Introduction:

X-ray diffraction techniques are very useful for crystal

structure analysis and identification of different types of
crystals.

Experimental study of crystalline materials became
possible only after the discovery of x-rays.

Diffraction occurs when waves traveling through an
aperture whose dimensions are order of integral
multiples of wavelength.

Typical inter atomic spacing in crystals is 2-3A. These
wavelengths lies in x-ray spectra.

Hence x-rays diffraction is used to study the crystal
structures.

Braggs law:

It states that, the path difference between the
two reflected rays from parallel planes of a
crystal should be always equal to integral
multiples of wavelength of x-rays so as to
produce maxima or constructive interference.

The crystal acts like a series of parallel
reflecting planes.

Consider a ray PA reflected at an atom A, in
the direction AR from plane 1 and another
ray QB reflected from plane 2 at another atom
B in the direction BS.


Plane 1
Plane 2
Plane 3
A
B
C D
P
Q
R
S
d
90

90


Therefore the path difference between these two
rays = CB+BD

When path difference is equal to the integral multiple
of wave length, the two rays will reinforce with each
other subsequently an intense spot is produced.

The path length traveled by x-rays along QCBDS is
greater than that of the path length traveled along
PAR.
Thus the path difference = QCBDS PAR.
= (QC + CB + BD + DS) (PA + AR)
since QC = PA and DS = AR (from fig.)
CB+BD=n
CB=BD=d sin (from Fig)
2d sin= n

Where n = 1,2,3,.. represents the first
order, second order n
th
order spectra.
For 1
st
order sin
1
= /2d.
For 2
nd
order sin
2
= 2 / 2d.
For 3
rd
order sin
3
= 3 / 2d.
where
1
,
2
and
3
are the glancing
angles for n=1,2 and 3 respectively.

Let d
1 0 0
, d
1 1 0
and d
1 1 1
represents the inter planar distances of (1 0
0) , (1 1 0) and (1 1 1 ) planes. Let the corresponding glancing angles
are 1, 2 and 3 respectively for the same wavelength using
Braggs law we get
2d
1 0 0
sin
1
= n
2d
1 1 0
sin
2
= n and
2d
1 1 1
sin
3
= n
From above relations it is very clear that sin 1/d
Therefore sin
1
: sin
2 :
sin
3
= 1/d
1 0 0
: 1/d
1 1 0
: 1/d
1 1 1

When above ratio satisfies then it is
conformed to be simple cubic system.
If it satisfies then it is BCC.

And for the ratio it is FCC.
Thus, the Braggs law can help in determining the crystal structures
2
3
: 2 : 1
3 :
2
1
: 1
3 : 2 : 1
Crystal Defects

Any deviation from the perfect periodicity of
arrangement of atoms or molecules or ions in a
crystal is called Imperfection or Defect.

All crystals have some defects. The defects can be
of different types depending on their magnitude. The
properties like Physical, Chemical, Electrical,
Electronic, Mechanical, Magnetic etc.. can be
varied enormously with imperfections.

The classification of defects are as follows
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
Point defects
These are the places where an atom is missing or
irregularly placed in the lattice structure. Point defects
include lattice vacancies, self-interstitial atoms, substitution
impurity atoms, and interstitial impurity atoms.
Linear defects
Missing of groups of atoms in a plane is called Line defects
are commonly known as dislocations.
Planar defects
These are interfaces between homogeneous regions of the
material. Planar defects include tilt, twin and grain
boundaries. The stacking faults and external surfaces also
comes under these defects.
Volume defects
Cracks, voids or air bubbles represents these defects.

Different types of point defects are shown in figure below.
(a)Self interstitial atom. (c) Substitutional atom
(b) Interstitial impurity atom. (d) a vacancy.

vacancy
Interstitial
impurity
Substitutional
impurity
Point Defects

Vacancies: Missing of atoms at their regular sites in crystals is
called Vacancies. These are common, especially at high
temperatures when atoms are frequently and randomly change their
positions leaving behind empty lattice sites. Thus the vacancies are
not permanent sites. They can be created and destroyed.

