Point Defects

DEFECTS IN CRYSTALS
Point defects
Line defects
Surface Imperfections
PROPERTIES
Structure sensitive Structure Insensitive
E.g. Yield stress, Fracture toughness E.g. Density, elastic modulus
0D
(Point defects)
CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY
1D
(Line defects)
2D
(Surface / I nterface)
3D
(Volume defects)
Vacancy
Impurity
Frenkel
defect
Schottky
defect
Dislocation
Surface
Interphase
boundary
Grain
boundary
Twin
boundary
Twins
Precipitate
Faulted
region
Voids /
Cracks
Stacking
faults
Disclination
Dispiration
Thermal
vibration
Anti-phase
boundaries
Translation
SYMMETRY ASSOCIATED DEFECTS
Rotation
Screw
Atomic
Level
Dislocation Disclination Dispiration
Mirror
SYMMETRY ASSOCIATED DEFECTS
Rotation
Inversion
Twins
Multi-atom
Topological
DEFECTS
Non-topological
Based on
symmetry
breaking
Hence association
with symmetry
Random
DEFECTS
Structural
Random
DEFECTS
Ordered
Based on
origin
Based on
position
Vacancies, dislocations,
interface ledges
THE ENTITY IN QUESTION
GEOMETRICAL PHYSICAL
E.g. atoms, clusters etc. E.g. spin, magnetic moment
THE OPERATION DEFINING A DEFECT CANNOT
BE A SYMMETRY OPERATION OF THE CRYSTAL
A DEFECT ASSOCIATED WITH A SYMMETRY
OPERATION OF THE CRYSTAL
TOPOLOGICAL DEFECT
0D
(Point defects)
Vacancy
Impurity
Frenkel defect
Schottky defect
Non-ionic
crystals
Ionic
crystals
Imperfect point-like regions in the crystal about the size of 1-2 atomic
diameters
Interstitial
Substitutional
Other ~
Vacancy
Missing atom from an atomic site
Atoms around the vacancy displaced
Tensile stress field produced in the vicinity
Tensile Stress
Fields ?
Impurity
Interstitial
Substitutional
SUBSTITUTIONAL IMPURITY
- Foreign atom replacing the parent atom in the crystal
- E.g. Cu sitting in the lattice site of FCC-Ni
INTERSTITIAL IMPURITY
- Foreign atom sitting in the void of a crystal
- E.g. C sitting in the octahedral void in HT FCC-Fe
Compressive stress
fields
Tensile Stress
Fields
Compressive
Stress
Fields
Relative
size
Interstitial C sitting in the octahedral void in HT FCC-Fe
r
Octahedral void
/ r
FCC atom
= 0.414
r
Fe-FCC
= 1.29 r
Octahedral void
= 0.414 x 1.29 = 0.53
r
C
= 0.71
Compressive strains around the C atom
Solubility limited to 2 wt% (9.3 at%)
Interstitial C sitting in the octahedral void in LT BCC-Fe
r
Tetrahedral void
/ r
BCC atom
= 0.29 - r
C
= 0.71
r
Fe-BCC
= 1.258 r
Tetrahedral void
= 0.29 x 1.258 = 0.364
But C sits in smaller octahedral void- displaces fewer atoms
Severe compressive strains around the C atom
Solubility limited to 0.008 wt% (0.037 at%)
ENTHALPY OF FORMATION OF VACANCIES
Formation of a vacancy leads to missing bonds and distortion of the
lattice
The potential energy (Enthalpy) of the system increases
Work required for the formaion of a point defect
Enthalpy of formation (AH
f
) [kJ/mol or eV / defect]
Though it costs energy to form a vacancy its formation leads to
increase in configurational entropy
above zero Kelvin there is an equilibrium number of vacancies
Crystal Kr Cd Pb Zn Mg Al Ag Cu Ni
kJ / mol 7.7 38 48 49 56 68 106 120 168
eV / vacancy 0.08 0.39 0.5 0.51 0.58 0.70 1.1 1.24 1.74
AG = AH T AS
AG (putting n vacancies) = nAH
f
T AS
config

Let n be the number of vacancies, N the number of sites in the lattice
Assume that concentration of vacancies is small i.e. n/N << 1
the interaction between vacancies can be ignored
AH
formation
(n vacancies) = n . AH
formation
(1 vacancy)
Let AH
f
be the enthalpy of formation of 1 mole of vacancies
AS = AS
thermal
+ AS
configurational

|
.
|
\
|

=
c
A c
n
n N
k
n
S
config
ln
n
S
T
n
H
n H
n
G
config f
f
c
A c
c
A c
+ A =
c
A c
zero
0 =
c
A c
n
G
For minimum
Larger contribution
|
|
.
|
\
|
A
=
kT
H
N
n
f
exp Considering only configurational entropy
|
.
|
\
|

=
A
n
n N
kT
H
f
ln

User R instead of k if AH
f
is in J/mole
Assuming n << N
|
|
.
|
\
|
A
|
.
|
\
|
c
A c
=
kT
H
n
S
k N
n
f
thermal
exp
1
exp
Using AS = AS
thermal
+ AS
configurational

Independent of temperature, value of ~3
?
T (C) n/N
500 1 x 10
10

1000 1 x 10
5
1500 5 x 10
4
2000 3 x 10
3
AH
f
= 1 eV/vacancy
= 0.16 x 10
18
J/vacancy
G

(
G
i
b
b
s

f
r
e
e

e
n
e
r
g
y
)
n (number of vacancies)
AG
min
Equilibrium
concentration
G (perfect crystal)
Certain equilibrium number of vacancies are preferred at T > 0K
At a given T
Ionic Crystals
Overall electrical neutrality has to be maintained
Frenkel defect
Cation (being smaller get displaced to interstitial voids
E.g. AgI, CaF
2

Schottky defect
Pair of anion and cation vacancies
E.g. Alkali halides
Other defects due to charge balance
If Cd
2+
replaces Na
+
one cation vacancy is created
Defects due to off stiochiometry
ZnO heated in Zn vapour Zn
y
O (y >1)
The excess cations occupy interstitial voids
The electrons (2e
) released stay associated to the interstitial cation

FeO heated in oxygen atmosphere Fe
x
O (x <1)
Vacant cation sites are present
Charge is compensated by conversion of ferrous to ferric ion:
Fe
2+
Fe
3+
+ e

For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions provides the 2 electrons required by excess oxygen

Point Defects

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Point Defects

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DEFECTS IN CRYSTALS

) released stay associated to the interstitial cation

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