X=the entity occupying the defect site (M,X,V or substituitional
The cation (more electropositive) component is metallic elements)
element and designated as M Y= type of site occupied (M,X,i)
Z=the excess charge associated with the site
A vacant lattice site is designated as V (• = positive, ’ = negative, X = neutral)

Atoms or ions can occupy cation (M) sites, anion (X) 0r

interstitial (i) sites

To facilitate the description, Kroger-Vink

notation are widely accepted

Kroger-Vink notation Kroger-Vink notation

Defect of a compound with composition MX and normal Cont….
valance of M as +2, X as -2 symbol Excess defects
charge
symbol Excess defects XM’’’’ -4 X atom on M site
charge 0 Divacancy on M and X sites
VM VX
VM’’ -2 vacancy on M sublattice
+1 Solute cation L with +3 charge on M site
LM ˙
+2 vacancy on X sublattice
VX ˙˙
+1 Solute cation Y with -1 charge on M site
+2 M atom in interstitial site YX˙
Mi˙˙
Xi’’ -2 X atom in interstitial site e’ -1 Free electron
+1 Electron holes
Mx˙˙˙˙ +4 M atom on X site h˙

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 Important clues 6.2 Frenkel Defect
1. Superscript (x) is used if entity occupying the site carries
Example: Al2O3 normal sites would be AlAlx Oox A frenkel defect is formed on the cation sublattice by
removing an M ion from a normal M site and placing it in an
Cromium ion on a cation site in alumina CrAlx
interstitial site.
because it carries same charge
Mi˙˙
2. Cation vacancies- leaves excess negative charge A frenkel defect is called
an intrinsic defect
Anion vacancies-leaves excess positive charge
because it can formed
Example: Cation vacancy in KCl – Vk’ without any interaction
Al2O3-VAl’’’ with the surroundings of VM’’
MgO – VMg’’ the crystal.

Consider a crystal MX in which the normal valance of M The condition at equilibrium

is +2 and X is -2. If this crystal contains frenkel defects
derived from cation sites, four distinct entites exist in such  S    H fd 
crystal X .X  exp  fd  exp  
VM Mi  k   kT 
Since the number of vacancies same as number of interstitial,
Mi˙˙, VM’’, MMx , XXx X X
V M M i

X .X
V M
M
 X
V
2
i
 
  X fd 
M
2

Therefore, equilibrium concentration of frenkel defects is

Kroger-Vink notation for frenkel defect can be written as
MM=Mi˙˙ +VM’’ S f  H f
since all X atoms remain on anion sites while M atoms X fd  exp[ ] exp[ ]
2k 2 kT
are distributed over cation and interstitial sites.
Furthermore each frenkel defect consists of one vacancy
and one interstitial atom.

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6.3 Schottky defects
In an MX crystal, a schottky defect consists of a vacant
Equilibrium concentration of schottky defects is
cation site and a vacant anion site.

The formation of S sd Hsd

Schottky defect does X sd  exp[ ] exp[ ]
2k 2kT
not disturb the
electrical neutrality of
the crystal-intrinsic
defect

For a crystal with formula

MX
Null=V x˙+VM’
which describe the formation of two vacancies in a region
that is initially a prefect crystal. In this context, null means
the initially defect free crystal

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