Self interstitialcy: An extra atom that occupies the vacancy
position where an atom is normally missed at the lattice point. Self
interstitial atoms occur only in the low packing concentrations of
metals.

Interstitial Impurity: It is the position where an extra atom that
can be introduced which is not of the regular atomic site. If the
size of the impurity atom is substantially small then the structure
can not be dislodged. The converse is true.







These are much smaller than the atoms in the bulk matrix. Thus
the interstitial impurity atoms fit into the open space between
the bulk atoms of the lattice structure.
Example: The carbon atoms that are added to iron to make
steel. Carbon atoms, with a radius of 0.071 nm, fit nicely in the
open spaces between the larger (0.124 nm) iron atoms.

Substitutional impurity : It is an atom of a different type
which replaces one of the parent atoms. Substitutional impurity
atoms are usually with approximately 15% of the parent atoms.
Example:- Zinc atoms in brass.
In brass, zinc atoms with a radius of 0.133 nm have replaced
some of the copper atoms, which are of radius 0.128 nm.


Defects in ionic
solids
Schottky Defects:-

Missing of a pair of ions i.e. one cat-ion and one anion from an
ionic crystal is known as Schottky Defect. Such pair of vacant ion
sites are called Schottky imperfections

Schottky
defect
Cation vacancy
+
anion vacancy
This kind of defect is dominant in Alkali Halides and in these Crystals
overall electrical neutrality is maintained. It occurs in low packing density
crystals.


Frenkel defects:

In ionic crystals the displacement of a cat-ion from its regular site to an interstitial
site is called Frenkel imperfection.

.
Frenkel
defect
Cation vacancy
+
cation interstitial
This kind of defect is dominant in Silver Halides and in these Crystals overall electrical
neutrality is maintained. It occurs in high packing density crystals.

Energy of formation of a vacancy
Thermal energy in a solid results in elastic vibrations of the
lattice atoms. Large displacement may cause atoms to jump
from normal to interstitial positions. This results in creation of
both interstitial atoms and vacant lattice sites.
The number of vacancies is determined by the temperature T,
the total number of atoms / ions N, and the average energy E
v

required to create a vacancy.
n = f (N, E
v
, T)
(1)
Equation (1) gives average energy formation of a vacancy in a
crystal. This is the energy required to remove an atom from a lattice
site inside the crystal to a lattice site on the surface. This is called the
enthalpy of formation of the point imperfection.
From the law of statistical mechanics
Number of vacancies at any temperature in
elemental solids:
(1)
From eqn. (1)
If n<<N
In general, the number of vacancies n is always very small
compared to the total number of metal ions/ atoms. Hence the
equation (3) can be used to calculate the number of vacancies
when temperature is much below the melting point.
(2)
(3)
Schottky defects in ionic crystals at Equiliobrium
In ionic crystals Schottky defect is due to the missing of cat-ion
anion pair (i. e., A
+
, B
-
) from the respective lattice positions.

Let E
s
be the average energy required to create a Schottky defect
and n be the number of Schottky defects produced by removing n
number of A
+
cat-ions and n number of B
-
anions. If N be the total
number cat-ion anion pairs, the number of Schottky defects is
If n<<N
Thus the number of Schottky defects depends on (i) total number
of ionic pairs (ii) temperature and (iii) the energy.
Frenkel defects in ionic crystals at Equilibrium
Let E
f
be the average energy required to displace a cation from the
normal lattice position to an interstial site and N
i
be the number of
interstitial sites. If N be the total number of cations (in an ionic
crystal A
+
, B
-
), the number of Frenkel defects is
Hence at low temperature, the number of Frenkel defects is small.
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 =
v B
v B
N!
F nE -K Tlog( )
(N n)!n!
F nE K T{logN! log(N n)! logn!}
=

