Crystal Structure

To study the physical properties of solids a special branch of physics called solid state physics. It
is mainly devoted to the study of solids particularly and the arrangement of atoms in the crystal
structure. Solid are classified in to two categories one is define as crystalline solid and other one
is amorphous solids.

Amorphous

The amorphous solids are those which lack the regular arrangement of atoms or
molecules in long range. Example is plastics etc.

Crystalline

The crystalline solids are those which contain the regular arrangement and
repeated pattern of atoms and molecules, and hence a long range order of atoms and molecules.
The examples of crystalline solids are diamond, quartz etc.

A crystal structure of a solid are can be describe with the aid of a simple geometric concept
namely a space lattice. The space lattice may be defined as an array of point in space such that
the environment about each point is same.

Crystal structure

We know that a periodic arrangement of points in the space is called lattice. For
proper definition of a crystal structure if a motif (basis) is added at each point in the lattice. The
basis is identical in all point in the crystal structure. So the crystal appears exactly same at one
point as does at other equivalent points. When the basis or motif is attached at each point in the
lattice the crystal structure is obtain. So the crystal structure is define as

CRYSTAL STRUCTURE = LATTICE + BASIS

 Hear points represent the lattice and hollow dotes represent the
basis the atoms and molecules. If we minimum one atom is attach
with the lattice and maximum 1000(approximately) atoms are
attached with a single lattice point.

The crystal structure can be classified in to two groups

Two dimensional crystal structures

Three dimensional crystal structures

Two dimensional structures

The two dimensional crystal structure also called as space lattice and a space lattice can be define
as an array of points arrange in a regular or periodic fashion in two dimensional plane. Each
point in the lattice is identical to its surrounding atoms. If the distance between two neighbouring
atoms is define as ‘a’ in the particular direction and the distance between successive points is
same ‘a’. So is called periodicity in the particular direction (axes).The same environment would
be found after equal intervals of distance in the same direction and environment would be
different in different direction. There are generally five types of two dimensional lattice are
present [Link] [Link] [Link] [Link] [Link] rectangular.

Three dimensional structures

In 1848 A. Bravais a French scientist proved that there are 14 space lattices in total, which are
required to describe all possible arrangement of points in space. It is already shown that each
lattice has exactly same environment these type of lattice are come t=in to three dimensional
lattice type or are define as Bravais lattice.

Unit cell, Translation vector and Crystal Parameter

Unit cell is a smallest geometrical figure the representation of

which gives the actual crystal structure. It is the fundamental
elementary pattern of minimum .no. of atom or molecules which
are represent fully all the characteristics of a crystal structure.

The periodicity repeating arrangement of points in a space lattice can

be described by the operation operates on the crystal constants. This operation is known as
translation operation.

Let us consider a two dimensional net or a regular

arrangement of points. In the net a point O is
consider after a traveling a distance ‘a’ a point F is
obtain again after a distance ‘a’ the same type of
point is present. So we can say that the position of
any point alone the row is given by l =pa where p is
an integer and a is called translation vector in the particular axes (direction). If we
simultaneously consider two direction on is x and other one y then from point o position of a
point O’ is define as l = pa+qb the translation vector a,b,c are called lattice parameter or basis
vector or primitive vector. If we consider above mathematics in the three dimensional form then
in this case an another axes z is also coming and the operation is define as l = pa+qb+rc angle
between a,b,c is denoted by α,β,γ. The size of the unit cell is extremely small for example in case
of copper on side length is 3.6Ao so if we calculate no of cell present in 1 mm is defined as 10 -
3
m/3.6x10-10=2.8x106.

Unit cell Vs primitive cell

Primitive cell may be define as a geometrical

shape which is repeated infinite in three dimensional
space and fill all the space and is ebullient to one
lattice point i.e. the unit cell that contain one
lattice point only at the corners is known as
primitive cell the difference between unit cell
and primitive cell is that primitive cell is not
restricted to being the ebullient to one lattice point.
In some cases two lattice points coincide on one
primitive cell. We can say that unit cell may be a
primitive cell but a primitive cell is not a unit cell
always.

The crystal system

A crystal system can be classify in to seven groups on the basis of their internal structure. These
seven crystal system are distinguish between one another by the three different value of their
translation vector (a,b,c,α,β,γ). Some of the crystal system is sub divided in to other group and
over all there are fourteen type of crystal structure.

Name of the structure Parameter Sub Group

Cubic a=b=c and α=β=γ P,I,F
Tetragonal a=b≠c and α=β=γ=900 P,I
Orthorhombic a≠b≠c and α=β=γ=900 P,I,F,C
Hexagonal a=b≠c and α=β, γ=1200 P
Monoclinic a≠b≠c and α=β=900 ,γ=1200 P,C
Triclinic a≠b≠c and α≠β≠γ≠900 P
Trigonal a=b=c and α=β=γ≠900 P

P=Primitive, I=Body centre, F=Face centre, C= Side centre

Simple cubic crystal structure

The simplest and easiest structure to describe is the simple cubic crystal
structure. In a simple cubic lattice there is one lattice point at each eight corners
of the unit cell. If we taken an atom at one corner as the centre, it is
observed that this atom is surrounded by 6 equidistance nearest neighbours
and hence the coordination number of a simple cubic lattice is six. In
this structure each corner atom is shared by eight unit cells. Hence the share of each corner atom
to a unit cell is one eighth of an atom.

It is the way the total no of atoms in one unit cell will be atom. In other words the effective no of
lattice point in a simple cubic cell is one. Thus sc is the primitive cell. In this structure the atom
touches each other along the edges. Example of SC structure is Li, Na, Al, K, Cr, Fe, Ir, Pt, Au
etc.

Body Center Cubic structure

The base centre cubic structure is defined as in a unit call of this structure. There
are 8 atoms at the eight corners and other atoms at the body centre. As the body
centre atom is contained entirely within the unit call and is not shared by the
any surrounding unit cell.

Face Center Cubic Structure

In the case of FCC lattice, there are eight atoms at the eight corners of the unit
cell and one atom at the centre of the each face. Considering the atom at the face
centre as the origin, it can be observed that this face is common to two
unit cells and there are twelve points surrounding it situated at a distance equal
to the face diagonal of the unit cell. So the coordination no of the FCC
structure is twelve.

Some relevant parameter

Coordination Number (CN)

The coordination no. is defined as the number of equidistance nearest neighbour that an atom has
in the given structure. Greater is the coordination no. the more closely packed structure.

Effective number of atoms per unit cell (Z)

The effective no of atoms per unit cell is equal to the product of the number of atoms per lattice
point and the no of lattice point per unit cell. If we take an example of simple cubic unit cell
there are eight unit cell built around each corner of the cube. That is each unit cell receive 1/8th
contribution from each corner atoms.

Atomic packing fraction (APF)

The fraction of space occupied by atoms in a unit cell is known as the atomic packing fraction it
is define as the ratio of volume of effective no of atoms in the unit cell to the total volume of the
unit cell.

(number of atom per unit cell) (volume of each atom)

APF =
(Volume of the unit cell)

Zv
APF =
V

The APF denotes the efficiency with which the available space in a unit cell is utilized.

Void space

The void space in the unit cell is the vacant space left unutilized in the cell. It is equal to (1-
APF). It is often expressed as percentage. Thus void space =(APF-1)x100

The void space is more commonly expressed as interstitial space.

Density

As the unit cell possesses all the structure properties of a bulk crystal, the density of the unit cell
must be the same as that of the bulk crystal. Thus

Density, ρ=mass /volume =ZW/V

Where W is mass of each atom and is define as

W=M/NA where M is the molecular weight of the material and NA is Avogadro number.

