Crystal

Defects
AUTONOMOUS
An ideal crystal can be described in terms
a three-dimensionally periodic
arrangement of points called lattice and an
atom or group of atoms associated with
each lattice point called Basis:
Crystal = Lattice + basis
However, there can be deviations from this
ideality.
These deviations are known as crystal defects.
Crystalline imperfections can be classified on
they basis of their geometry under four main
divisions namely
1.Vacancies or Schottky
2.Interstitialcies or Frenkel
3.Compositional defects.
a. Substitutional
b. interstitial
4.Electronic defects
Defects
Point defects
(0-dimensional)
Line defects
(1-dimensional)
Surface defects
(2-dimensional)
Volume defects
(3-dimensional)
1.Edge dislocation
2.Screw dislocation
1.Grain boundaries
2.Tilt boundaries
3.Twin boundaries
4.Stacking faults
1.Cracks
2.Voids or air bubbles
Defects Dimensionality Examples
Point 0 Vacancy
Line 1 Dislocation
Surface 2 Free surface,
Grain boundary
Volume
3
Non crystalline
region of dimension
Point
Defects
Vacancy
Vacancy: A point defect
Vacancy:
A vacancy refers to an atomic site from where
the atom is missing.
Point Defects:
Point imperfections are also called zero
dimensional imperfections. One or two atomic
diameters is the typical size of a point
imperfection.
Introduction of point defect into a crystal
increases its internal energy and changes the
electrical resistance of the crystal.
Due to these point defects mechanical strength
is reduced and strain produced.
Compositional defects.
A substitutianal impurity is a
point imperfection and it refers
to a foreign atom that
substitutes for or replaces a
parent atom in the crystal.
A small sized atom occupying
the void space in the parent
crystal disturbing the parent
atoms from their regular sites is
a interstitial impurity.
vacancy
Interstitial
impurity
Substitutional
impurity
Point Defects
Frenkel
defect
Schottky
defect
Defects in ionic solids
Cation vacancy
+
cation interstitial
Cation vacancy
+
anion vacancy
anion
cation
Frenkel Defect: An atom leaves the regular site and
occupies interstitial position. Such defects are
called Frenkel defects.
The point imperfections in silver halides and CaF
2
are of the Frenkel type.
Schottky defect:
A pair of one cation and one anion can be missing
from an ionic crystal as shown in a figure. such a
pair of vacant ion sites is called schottky defect.
Electronic defects:
Errors in charge distribution in solids are
called electronic defects.
These defects are produced, when the
composition of an ionic crystal does not
correspond to the exact Stoichiometric
formula.
Calculation of number of vacancies at a given
temperature.
All most in all crystals vacancies are present and the main
cause for these defects is thermal agitation.
Let us consider E
v
is the energy required to move an atom from
lattice site inside the crystal to lattice site on the surface.
Therefore the amount of energy required to produce n number
of isolated vacancies can be written as
v
nE U =
The total number of ways to move n number of
atoms out of N number of atoms in a crystal on
to its surface will be
! )! (
!
n n N
N
P

=
The increase in entropy due to formation of
n vacancies can be written as
} log{
log
! )! (
!
n n N
N
B
B
K
P K S

=
=
But the free energy
TS U F =
} ! log )! log( ! {log
)
! )! (
!
log(
n n N N T K nE F
n n N
N
T K nE F
B v
B v
=

=
Using Stirling approximation, log x! = x log x - x
} log ) log( ) ( log { n n n N n N N N T K nE F
B v
=
At thermal equilibrium, free energy is constant
and minimum
with respect to n, hence
} exp{
} log{
} log 1 ) log( 1 {
0 }) log ) log( ) ( log { (
T K
E
n
n N
n
n N
T K E
n n N T K E
n n n N n N N N T K nE
dn
d
o
dn
dF
B
v
B v
B v
B v
=