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

~
<<
=

=
+ =
=
=
Hence equilibrium concentration of vacancies
decreases with increase of 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 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
B p
]
n! n)! (N
N!
Tlog[ K nE F
TS U F

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

+ + =

At thermal equilibrium, free energy is constant and

minimum with respect to n, hence
}
T 2K
E
Nexp{ n
N n if
}
T 2K
E
n)exp{ (N n
]
n
n N
log[
T 2K
E
]
n
n N
Tlog[ 2K E
0 ]
dn
dF
[
B
p
B
p
B
p
B P
T

~
<<<

=
=
Calculation of number of Frenkel Defects at given
temperature:

In ionic crystal an ion may be displaced from the regular
lattice to an interstitial site or void space.
If it is so, then a vacancy and an interstitial defect will be
formed.

A Frenkel imperfection in silver halides and calcium
fluoride are of the Frenkel type.

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,
]}
n! n)! (N
! N
][
n! n)! (N
N!
Tlog{[ K nE F
TS U freeenergy
]}
n! n)! (N
! N
][
n! n)! (N
N!
log{[ K S
logp K entropy
]
n! n)! (N
! N
][
n! n)! (N
N!
[ p
i
i
B i
i
i
B
B
i
i

=
=

=
=

=
} 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
Line defects are one dimensional
imperfections in the geometrical sense.

These are also called dislocations. The
dislocations are of two types .
1. Edge dislocation
2. Screw 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
depending on whether the incomplete plane starts from the
top or from the 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
A complete plane in a
Crystal
Perfect crystal
Edge dislocated crystal
Extra half plane
Slip plane
The edge dislocation containing an extra half plane
of atoms lying above the positive slip plane (or) is
called the positive edge dislocation.

If the extra half plane of atoms containing below
the slip plane is called the negative edge dislocation.


Positive and negative dislocations
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
Displacement of the atoms in one part of a crystal
relative to the rest of the crystal, forming a spiral ramp
around the dislocation is called Screw dislocation.

In this, the atoms are displaced in two separate planes
perpendicular to each other.

In a figure the plane ABCD is the slipped area.
The upper portion of the crystal has been sheared by an
atomic distance to the right relative to the lower
portion.

No slip has taken place to the right of AD and AD is a
dislocation line.
A
B
C
D
Here, the dislocation is parallel to its Burgers
vector or shear vector.

The dislocation is terminated at AD
b
t
b || t
1
2
3
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
Missing half plane A Defect
An extra half plane
or a missing half plane
An extra half plane
or a missing half plane
Edge
Dislocation
This is a line defect called an
EDGE DISLOCATION


Positive Edge dislocation Negative Edge dislocation
The atom positions around an edge dislocation; extra half-plane of atoms shown
in perspective.
Burgers Vector
The magnitude and the direction of the displacement of atoms in
planes are defined by a vector called the Burgers vector.

Burger vector is perpendicular to the edge dislocation.

Burger vector = FS = b
1
2
7
6
5
4
3
8
9
1 8 2 3 4 5 6 7 9 10 1
1
12 13
1
2
3
4
5
6
7
8
9
1 8 2 3 4 5 6 7 9 1
0
1
1
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 1
1
12 13 14 15
1
2
3
4
5
6
7
9
1 2 3 4 5 6 8 7 9 10 1
1
12 13 14 15
8
16
S
b
16
F


Burger vector = FS = b
Perfect crystal
P
An incomplete plane in a
Crystal results in an edge
dislocation
P
Q
b
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 above fig it is very clear that we
end up at Q instead of the starting point
P.
Therefore we have to move an extra
step QP to reach the original position P
in order to close the burgers circuit.

The magnitude and the direction of the
step defines the Burgers vector (BV)
BV = QP = b
1
2
7
6
5
4
3
8
9
1 8 2 3 4 5 6 7 9 10 1
1
12 13 14 15
1
2
3
4
5
6
7
9
1 2 3 4 5 6 8 7 9 10 1
1
12 13 14 15
8
16
S
16
F

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
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
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.
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
THE END