Atomic radius (r)

Atomic radius is defined as half of the distance between nearest neighboring atoms in the
crystalline solid without any impurity.

Nearest neighbour distance (2r)

The distance between the centers of the two nearest neighbouring atoms is called neighbour
distance. It will be 2r if r is radius of atom.

Study of crystal structure on the basis of relevant parameter:

1. Coordination No
Coordination number of simple cubic structure is define as 6 as each atom shared by 6 atoms
with a distance between neighbouring atoms Is ‘a’. this is shown in the figure. Figure:-
Coordination number of simple cubic=6

Coordination no of bcc crystal structure it is equal to eight because every corner atom of unit
cell is at a distance 3a / 2 to body centre atom.

Figure:- Coordination number of base centre Cubic=8

Coordination number of face centre cubic structure is there are four corners atoms which are
at the same distance from the face centre atoms and eight face centre atoms are also at a
same

Distance a . All the three types of crystal structure can be understood by the figure.
2

Figure:- Coordination number of face centre cubic =12

2. Effective number of atoms per unit cell

A simple cubic cell has eight lattice points at its eight corners, which are occupied by the eight
atoms in is a primitive cell with lattice points at the eight corners of the cubes. In the three
dimensional array, each corner atom is linked to eight surrounding unit cells. It therefore
contributes equally its volume and mass to the eight adjacent cells. It is seen that each corner
atom in effect contributes only 1/8th of its content to a unit cell

1  atom   corner 
Z=    8 
8  corner   cell 
Z =1

Similarly in case of BCC structure there is one centre atom is also situated at the centre. So the
effective no. of atoms per unit cell can be define as
  bodycenteratom  1  atom   corner 
Z = 1     8 
 cell  8  corner   cell 
Z = 1+1 = 2

And in case of FCC structure one extra atom is place in middle of each face. Now the effective
number of atom is defining as in case of a FCC structure.

1  Atom   face  1  atom   corner 

Z=    6 +  8 
2  face   cell  8  corner   cell 
Z = 3 +1 = 4

3. Atomic Radius

Simple cubic:-

Atom is in contact along the edge of the cube so

2r = a
r = a/2

Body cantered:-

In case of body centre structure each corner atom is also connect with the body diagonal or
centre atom. Now if we consider the body diagonal then from the figure

AB = a; BC = a

Now by the Pythagoras theorem

( AC )2 = ( AB )2 + (BC )2
( AC )2 = 2a 2
Now by the figure

( AC )2 = 2a 2
AD = 4r
AC = 2 a

By the Pythagoras theorem

 (4r )2 = 2a 2 + a 2
a
r= 3
4

Face cantered:-

In case of face centre cubic structure by figure atoms are in contact along the face diagonal of the
cube, now by the figure

ABC
AB = a
DC = a

Now

( AC )2 = a 2 + a 2

(4r )2 = 2a 2 4r = 2a r=
a
2 2

4. Nearest Neighbour distance

Simple cubic

In simple cubic structure atom are in contact with the edge of the cube length of one edge side is
a and radius of the atom is r so neighbour distance can be define in case of SC structure

2r=a

a=2r

Body cantered

a 3
r=
4
a 3
2r =
2

Face cantered
 a
r=
2 2
a
2r =
2

5. Atomic packing fraction

Simple cubic

Zv
APF =
V
4
z = 1; v = r 3 ;V = a 3
3

4
1. r 3
APF = 3 3
a
r = a/2
a = 2r

APF = = 0.52
6

Body centre

a 3
z = 8; r =
4
8.3 3r 3
APF = = 0.68
3x64r 3

Face centre

a
z = 4; r =
2 2
4
4. r 3
APF = 3 3 = 0.74
a

6. Void Space

Simple Cubic
 Void space=(1-APF)

Void space=(1-0.52)=0.48

Body center

Void space=(1-APF)

Void space=(1-0.68)=0.32

Face center

Void space=(1-APF)

Void space=(1-0.74)=0.26

Important cubic structure

NaCl (sodium chloride)

In sodium chloride, sodium loses its outermost electron and acquires an excess of positive charge
while the chlorine atom accepts one electron from sodium and becomes a negative ion. Now, due
to the electrostatic forces between the excess charges, the two ions attract each other. But due to
strong forces of repulsion by their outer electron shells come into account and due to this
repulsive force they reach each other at a certain distance. When repulsion and attraction is
balance then equilibrium is obtain. The Bravais lattice is fce center lattice structure. There are
four NaCl molecules in a unit call, with ions in the position:-

Figure:- NaCl crystal structure.

1 1 1 1 1 1
Na = , , ;0,0, ;1,0, ; ,0,0
2 2 2 2 2 2
1 1 1 1 1 1
Cl = 0,0,0; , ,0; ,0, ;0, ,
2 2 2 2 2 2
In this structure, each ion is surrounded by six nearest neighbours of the opposite kind. The
coordination number is therefore six. There are twelve next nearest neighbours of same kind as
the reference ions. Examples of such type of crystal structure are KCl, KBr, MgO, AgBr etc.

CsCl (Cesium Chloride)

The cesium chloride, CsCl structure is a simple cubic space lattice. There is one molecule per
unit cell, with atoms in the body cantered position.

Cs:-000

Cl:-1/2,1/2,1/2

Each atom is at the centre of the cube of the opposite kind, so that the coordination number is 8.
So the CsCl crystal structure is the two interpenetrating simple cubic structure. The corner of one
such lattice is centre atom of some other lattice. One sub lattice is occupied by Cs + and other by
Cl- ions. Other crystal having the CsCl structure is NH4Cl, CuZn, AlNi etc.

Figure:- CsCl Crystal Structure

Small ball = Cl, Big ball = Cs

Discuss diamond structure and calculate the packing efficiency.

The diamond structure is a FCC structure with the basis of two carbon atoms one located at
the (0,0,0) and other at (a/4,a/4,a/4) associated with each lattice point.

Each carbon atom joins four other carbon atoms in regular tetrahedrons (triangular prisms).
Diamond based on the cubic form and its highly symmetrical arrangement of atoms. The point 0
and ½ are on the FCC lattice while those at ¼ and ¾ are on a similar lattice displaced along the
body diagonal by one fourth of its length. In this way the diamond structure is a combination of
two interpenetrating face center cubic sub lattice. Each atom in this structure has four nearest
neighbors occupying the corner point of a regular tetrahedral bond to which they are bound by
strong covalent bonds.
There are 8 atom per unit cell.
a 3
Atomic radius is r =
8
Atomic packing fraction is 34%.

Miller indices

We know that the crystal is made up of a large number of parallel equidistance planes
(passing through lattice points) called the lattice planes. The lattice planes can be chosen in
a various number of different ways (se figure 1) the perpendicular distance between
adjacent planes is called interplanar spacing. A given space lattice may have infinite sets of
lattice planes each having its characteristics interplanar spacing. The directions of these
planes are specified by miller indices h k and l. These indices are defined as the reciprocals
of the intercepts made by the plane on the three rectangular axes. The miler h k l for any
planes can be obtained by the following procedure: by number of planar al In the crystal
there exists direction and planes which contain a large concentration of atoms. It is necessary to
locate these direction and planes for crystal analysis. These planes are called lattice planes. For a
given lattice, plane can be chosen in a different no of ways. In the figure there are many planes
passing through same nine atoms with different plane lattice with different interplaner spacing
D1 and D2. One scientist, miller developed a procedure by using three numbers (hkl), known as
miller indices to designate the plane. He introduces the way to represent the position of all types
of plane in crystal structure with in the unit cell. Miller plane are represent by (hkl) and their
family by {hkl}. Direction of miller plane are given by <hkl >.The miller indices are the set of
three smallest possible integers which have the same ratio as the reciprocals of the intercepts of
the plane concerned on the three crystallographic axes.