=
+ =
=
=
} exp{
T K
E
N n
N ifn
B
v

~
<<
Hence equilibrium concentration of vacancies
decreases with temperature.
Calculation of number Schottky defects at a given
temperature.
In ionic crystals, the number of schottky defects at a given
temperature, can be calculated assuming an equal number of
positive and negative ion vacancies are present.
Let us consider E
p
is the energy required to move an ion Pair
from lattice site inside the crystal to a lattice site on the
surface.
Therefore the amount of energy required to produce n
number of isolated ion pair vacancies will be
p
nE U =
The total number of ways that to move n numbers
of ion pairs out of N number of ionic molecules in
a crystal on to the surface will be
2
2
]
! )! (
!
log[
log
]
! )! (
!
[
n n N
N
K S
P K S
n n N
N
P
B
B

=
=

=
The free energy.
2
]
! )! (
!
log[
n n N
N
T K nE F
TS U F
B p

=
=
Using stirling approximation
x x x x = log ! log
] log ) log( ) ( log [ 2
] log ) log( ) ( log [ 2 ]
! )! (
!
log[
] log ) ( ) log( ) ( log [ 2 ]
! )! (
!
log[
2
2
n n n N n N N N T K nE F
n n n n N n N N N
n n N
N
n n n n N n N n N N N N
n n N
N
B v
=
+ =

+ + =

At thermal
equilibrium, free
energy is constant
and minimum with
respect to n,
hence
}
2
exp{
}
2
exp{ ) (
] log[
2
] log[ 2
0 ] [
T K
E
N n
N ifn
T K
E
n N n
n
n N
T K
E
n
n N
T K E
dn
dF
B
p
B
p
B
p
B P
T

~
<<<
=

=
=
Calculation of number of Frenkel Defects at given
temperature:
In ionic crystal ion may be displaced from the
regular lattice into an interstitial site or void
space.
If it is so, then a vacancy and an interstitial defect
will be formed.
Frenkel and Schottky defects together are called
Intrinsic defects.
Let us consider E
i
is the energy required to move
an atom from lattice site inside the crystal to a
lattice site on the surface.
The amount of energy required to produce n
number of isolated vacancies
i
nE U =
The total number of ways to move n numbers of
ions out of N number ionic molecules in a crystal
on to the surface will be,
]}
! )! (
!
][
! )! (
!
log{[
]}
! )! (
!
][
! )! (
!
log{[
log
]
! )! (
!
][
! )! (
!
[
n n N
N
n n N
N
T K nE F
TS U freeenergy
n n N
N
n n N
N
K S
p K entropy
n n N
N
n n N
N
p
i
i
B i
i
i
B
B
i
i

=
=

=
=

=
Ni isNumber
of
interstial
ions
} log 2 ) log( ) ( ) log( ) ( log log {
log 2 ) log( ) ( ) log( ) ( log log
]}
! )! (
!
][
! )! (
!
log{[
n n n N n N n N n N N N N N T K nE F
n n n N n N n N n N N N N N
n n N
N
n n N
N
i i i i B i
i i i i
i
i
+ =
+ =

At equilibrium, the free
energy
is constant and
minimum with
respect to n, hence
T K
E
NN n
T K
E
NN n
n NN T K E
n
NN
T K
n N n N
n
n N n N
T K E
dn
dF
B
i
i
B
i
i B i
i
B
i
i
B i
T
2
exp ) (
2
} log{
2
1
log
] log 2 } [log{
} log{
,
}
) )( (
log{
0 ] [
2
1
2
2

~
~
~
~
>> >>

=
=
Hence it is concluded
that number
of Frenkel defects,
is proportional (NN
i
)
1/2
Line Defects
Dislocations
Line defects
Line defects are one dimensional imperfections in
the geometrical sense.
Line imperfections are called disocation.
There are in general two types of dislocations:
1. Edge dislocation
2. Screw dislocation
Missing half plane A Defect
An extra half plane
or a missing half plane
What kind of
defect is this?
A line defect?
Or a planar
defect?
Extra half plane
No extra plane!
Missing plane
No missing plane!!!
An extra half plane
or a missing half plane
Edge
Dislocation
Edge dislocation
In a perfect crystal, atoms are arranged in both vertical
and horizontal planes parallel to the side faces.
If one of these vertical planes does not extended to full
length but ends in between, within the crystal as shown in
figure, it is called edge dislocation.
Edge dislocations are symbolically represented by or
or depending on whether the incomplete plane starts from
the top or fromthe bottom of the crystal.
These two configurations are referred to as positive and
negative edge dislocations.
Perfect crystal
An incomplete plane in a
Crystal results in an edge
dislocation