The rules to find Miller Indices:-

1. Determine the intercepts of plane on three coordinate axes.

2. Take reciprocals of these.
3. Reduce the reciprocals in to whole number by LCM.

Take an example:-

Intercept are 2, 2, 2

Take the reciprocals are 1/2, 1/2, 1/2

LCM of the denominators of the LCM is 2

Hence multiply all the reciprocals with 2. We get 1,1,1 . Hence the miller indices are (111).
Some crystal planes

Figure:- Some Plans (100),(111),(110)

Thus the miller indices may be define as the reciprocals of the intercepts made by the plane on
the crystallographic axes when reduce to the smallest number.

Impotents point on Miller Indices:

1. All the parallel equidistance planes have the same miller indices. Thus the miller indices
define as a set of parallel planes.
2. A plane parallel to one of the coordinate’s axes has an intercepts on infinity.
3. If the miller indices of two planes have the same ratio i.e. (844),(422) and (211), then the
plane are parallel to each other.
4. If (hkl) are miller indices of a plane, then the plane cuts the axes in to h,k,l equal segment
respectively.

Separation between lattice plane in a cubic crystal:

The cube edge is a. let (hkl) be the miller indices of the plane ABC. This plane belongs to the
family of planes whose miller indices are (hkl) because miller indices represent a set of planes.
ON is the perpendicular drawn from the origin to this plane. This distance ON represent the
interplaner distance “d” of the family of plane with one plane at the origin. Let are
the angle between the coordinates axes X, Y, Z so by the figure

So we can say that

a a a
OA = ; OB = ; OC =
h mk l

By figure we know that OA:OB:OC= m1a:m2b:m3c

Now divide the LHS by m1m2m3 then

a a a
OA : OB : OC = : :
m2 m3 m1m3 m1m2
Now m2m3 = h; m1m3 = k; m1m2 = l then,

Because if OA, OB, OC are intercept then

 1   1   1 
h=  a, k =   a, l =  a
 OA   OB   OC 

Here a is the LCM of OA, OB, OC and also the length of the cube as shown in the figure

ON d ON d ON d
cos  = = : cos  = = : cos  = =
OA OA OB OB OC OC

Now from the figure

ON = x 2 + y 2 + z 2

x
= cos  : x = d1 cos  similerly y = d1 cos  ; z = d1 cos 
d1

Using above equation

d1 = (d1 cos  )2 + (d1 cos  )2 + (d1 cos  )2

cos 2  + cos 2  + cos 2  = 1

2 2 2
 d1   d 1   d1 
  +  +  =1
 OA   OB   OC 

Using equation
  d1 2 ( h 2 + k 2 + l 2 ) 
 2  =1
 a 
a
d1 =
(h + k 2 + l 2 )
2

In case of another plane

Let ON’=d2 be the perpendicular distance of the next A’.B’,C’ plane now between the plane

2a 2a 2a
OA' = ; OB ' = ; OC ' =
h k l

ON ' ON ' ON '

cos  ' = : cos  ' = : cos  ' =
OA' OB ' OC '

ON '2 = d 2 = (d 2
2
) (
2
cos  ' + d 2 cos  ' + d 2 cos  '
2
) (
2 2
)
2

(cos  ')2 + (cos  ')2 + (cos  ')2 = 1

2 2 2
 d2   d2   d2 
  +  +  =1
 OA'   OB '   OC ' 

Put the value of OA’OB’OC’

2 2 2
 d 2 h   d 2 k   d 2l 
  +  +  =1
 2a   2a   2a 

( )
2
d2
h2 + k 2 + l 2 = 1
4a 2
2a
d2 =
(
h2 + k 2 + l 2 )
Now separation between the two planes d1 and d2 is define as

d = d 2 − d1
2a a
d= −
(h 2
+ k2 +l2 ) (h 2
+ k2 +l2 )
a
d=
(h 2
+ k2 +l2 )
This is the relation between d and a using (hkl)

Imperfection in crystals:

An ideal crystal does have a very long range of order in their atomic arrangement. However ideal
crystal nighters occur in nature nor can be produce by the artificial methods. The deviation from
the ideal crystalline structure is called defects. Their nature and effects are often very important
in understanding the properties of crystals. This is because some properties of material such as
stiffness, density and electrical conductivity which are known a structure-insensitivity are not
affected in the presence of the crystals while many of the properties of the greatest technical
importance such as mechanical strength, crystal growth, magnetic hysteresis, dielectric
strength, conduction in semiconductor, which are termed structure- sensitive are greatly
affected by relatively minor change in crystal structure caused by defect.

The structural imperfection can be classified on the basis of their geometry as point, line, and
surface and volume imperfection. These defects are further classified in too many categories:

Point defects:

They are imperfection point like region in the crystal and therefore they are imperfect in point
like region in the crystal so they may be referred as zero dimension imperfection. A point
imperfection comes about as a rule because of the absence or a matrix atom in the wrong place.
The most common point defect in a crystal of a pure element is described as.

Vacancy:

A vacancy is the simplest point defect in the crystal. This refers to a missing atom or a vacant
atomic site. Such defect may arise either from imperfect packing during the original
crystallization. I the latter case, when the thermal energy due to vibration is increased there is an
increased probability that individual atom will jump out of their position of lower energy.

Figure: Point defect in the crystal.

Interstitialcies:

In a closed packed structure if the atomic packing fraction is low an extra atom may be logged
within the structure. This is known as interstialcies. An atom can enter the interstials void or
space between the regularly positioned atoms only when it is smaller then the parent atoms.
Otherwise they will produce atomic distortion. Interstialcies may be di-interstialcies , tri-
interstialcies etc. the vacancy and interstialcies are inverse phenomenon.
 Figure: Interstialcies in the crystal structure.

When a normal atom moves into interstices it leaves behind its original position which is now
vacant and thus produces a pair of defects. In ionic crystal when a cationic goes into interstices
position and create a cation and anion pair this defect is known as Schottkey defects. A foreign
atom goes in to interstices position when it is smaller than the host atoms. Therefore normally
anion leaves its parent site and occupies interstitial space. These vacancies are called Frenkel
defect. For many such defects might be produced by plucking an interior atom out of its regular
lattice and placing it on the surface. These acts require energy. The disorder increases entropy of
the system. In thermal equilibrium certain lattice vacancies are always present so If Ev is the
energy requires taking an atom from a lattice site inside to a lattice site on the surface. This
energy is called enthalpy for formation of the point imperfection. nEv is the increases in energy
associated with the generation of n isolated vacant sites. Now by the probability total no of ways
in which we can pick up n-atoms from the crystal consisting of N atoms is given by

N!
P=
( N − 1)!n!

Since dislocation is increases due to the creation of n vacancies the corresponding increases in
entropy is given by:

S = K B log P
N!
S = K B log
( N − 1)!n!

This formation change the free energy F,

F = U − TS
N!
F = nEV − K B log
( N − 1)! n!

The second term can be solve by the string theorem log x! = x log x − x

F = nEV − K BT N log N − ( N − n) log( N − n) − n log n

Free energy is constant at equilibrium so,

 H
T = 0
n
( N − n)
EV = K B T log
n

( N − n) E
log  V
n K BT
EV
( N − n)
= e K BT
n

When n  ( N − n) = N so

EV

N = ne K BT

Hence the number of schottkey defects, n, depends up on

1. Total number of ion-pairs N.

2. Average energy required to produce a schottkey defects pair (Ev)
3. Temperature of the material

Frenkel defects:

Hear a vacancy is created in any material by the movement of an atom/ion to the surface. So in a
material vacancy – interstitial pair is formed. This creation of such pairs is called frenkel defects.

He energy absorbed during this creation is more then compensated by the resultant disorder in
the lattice or structure. The vacancies are always present in a crystal due to thermal condition
variations. This process required energy. When this disorder increases then entropy of the system
is also increases in thermal equilibrium a certain number of lattice vacancies are always
[Link] n and N are the concentration of frenkel defects produce and the total no of cation
present in the material respectively.

If Ni and Ef are the total concentration of interstitial sites and average energy required to produce
a single frenkel defects. The total no of different way in which n frenkel defect can be produce

 N!   N! 
W =   
 ( N − n)!n!  ( N i − n)!n!

The first part on RHS represent the no of ways the n cation or anion vacancies are formed among
total N ions and the second part gives the no of ways the n vacancies can combined the N i
interstitial sites. Thus the increases in entropy is
 S = K B log W
 N!   N! 
S = K B log    
 ( N − n)! n!  ( N i − n)! n!

This produce a change in Helmholtz free energy, H, as

H = E − TS
 N! N! 
H = nE f − K BT log  x 
 ( N − n)!n! ( N i − n)!n!

Using string approximation:

 N! N!   N!   N! 
log  x  = log   + log  
 ( N − n)! n! ( N i − n)! n!  ( N − n)! n!  ( N i − n)! n!

= N log N + N i log N i − (N − n)log (N − n) − (N i − n)log (N i − n) − 2n log n Put this term in free

energy equation

 N log N + N i log N i − (N − n ) log (N − n )

H = nE f − K B T  
− (N i − n ) log (N i − n ) − 2n log n 

Differentiating the above equation with respect to n on constant temperature we get

H
= E f − K BT log (N − n )(N i − n ) − 2 log n
n T

H  ( N − n )(N i − n ) 
= E f − K BT log  
n T  n2 

Free energy is constant at equilibrium

H
=0
n T

 ( N − n )( N i − n ) 
E f − K BT log  =0
 n2 
 ( N − n )( N i − n ) 
E f = K BT log  
 n2 

As we know that N >> n and Ni >> n

  NN 
E f = K BT log  2 i 
 n 

E f = K BT log NN i − 2 log n

1 Ef
log n = log NN i −
2 2 K BT

Ef
−
n = (NN i ) e
1/ 2 2 K BT

This statement shows that

1. n is proportional to (NNi)1/2 ,
2. n is proportional to average energy required to produce the frankal’s defect
3. n is proportional to temperature of the material

Why X-ray is used for crystal structure analysis?

X-ray are electromagnetic in nature and have the wavelength ( =1A 0) much shorter than the
wavelength of visible light. It is known that a wave shows the diffraction effect if the wavelength
of the wave is of the order of the dimensions of the diffracting substance. When the wave nature
of the X ray is confirmed, attempts were made to measure the wavelength of X ray. Therefore in
order to diffract X rays, grating with much finer rulings, having distance between lines
comparable with the wavelength of X ray.

What is Bragg’s law? Write down the statement of Bragg’s law.

The fundamental law of x-ray crystallography, nλ = 2dsinθ, where n is

an integer, λ is the wavelength of a beam of x-rays incident on a crystal
with lattice planes separated by distance d, and θ is the Bragg angle.

Draw some crystal planes.(100),(110)

Find the set of miller indices for a plane of intercept 3a, 2b, and 4c.

Intercept of plane are:- X = 3a,Y = 2b,Z = 4c

Take reciprocals of these:-h = 1/3, k = 1/2, l = 1/4

4+6+3
Reduce the reciprocals in to whole number by LCM:-
12

(hkl) = (4 6 3)

Show that the c/a ratio for an ideal HCP structure is 8 / 3 .Give its co-ordination no. and
packing fraction.

In the hexagonal structure a unit cell consist of three layers. The bottom layer has 6 atoms at the
corners and one face centered atom and the upper layer contain also the 6 atoms in between these
layer one layer is present. In this layer three atoms are present. Each of the atom touches three
atoms of the below plane.
Let ‘c’ be the height of the unit cell along z axis and’a’ be its edge. The three body atoms lie in
the horizontal plane at c/2. these three atoms just on the rest on the three atoms at the corner of
the triangle. By the triangle

AY
Cos 30o =
AB
a 3
AY = a Cos 30o =
2
( AZ ) = ( AX ) = ( ZX )
2 2 2

a2 c2  2 2a 3 a 
a2 = + AXZ , AX = AY = = 
3 4  3 3 2 3
c2 a 2 2a 2
= a2 − =
4 3 3
c2 8
=
a2 3

Coordination number of a unit cell is 12

And atomic packing fraction is 0.74 or 74 %

Derive the relation of Bragg’s law for diffraction on X ray.

Let us consider rays LMN and PQR, which are
reflected by two atoms M and Q. the atom Q is
vertically below to M. length of the path PQR is
greater then path LMN. The path difference is
(AQ+QB) and according to the condition of
interference by reflection, we have
(AQ+QB)
= nλ

AQ = QB = d sin θ
2d sin θ = nλ

This is known as Bragg’s Law and given the condition for reflection of X ray from series of
atomic layers in a given plane. For a given set up with monochromatic radiation, the wavelength
λ is fixed. Different direction in which intense reflection will be observed by giving the different
value of θ. For first maxima:-

sin 1 =
2d
Second maxima:-
2
sin  2 =
2d
Third maxima:-
3
sin  3 =
2d
When a beam of monochromatic X ray falls on a crystal, each atom become the source of
scattering radiation

What is different type of bonding in solids?

Ionic Bonds

An ionic bond is a chemical bond formed by the electron attraction between positive and
negative ions. Ionic bonds are made when an electron from the valence shell of one atom is
transferred to the valence shell of another atom. The atom that lost an electron becomes a
positive ion and the atom that gains the electron becomes a negative ion. In NaCl the sodium ion
has one less electron than protons so it has a positive charge. The chlorine ion has one more
electron than protons so it has a negative charge. Since positives are attracted to negatives the
two ions are attracted to each other. The atom that loses an electron becomes a cation which is
positive, and the atom that gains an electron becomes an anion which is negative. The nature of
the ionic bonds facilitates the formation of ionic solids by attracting other charged atoms to form
a solid. The ions are arranged in a crystalline structure with each Na+ ion attracted to several Cl-
ions and each Cl- ion attracted to several Na+ ions. There are no NaCl molecules.

Covalent Bonds

Covalent Bonds are chemical bonds formed by the sharing of a pair of electrons between atoms.
The nuclei of two different atoms are attracting the same electrons. Therefore, unlike ionic bonds
where an electron is moved from one atom to another the electrons are shared.

The Octet Rule is a tendency of atoms in molecules to have eight electrons in their valence
shells. (Two for hydrogen atoms.) The octet rule is a general rule, but is not followed by all
molecules.

Multiple Bonds are sometimes found in molecules so that the molecules satisfy the octet rule. A
single bond (which was discussed earlier) is when a single pair of electrons is shared between the
two atoms. A double bond is when two pairs of electrons are shared between two atoms. A triple
bond is when three pairs of electrons are shared between two atoms. (Notice a trend?) Double
and triple bonds mostly occur when the elements Carbon(C), Nitrogen(N), Oxygen(O) and
Sulfur(S) are involved. An example of a molecule with double bonds is Carbon Dioxide (CO2).
Notice that each element ends up with eight electrons around it.

Metallic bond:-

In case of metals the valence electron are mobile and are not bound to any particular atom. A
metallic bond is formed when the force of attraction between the positive ion core and electron
gas.