Edge Dislocation
432 atoms
55 x 38 x 15 cm
3
This is a line defect called an
EDGE DISLOCATION
The edge dislocation containing an extra plane of
atoms lying above the positive slip plane (or)
Burgers plane are conventionally called the
positive edge dislocation.
If the extra half plane of atoms containing below
the slip plane called the negative edge dislocation.
Positive and negative dislocations
Burgers vector
Johannes Martinus
BURGERS
Burgers vector
1
2
7
6
5
4
3
8
9
1 8 2 3 4 5 6 7 9 10 11 12 13
1
2
3
4
5
6
7
8
9
1 8 2 3 4 5 6 7 9 10 11 12 13
A closed
Burgers
Circuit in an
ideal crystal
S
F
14 15 16
14 15 16
1
2
7
6
5
4
3
8
9
1 8 2 3 4 5 6 7 9 10 11 12 13 14 15
1
2
3
4
5
6
7
9
1 2 3 4 5 6 8 7 9 10 11 12 13 14 15
8
16
S
b
16
F

Map the same

Burgers circuit on a
real crystal
1
2
7
6
5
4
3
8
9
1 8 2 3 4 5 6 7 9 10 11 12 13 14 15
1
2
3
4
5
6
7
9
1 2 3 4 5 6 8 7 9 10 11 12 13 14 15
8
16
S
16
F

Burgers vector
The magnitude and the direction of the
displacement are defined by a vector
called the Burgers vector.
Consider two crystals one perfect and
another with edge dislocation.
Perfect crystal
P
An incomplete plane in a
Crystal results in an edge
dislocation
Fig 1.
Fig 2.
P Q
b
From fig. 1.
Starting from the point P, we go up by 6 steps, then move
towards right by 5 steps, and move down by 6 steps and
finally move towards left by 5 steps to reach the starting
point P, the burgers circuit gets closed.
From fig 2.
We end up at Q instead of the starting point P.
Now we have to move an extra step QP 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 Burgers vector is perpendicular to the edge
dislocation line.
Screw Dislocation
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
slip
no slip
boundary
= edge dislocation
Slip plane
b
Burgers vector
Slip plane
slip no slip
d
i
s
l
o
c
a
t
i
o
n
b
t
Dislocation: slip/no
slip boundary
b: Burgers vector
magnitude and
direction of the slip
t: unit vector
tangent to the
dislocation line
Dislocation Line:
A dislocation line is the boundary between
slip and no slip regions of a crystal
Burgers vector:
The magnitude and the direction of the
slip is represented by a vector b called
the Burgers vector,
Line vector
A unit vector t tangent to the dislocation
line is called a tangent vector or the line
vector.
1 2 3 4 5 6 7 8 9
1 2 3 4 5 6 7 8 9
slip
no slip
boundary
= edge dislocation
Slip plane
b
Burgers vector
t
In general, there can be any angle
between the Burgers vector b (magnitude
and the direction of slip) and the line
vector t (unit vector tangent to the
dislocation line)
b t Edge dislocation
b t Screw dislocation
b t , b t Mixed dislocation
b
t
b || t
1
2
3
Screw dislocation results from a displacement of the
atoms in one part of a crystal relative to the rest of
the crystal,forming a spiral ramp around the
dislocation line
Screw Dislocation
525 atoms
45 x 20 x 15 cm
3
Screw Dislocation (another view)
Edge
Dislocation
Screw
Dislocation
Positive Negative
Extra half
plane above
the slip plane
Extra half
plane below
the slip plane
Left-handed
spiral ramp
Right-handed
spiral ramp
b parallel to t b antiparallel to t
Surface
Defects
Surface defects
Surface defects refer to region of distortions
that lie about surface having a thickness of a
few atomic diameters.