Crystal Structure

To study the physical properties of solids a special branch of physics called solid state physics. It
is mainly devoted to the study of solids particularly and the arrangement of atoms in the crystal
structure. Solid are classified in to two categories one is define as crystalline solid and other one
is amorphous solids.

Amorphous

The amorphous solids are those which lack the regular arrangement of atoms or
molecules in long range. Example is plastics etc.

Crystalline

The crystalline solids are those which contain the regular arrangement and
repeated pattern of atoms and molecules, and hence a long range order of atoms and molecules.
The examples of crystalline solids are diamond, quartz etc.

A crystal structure of a solid are can be describe with the aid of a simple geometric concept
namely a space lattice. The space lattice may be defined as an array of point in space such that
the environment about each point is same.

Crystal structure
 We know that a periodic arrangement of points in the space is called lattice. For
proper definition of a crystal structure if a motif (basis) is added at each point in the lattice. The
basis is identical in all point in the crystal structure. So the crystal appears exactly same at one
point as does at other equivalent points. When the basis or motif is attached at each point in the
lattice the crystal structure is obtain. So the crystal structure is define as

CRYSTAL STRUCTURE = LATTICE + BASIS

Hear points represent the lattice and hollow dotes represent the basis the atoms and molecules. If
we minimum one atom is attach with the lattice and maximum 1000(approximately) atoms are
attached with a single lattice point.

The crystal structure can be classified in to two groups

Two dimensional crystal structures

Three dimensional crystal structures

Two dimensional structures

The two dimensional crystal structure also called as space lattice and a space lattice can be define
as an array of points arrange in a regular or periodic fashion in two dimensional plane. Each
point in the lattice is identical to its surrounding atoms. If the distance between two neighbouring
atoms is define as ‘a’ in the particular direction and the distance between successive points is
same ‘a’. So is called periodicity in the particular direction (axes).The same environment would
be found after equal intervals of distance in the same direction and environment would be
different in different direction. There are generally five types of two dimensional lattice are
present [Link] [Link] [Link] [Link] [Link] rectangular.

Three dimensional structures

In 1848 A. Bravais a French scientist proved that there are 14 space lattices in total, which are
required to describe all possible arrangement of points in space. It is already shown that each
lattice has exactly same environment these type of lattice are come t=in to three dimensional
lattice type or are define as Bravais lattice.
Unit cell, Translation vector and Crystal Parameter

Unit cell is a smallest geometrical figure the representation of

which gives the actual crystal structure. It is the fundamental
elementary pattern of minimum .no. of atom or molecules which
are represent fully all the characteristics of a crystal structure.

The periodicity repeating arrangement of points in a space lattice can

be described by the operation operates on the crystal constants. This operation is known as
translation operation.

Let us consider a two dimensional net or a regular

arrangement of points. In the net a point O is
consider after a traveling a distance ‘a’ a point F is
obtain again after a distance ‘a’ the same type of
point is present. So we can say that the position of
any point alone the row is given by l =pa where p is
an integer and a is called translation vector
in the particular axes (direction). If we
simultaneously consider two direction on is x
and other one y then from point o position of a point
O’ is define as l = pa+qb the translation vector
a,b,c are called lattice parameter or basis vector or primitive vector. If we consider above
mathematics in the three dimensional form then in this case an another axes z is also coming and
the operation is define as l = pa+qb+rc angle between a,b,c is denoted by α,β,γ. The size of the
unit cell is extremely small for example in case of copper on side length is 3.6A o so if we
calculate no of cell present in 1 mm is defined as 10-3m/3.6x10-10=2.8x106.

Unit cell Vs primitive cell

Primitive cell may be define as a geometrical

shape which is repeated infinite in three dimensional
space and fill all the space and is ebullient to one
lattice point i.e. the unit cell that contain one
lattice point only at the corners is known as
primitive cell the difference between unit cell
and primitive cell is that primitive cell is not
restricted to being the ebullient to one lattice point.
In some cases two lattice points coincide on one
primitive cell. We can say that unit cell may be a
primitive cell but a primitive cell is not a unit cell
always.

The crystal system

A crystal system can be classify in to seven groups on the basis of their internal structure. These
seven crystal system are distinguish between one another by the three different value of their
translation vector (a,b,c,α,β,γ). Some of the crystal system is sub divided in to other group and
over all there are fourteen type of crystal structure.

Name of the structure Parameter Sub Group

Cubic a=b=c and α=β=γ P,I,F
Tetragonal a=b≠c and α=β=γ=900 P,I
Orthorhombic a≠b≠c and α=β=γ=900 P,I,F,C
Hexagonal a=b≠c and α=β, γ=1200 P
Monoclinic a≠b≠c and α=β=900 ,γ=1200 P,C
Triclinic a≠b≠c and α≠β≠γ≠900 P
Trigonal a=b=c and α=β=γ≠900 P

P=Primitive, I=Body centre, F=Face centre, C= Side centre

Simple cubic crystal structure

The simplest and easiest structure to describe is the simple cubic crystal
structure. In a simple cubic lattice there is one lattice point at each eight corners
of the unit cell. If we taken an atom at one corner as the centre, it is
observed that this atom is surrounded by 6 equidistance nearest neighbours
and hence the coordination number of a simple cubic lattice is six. In
this structure each corner atom is shared by eight unit cells. Hence the share of each corner atom
to a unit cell is one eighth of an atom.

It is the way the total no of atoms in one unit cell will be atom. In other words the effective no of
lattice point in a simple cubic cell is one. Thus sc is the primitive cell. In this structure the atom
touches each other along the edges. Example of SC structure is Li, Na, Al, K, Cr, Fe, Ir, Pt, Au
etc.

Body Center Cubic structure

The base centre cubic structure is defined as in a unit call of this structure. There
are 8 atoms at the eight corners and other atoms at the body centre. As the body
centre atom is contained entirely within the unit call and is not shared by the
any surrounding unit cell.

Face Center Cubic Structure

In the case of FCC lattice, there are eight atoms at the eight corners of the unit
cell and one atom at the centre of the each face. Considering the atom at the face
centre as the origin, it can be observed that this face is common to two
unit cells and there are twelve points surrounding it situated at a distance equal
to the face diagonal of the unit cell. So the coordination no of the FCC
structure is twelve.
Some relevant parameter

Coordination Number (CN)

The coordination no. is defined as the number of equidistance nearest neighbour that an atom has
in the given structure. Greater is the coordination no. the more closely packed structure.

Effective number of atoms per unit cell (Z)

The effective no of atoms per unit cell is equal to the product of the number of atoms per lattice
point and the no of lattice point per unit cell. If we take an example of simple cubic unit cell
there are eight unit cell built around each corner of the cube. That is each unit cell receive 1/8th
contribution from each corner atoms.

Atomic packing fraction (APF)

The fraction of space occupied by atoms in a unit cell is known as the atomic packing fraction it
is define as the ratio of volume of effective no of atoms in the unit cell to the total volume of the
unit cell.

(number of atom per unit cell) (volume of each atom)

APF =
(Volume of the unit cell)

Zv
APF =
V

The APF denotes the efficiency with which the available space in a unit cell is utilized.

Void space

The void space in the unit cell is the vacant space left unutilized in the cell. It is equal to (1-
APF). It is often expressed as percentage. Thus void space =(APF-1)x100

The void space is more commonly expressed as interstitial space.

Density

As the unit cell possesses all the structure properties of a bulk crystal, the density of the unit cell
must be the same as that of the bulk crystal. Thus

Density, ρ=mass /volume =ZW/V

Where W is mass of each atom and is define as

W=M/NA where M is the molecular weight of the material and NA is Avogadro number.
Atomic radius (r)

Atomic radius is defined as half of the distance between nearest neighboring atoms in the
crystalline solid without any impurity.

Nearest neighbour distance (2r)

The distance between the centers of the two nearest neighbouring atoms is called neighbour
distance. It will be 2r if r is radius of atom.

Study of crystal structure on the basis of relevant parameter:

1. Coordination No

Coordination number of simple cubic structure is define as 6 as each atom

shared by 6 atoms with a distance between neighbouring atoms Is ‘a’. this is
shown in the figure. Figure:- Coordination number of simple cubic=6

Coordination no of bcc crystal structure it is equal to eight because

every corner atom of unit cell is at a distance 3a / 2 to body centre atom.

Figure:- Coordination number of base centre Cubic=8

Coordination number of face centre cubic structure is there are four corners atoms which are
at the same distance from the face centre atoms and eight face centre atoms are also at a
same

Distance a . All the three types of crystal structure can be understood by the figure.
2

Figure:- Coordination number of face centre cubic =12

2. Effective number of atoms per unit cell

A simple cubic cell has eight lattice points at its eight corners, which are occupied by the eight
atoms in is a primitive cell with lattice points at the eight corners of the cubes. In the three
dimensional array, each corner atom is linked to eight surrounding unit cells. It therefore
contributes equally its volume and mass to the eight adjacent cells. It is seen that each corner
atom in effect contributes only 1/8th of its content to a unit cell

1  atom   corner 
Z=    8 
8  corner   cell 
Z =1

Similarly in case of BCC structure there is one centre atom is also situated at the centre. So the
effective no. of atoms per unit cell can be define as

 bodycenteratom  1  atom   corner 

Z = 1     8 
 cell  8  corner   cell 
Z = 1+1 = 2

And in case of FCC structure one extra atom is place in middle of each face. Now the effective
number of atom is defining as in case of a FCC structure.

1  Atom   face  1  atom   corner 

Z=    6 +  8 
2  face   cell  8  corner   cell 
Z = 3 +1 = 4

3. Atomic Radius

Simple cubic:-

Atom is in contact along the edge of the cube so

2r = a
r = a/2

Body cantered:-

In case of body centre structure each corner atom is also connect with the body diagonal or
centre atom. Now if we consider the body diagonal then from the figure

AB = a; BC = a

Now by the Pythagoras theorem

 ( AC )2 = ( AB )2 + (BC )2
( AC )2 = 2a 2
Now by the figure

( AC )2 = 2a 2
AD = 4r
AC = 2 a

By the Pythagoras theorem

(4r )2 = 2a 2 + a 2
a
r= 3
4

Face cantered:-

In case of face centre cubic structure by figure atoms are in contact along the face diagonal of the
cube, now by the figure

ABC
AB = a
DC = a

Now

( AC )2 = a 2 + a 2

(4r )2 = 2a 2 4r = 2a r=
a
2 2

4. Nearest Neighbour distance

Simple cubic

In simple cubic structure atom are in contact with the edge of the cube length of one edge side is
a and radius of the atom is r so neighbour distance can be define in case of SC structure

2r=a

a=2r
Body cantered

a 3
r=
4
a 3
2r =
2

Face cantered

a
r=
2 2
a
2r =
2

5. Atomic packing fraction

Simple cubic

Zv
APF =
V
4
z = 1; v = r 3 ;V = a 3
3

4
1. r 3
APF = 3 3
a
r = a/2
a = 2r

APF = = 0.52
6

Body centre

a 3
z = 8; r =
4
8.3 3r 3
APF = = 0.68
3x64r 3

Face centre
 a
z = 4; r =
2 2
4
4. r 3
APF = 3 3 = 0.74
a

6. Void Space

Simple Cubic

Void space=(1-APF)

Void space=(1-0.52)=0.48

Body center

Void space=(1-APF)

Void space=(1-0.68)=0.32

Face center

Void space=(1-APF)

Void space=(1-0.74)=0.26

Important cubic structure

NaCl (sodium chloride)

In sodium chloride, sodium loses its outermost electron and acquires an excess of positive charge
while the chlorine atom accepts one electron from sodium and becomes a negative ion. Now, due
to the electrostatic forces between the excess charges, the two ions attract each other. But due to
strong forces of repulsion by their outer electron shells come into account and due to this
repulsive force they reach each other at a certain distance. When repulsion and attraction is
balance then equilibrium is obtain. The Bravais lattice is fce center lattice structure. There are
four NaCl molecules in a unit call, with ions in the position:-
 Figure:- NaCl crystal structure.

1 1 1 1 1 1
Na = , , ;0,0, ;1,0, ; ,0,0
2 2 2 2 2 2
1 1 1 1 1 1
Cl = 0,0,0; , ,0; ,0, ;0, ,
2 2 2 2 2 2

In this structure, each ion is surrounded by six nearest neighbours of the opposite kind. The
coordination number is therefore six. There are twelve next nearest neighbours of same kind as
the reference ions. Examples of such type of crystal structure are KCl, KBr, MgO, AgBr etc.

CsCl (Cesium Chloride)

The cesium chloride, CsCl structure is a simple cubic space lattice. There is one molecule per
unit cell, with atoms in the body cantered position.

Cs:-000

Cl:-1/2,1/2,1/2

Each atom is at the centre of the cube of the opposite kind, so that the coordination number is 8.
So the CsCl crystal structure is the two interpenetrating simple cubic structure. The corner of one
such lattice is centre atom of some other lattice. One sub lattice is occupied by Cs + and other by
Cl- ions. Other crystal having the CsCl structure is NH4Cl, CuZn, AlNi etc.

Figure:- CsCl Crystal Structure

Small ball = Cl, Big ball = Cs

Discuss diamond structure and calculate the packing efficiency.

The diamond structure is a FCC structure with the basis of two carbon atoms one located at
the (0,0,0) and other at (a/4,a/4,a/4) associated with each lattice point.

Each carbon atom joins four other carbon atoms in regular tetrahedrons (triangular prisms).
Diamond based on the cubic form and its highly symmetrical arrangement of atoms. The point 0
and ½ are on the FCC lattice while those at ¼ and ¾ are on a similar lattice displaced along the
body diagonal by one fourth of its length. In this way the diamond structure is a combination of
two interpenetrating face center cubic sub lattice. Each atom in this structure has four nearest
neighbors occupying the corner point of a regular tetrahedral bond to which they are bound by
strong covalent bonds.
There are 8 atom per unit cell.
a 3
Atomic radius is r =
8
Atomic packing fraction is 34%.

Miller indices

We know that the crystal is made up of a large number of parallel equidistance planes
(passing through lattice points) called the lattice planes. The lattice planes can be chosen in
a various number of different ways (se figure 1) the perpendicular distance between
adjacent planes is called interplanar spacing. A given space lattice may have infinite sets of
lattice planes each having its characteristics interplanar spacing. The directions of these
planes are specified by miller indices h k and l. These indices are defined as the reciprocals
of the intercepts made by the plane on the three rectangular axes. The miler h k l for any
planes can be obtained by the following procedure: by number of planar al In the crystal
there exists direction and planes which contain a large concentration of atoms. It is necessary to
locate these direction and planes for crystal analysis. These planes are called lattice planes. For a
given lattice, plane can be chosen in a different no of ways. In the figure there are many planes
passing through same nine atoms with different plane lattice with different interplaner spacing
D1 and D2. One scientist, miller developed a procedure by using three numbers (hkl), known as
miller indices to designate the plane. He introduces the way to represent the position of all types
of plane in crystal structure with in the unit cell. Miller plane are represent by (hkl) and their
family by {hkl}. Direction of miller plane are given by <hkl >.The miller indices are the set of
three smallest possible integers which have the same ratio as the reciprocals of the intercepts of
the plane concerned on the three crystallographic axes.

The rules to find Miller Indices:-

4. Determine the intercepts of plane on three coordinate axes.

5. Take reciprocals of these.
6. Reduce the reciprocals in to whole number by LCM.

Take an example:-

Intercept are 2, 2, 2

Take the reciprocals are 1/2, 1/2, 1/2

LCM of the denominators of the LCM is 2

Hence multiply all the reciprocals with 2. We get 1,1,1 . Hence the miller indices are (111).

Some crystal planes

Figure:- Some Plans (100),(111),(110)

Thus the miller indices may be define as the reciprocals of the intercepts made by the plane on
the crystallographic axes when reduce to the smallest number.

Impotents point on Miller Indices:

5. All the parallel equidistance planes have the same miller indices. Thus the miller indices
define as a set of parallel planes.
6. A plane parallel to one of the coordinate’s axes has an intercepts on infinity.
7. If the miller indices of two planes have the same ratio i.e. (844),(422) and (211), then the
plane are parallel to each other.
8. If (hkl) are miller indices of a plane, then the plane cuts the axes in to h,k,l equal segment
respectively.

Separation between lattice plane in a cubic crystal:

The cube edge is a. let (hkl) be the miller indices of the plane ABC. This plane belongs to the
family of planes whose miller indices are (hkl) because miller indices represent a set of planes.
ON is the perpendicular drawn from the origin to this plane. This distance ON represent the
interplaner distance “d” of the family of plane with one plane at the origin. Let are
the angle between the coordinates axes X, Y, Z so by the figure

So we can say that

a a a
OA = ; OB = ; OC =
h mk l

By figure we know that OA:OB:OC= m1a:m2b:m3c

Now divide the LHS by m1m2m3 then

a a a
OA : OB : OC = : :
m2 m3 m1m3 m1m2

Now m2m3 = h; m1m3 = k; m1m2 = l then,

Because if OA, OB, OC are intercept then

 1   1   1 
h=  a, k =   a, l =  a
 OA   OB   OC 

Here a is the LCM of OA, OB, OC and also the length of the cube as shown in the figure

ON d ON d ON d
cos  = = : cos  = = : cos  = =
OA OA OB OB OC OC

Now from the figure

 ON = x 2 + y 2 + z 2

x
= cos  : x = d1 cos  similerly y = d1 cos  ; z = d1 cos 
d1

Using above equation

d1 = (d1 cos  )2 + (d1 cos  )2 + (d1 cos  )2

cos 2  + cos 2  + cos 2  = 1

2 2 2
 d1   d 1   d1 
  +  +  =1
 OA   OB   OC 

Using equation

 d1 2 ( h 2 + k 2 + l 2 ) 
  =1
 a2 
a
d1 =
(h 2 + k 2 + l 2 )

In case of another plane

Let ON’=d2 be the perpendicular distance of the next A’.B’,C’ plane now between the plane

2a 2a 2a
OA' = ; OB ' = ; OC ' =
h k l

ON ' ON ' ON '

cos  ' = : cos  ' = : cos  ' =
OA' OB ' OC '

ON '2 = d 2 = (d 2
2
) (
2 2
) (
2
cos  ' + d 2 cos  ' + d 2 cos  '
2
)
2

(cos  ')2 + (cos  ')2 + (cos  ')2 = 1

2 2 2
 d2   d2   d2 
  +  +  =1
 OA'   OB '   OC ' 

Put the value of OA’OB’OC’

 2 2 2
 d 2 h   d 2 k   d 2l 
  +  +  =1
 2a   2a   2a 

( )
2
d2
2
h2 + k 2 + l 2 = 1
4a
2a
d2 =
(
h + k2 + l2
2
)
Now separation between the two planes d1 and d2 is define as

d = d 2 − d1
2a a
d= −
(h 2
+k +l2 2
) (h 2
+ k2 +l2 )
a
d=
(h 2
+ k2 +l2 )
This is the relation between d and a using (hkl)

Imperfection in crystals:

An ideal crystal does have a very long range of order in their atomic arrangement. However ideal
crystal nighters occur in nature nor can be produce by the artificial methods. The deviation from
the ideal crystalline structure is called defects. Their nature and effects are often very important
in understanding the properties of crystals. This is because some properties of material such as
stiffness, density and electrical conductivity which are known a structure-insensitivity are not
affected in the presence of the crystals while many of the properties of the greatest technical
importance such as mechanical strength, crystal growth, magnetic hysteresis, dielectric
strength, conduction in semiconductor, which are termed structure- sensitive are greatly
affected by relatively minor change in crystal structure caused by defect.

The structural imperfection can be classified on the basis of their geometry as point, line, and
surface and volume imperfection. These defects are further classified in too many categories:

Point defects:

They are imperfection point like region in the crystal and therefore they are imperfect in point
like region in the crystal so they may be referred as zero dimension imperfection. A point
imperfection comes about as a rule because of the absence or a matrix atom in the wrong place.
The most common point defect in a crystal of a pure element is described as.

Vacancy:

A vacancy is the simplest point defect in the crystal. This refers to a missing atom or a vacant
atomic site. Such defect may arise either from imperfect packing during the original
crystallization. I the latter case, when the thermal energy due to vibration is increased there is an
increased probability that individual atom will jump out of their position of lower energy.

Figure: Point defect in the crystal.

Interstitialcies:

In a closed packed structure if the atomic packing fraction is low an extra atom may be logged
within the structure. This is known as interstialcies. An atom can enter the interstials void or
space between the regularly positioned atoms only when it is smaller then the parent atoms.
Otherwise they will produce atomic distortion. Interstialcies may be di-interstialcies , tri-
interstialcies etc. the vacancy and interstialcies are inverse phenomenon.

Figure: Interstialcies in the crystal structure.

When a normal atom moves into interstices it leaves behind its original position which is now
vacant and thus produces a pair of defects. In ionic crystal when a cationic goes into interstices
position and create a cation and anion pair this defect is known as Schottkey defects. A foreign
atom goes in to interstices position when it is smaller than the host atoms. Therefore normally
anion leaves its parent site and occupies interstitial space. These vacancies are called Frenkel
defect. For many such defects might be produced by plucking an interior atom out of its regular
lattice and placing it on the surface. These acts require energy. The disorder increases entropy of
the system. In thermal equilibrium certain lattice vacancies are always present so If Ev is the
energy requires taking an atom from a lattice site inside to a lattice site on the surface. This
energy is called enthalpy for formation of the point imperfection. nEv is the increases in energy
associated with the generation of n isolated vacant sites. Now by the probability total no of ways
in which we can pick up n-atoms from the crystal consisting of N atoms is given by

N!
P=
( N − 1)!n!

Since dislocation is increases due to the creation of n vacancies the corresponding increases in
entropy is given by:
 S = K B log P
N!
S = K B log
( N − 1)!n!

This formation change the free energy F,

F = U − TS
N!
F = nEV − K B log
( N − 1)! n!

The second term can be solve by the string theorem log x! = x log x − x

F = nEV − K BT N log N − ( N − n) log( N − n) − n log n

Free energy is constant at equilibrium so,

H
T = 0
n
( N − n)
EV = K B T log
n

( N − n) E
log  V
n K BT
EV
( N − n)
= e K BT
n

When n  ( N − n) = N so

EV

N = ne K BT

Hence the number of schottkey defects, n, depends up on

4. Total number of ion-pairs N.

5. Average energy required to produce a schottkey defects pair (Ev)
6. Temperature of the material

Frenkel defects:

Hear a vacancy is created in any material by the movement of an atom/ion to the surface. So in a
material vacancy – interstitial pair is formed. This creation of such pairs is called frenkel defects.

He energy absorbed during this creation is more then compensated by the resultant disorder in
the lattice or structure. The vacancies are always present in a crystal due to thermal condition
variations. This process required energy. When this disorder increases then entropy of the system
is also increases in thermal equilibrium a certain number of lattice vacancies are always
[Link] n and N are the concentration of frenkel defects produce and the total no of cation
present in the material respectively.

If Ni and Ef are the total concentration of interstitial sites and average energy required to produce
a single frenkel defects. The total no of different way in which n frenkel defect can be produce

 N!   N! 
W =   
 ( N − n)!n!  ( N i − n)!n!

The first part on RHS represent the no of ways the n cation or anion vacancies are formed among
total N ions and the second part gives the no of ways the n vacancies can combined the N i
interstitial sites. Thus the increases in entropy is

S = K B log W
 N!   N! 
S = K B log    
 ( N − n)! n!  ( N i − n)! n!

This produce a change in Helmholtz free energy, H, as

H = E − TS
 N! N! 
H = nE f − K BT log  x 
 ( N − n)!n! ( N i − n)!n!

Using string approximation:

 N! N!   N!   N! 
log  x  = log   + log  
 ( N − n)! n! ( N i − n)! n!  ( N − n)! n!  ( N i − n)! n!

= N log N + N i log N i − (N − n)log (N − n) − (N i − n)log (N i − n) − 2n log n Put this term in free

energy equation

 N log N + N i log N i − (N − n ) log (N − n )

H = nE f − K B T  
− (N i − n ) log (N i − n ) − 2n log n 

Differentiating the above equation with respect to n on constant temperature we get

 H
= E f − K BT log (N − n )(N i − n ) − 2 log n
n T

H  ( N − n )(N i − n ) 
= E f − K BT log  
n T  n2 

Free energy is constant at equilibrium

H
=0
n T

 ( N − n )( N i − n ) 
E f − K BT log  =0
 n2 
 ( N − n )( N i − n ) 
E f = K BT log  
 n2 

As we know that N >> n and Ni >> n

 NN 
E f = K BT log  2 i 
 n 

E f = K BT log NN i − 2 log n

1 Ef
log n = log NN i −
2 2 K BT

Ef
−
n = (NN i ) e
1/ 2 2 K BT

This statement shows that

4. n is proportional to (NNi)1/2 ,
5. n is proportional to average energy required to produce the frankal’s defect
6. n is proportional to temperature of the material

Why X-ray is used for crystal structure analysis?

X-ray are electromagnetic in nature and have the wavelength ( =1A 0)

much shorter than the wavelength of visible light. It is known that a
wave shows the diffraction effect if the wavelength of the wave is of the
order of the dimensions of the diffracting substance. When the wave
nature of the X ray is confirmed, attempts were made to measure the
wavelength of X ray. Therefore in order to diffract X rays, grating with
much finer rulings, having distance between lines comparable with the wavelength of X ray.

What is Bragg’s law? Write down the statement of Bragg’s law.

The fundamental law of x-ray crystallography, nλ = 2dsinθ, where n is an integer, λ is the

wavelength of a beam of x-rays incident on a crystal with lattice planes separated by distance d,
and θ is the Bragg angle.

Draw some crystal planes.(100),(110)

Find the set of miller indices for a plane of intercept 3a, 2b, and 4c.

Intercept of plane are:- X = 3a,Y = 2b,Z = 4c

Take reciprocals of these:-h = 1/3, k = 1/2, l = 1/4

4+6+3
Reduce the reciprocals in to whole number by LCM:-
12

(hkl) = (4 6 3)

Show that the c/a ratio for an ideal HCP structure is 8 / 3 .Give its co-ordination no. and
packing fraction.

In the hexagonal structure a unit cell consist of three layers. The bottom layer has 6 atoms at the
corners and one face centered atom and the upper layer contain also the 6 atoms in between these
layer one layer is present. In this layer three atoms are present.
Each of the atom touches three atoms of the below plane.
Let ‘c’ be the height of the unit cell along z axis and’a’ be its edge.
The three body atoms lie in the horizontal plane at c/2. these three
atoms just on the rest on the three atoms at the corner of the
triangle. By the triangle

AY
Cos 30o =
AB
a 3
AY = a Cos 30o =
2
( AZ ) = ( AX ) = ( ZX )
2 2 2

a2 c2  2 2a 3 a 
a2 = + AXZ , AX = AY = = 
3 4  3 3 2 3
c2 a 2 2a 2
= a2 − =
4 3 3
c2 8
=
a2 3

Coordination number of a unit cell is 12

And atomic packing fraction is 0.74 or 74 %

Derive the relation of Bragg’s law for diffraction on X ray.

Let us consider rays LMN and PQR, which are

reflected by two atoms M and Q. the atom Q is
vertically below to M. length of the path PQR is
greater then path LMN. The path difference is
(AQ+QB) and according to the condition of
interference by reflection, we have
(AQ+QB)
= nλ

AQ = QB = d sin θ
2d sin θ = nλ

This is known as Bragg’s Law and given the condition for reflection of X ray from series of
atomic layers in a given plane. For a given set up with monochromatic radiation, the wavelength
λ is fixed. Different direction in which intense reflection will be observed by giving the different
value of θ. For first maxima:-

sin 1 =
2d
Second maxima:-
2
sin  2 =
2d
Third maxima:-
 3
sin  3 =
2d
When a beam of monochromatic X ray falls on a crystal, each atom become the source of
scattering radiation

What is different type of bonding in solids?

Ionic Bonds

An ionic bond is a chemical bond formed by the electron attraction between positive and
negative ions. Ionic bonds are made when an electron from the valence shell of one atom is
transferred to the valence shell of another atom. The atom that lost an electron becomes a
positive ion and the atom that gains the electron becomes a negative ion. In NaCl the sodium ion
has one less electron than protons so it has a positive charge. The chlorine ion has one more
electron than protons so it has a negative charge. Since positives are attracted to negatives the
two ions are attracted to each other. The atom that loses an electron becomes a cation which is
positive, and the atom that gains an electron becomes an anion which is negative. The nature of
the ionic bonds facilitates the formation of ionic solids by attracting other charged atoms to form
a solid. The ions are arranged in a crystalline structure with each Na+ ion attracted to several Cl-
ions and each Cl- ion attracted to several Na+ ions. There are no NaCl molecules.

Covalent Bonds

Covalent Bonds are chemical bonds formed by the sharing of a pair of electrons between atoms.
The nuclei of two different atoms are attracting the same electrons. Therefore, unlike ionic bonds
where an electron is moved from one atom to another the electrons are shared.

The Octet Rule is a tendency of atoms in molecules to have eight electrons in their valence
shells. (Two for hydrogen atoms.) The octet rule is a general rule, but is not followed by all
molecules.

Multiple Bonds are sometimes found in molecules so that the molecules satisfy the octet rule. A
single bond (which was discussed earlier) is when a single pair of electrons is shared between the
two atoms. A double bond is when two pairs of electrons are shared between two atoms. A triple
bond is when three pairs of electrons are shared between two atoms. (Notice a trend?) Double
and triple bonds mostly occur when the elements Carbon(C), Nitrogen(N), Oxygen(O) and
Sulfur(S) are involved. An example of a molecule with double bonds is Carbon Dioxide (CO2).
Notice that each element ends up with eight electrons around it.

Metallic bond:-

In case of metals the valence electron are mobile and are not bound to any particular atom. A
metallic bond is formed when the force of attraction between the positive ion core and electron
gas.