Engineering Physics Complete Notes

UNIT – I
CRYSTALLOGRAPHY AND X-RAY DIFFRACTION

Crystal structure:
Crystal structure is a regular periodic arrangement of atoms or molecules or ions in three
dimensions.
Lattice points:
Lattice points are the points which are imagined instead of atoms, or molecules or ions in
crystal structure.
Lattice planes:
Any plane consisting lattice points, is called lattice plane.
Space lattice:
The regular periodic arrangement of lattice points in three dimensional, is called space lattice.
Unit cell:
Unit cell is a smallest entity in a crystal which exhibits the properties of the crystal and the
repetition of this in 3-dimentional gives crystal structure. The unit cell may be cube, rectangle
square etc.
Basis:
Crystal structure is obtained by attaching each atom or group of atoms(molecules) to lattice
points. The group of atoms attached to any lattice point is called basis of a crystal lattice
Hence
Crystal = Lattice + basis
Unit cell
(a) Lattice (b) Basis (c) Crystal structure

Lattice parameters: Z
c
α b
β γ Y
a
X
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Figure shows a unit cell. As shown in figure, the lines drawn parallel to the line of
intersection of any two faces of the unit cell which do not lie in the same plane are called
crystallographic axes X, Y & Z.
The angles between the three crystallographic axes represented by α, β & 𝛾, are called interfacial
angles or lattice angles. The intercepts a, b & c, which define the dimensions of the unit cell on
the respective crystallographic axes are called lattice constants or primitives of the unit cell. Thus
the three primitives a, b & c and three interfacial angles α, β & 𝛾 are known as the lattice
parameters.
Seven crystal systems:

Crystals are mainly classified into seven different types they are,
1. Cubic crystal system
2. Tetragonal system
3. Orthorhombic crystal system
4. Monoclinic crystal system
5. Triclinic crystal system
6. Trigonal crystal system
7. Hexagonal crystal system
1. Cubic crystal system :

In cubic crystal system, three lattice constants are same i.e. a=b=c. In this crystal system,
three crystal axes are mutually perpendicular to each other i.e. α=β=𝛾=900 example: Nacl.
2. Tetragonal crystal system :

In tetragonal crystal system, two lattice constants are same and third lattice vector is different
from these two lattice constants. i.e. a=b ≠c. In this crystal system, three crystal axes are
mutually perpendicular to each other i.e. α=β=𝛾=900 example: NiS𝑂4.
3. Orthorhombic crystal system :

In orthorhombic crystal system, three lattice constants are not equal i.e. a≠b≠c. In this crystal
system, three crystal axes are perpendicular to each other i.e. α=β=𝛾=900 example: BaS𝑂4 .
4. Monoclinic crystal system :

In monoclinic crystal system, three lattice constants are not equal i.e. a≠b≠c. In this crystal
system, any two lattice angles among crystal axes are 900 and third angle is not equal to 900 i.e.
α=β=900 ≠𝛾 example: Na2SO4
5. Triclinic crystal system :
In triclinic crystal system, three lattice constants are not same i.e. a≠b≠c. In this crystal
system, the lattice angles among crystal axes are different and not equal to 900 i.e. α≠β≠𝛾≠ 900
example: CuS𝑂4 .
6. Trigonal crystal system :
In trigonal system, three lattice constants are same i.e. a=b=c. In this crystal system, the
lattice angles among crystal axes are same but not equal to 900 i. e. α=β=𝛾 ≠ 900 example:
Cas𝑂4.
7. Hexagonal crystal system :

In hexagonal crystal system, any two lattice constants are same and third lattice constant is
different from these two lattice vectors i.e. a=b≠c. In this crystal system, two lattice angles
among crystal axes are 900 and third angle is equal to1200 . α=β= 900 , γ = 1200 . Example: SiO
and ice.
S.No Name of the Primitives and Unit cells of the crystal Examples
crystal system interfacial angles system
1 Cubic a=b=c NaCl, CaF2,NaClO2
0
α=β=𝛾=90
α
β
γ
2 Tetragonal a=b ≠c NiSO4, SnC2

α=β=𝛾=900
α
β
γ
3 Orthorhombic a≠b≠c KNO3, BaSO4,
α=β=𝛾=900
α
β
γ
4 Monoclinic a≠b≠c Na2SO4, FeSO4
α=β=900 ≠𝛾
α
β
γ
5 Triclinic a≠b≠c α CuSO4,K2SO4

β
α≠β≠𝛾≠ 900
γ

α
6 Trigonal a=b=c β CaSO4, Quartz
α=β=𝛾≠ 900 γ
7 Hexagonal a=b c
α=β=900 , 𝛾=1200 SiO2, AgI
α
β
γ
Bravais lattices:
There are 14 Bravais lattices regarding to the seven crystal i.e. 3 Bravais lattices in cubic
system, 2 Bravais lattices in tetragonal crystal system, 4 Bravais lattices in orthorhombic crystal
system, 2 Bravais lattices in monoclinic crystal system, 1 Bravais lattice in triclinic crystal
system, 1 Bravais lattice in trigonal crystal system and 1 Bravais lattice in Hexagonal crystal
system.
1. Cubic crystals:
(i). Simple cubic (ii) Face centred cubic (iii) Body centred cubic
2. Tetragonal crystals:
(i). Simple Tetragonal (ii) Body centred Tetragonal

3. Orthorhombic crystals:
(i). Simple cubic (ii) Face centred cubic (iii) Body centred (iv) Base centred
4. Monoclinic crystals:
(i). Simple Monoclinic (ii). Base centred Monoclinic
5. Triclinic crystals: 6. Trigonal crystals: 7. Hexagonal crystals:
(i). Simple Triclinic (i). Simple Trigonoal (i). Simple Hexagonal
Unit cell Parameters:
1. Nearest neighbor distance:

The distance between centers of two nearest neighboring atoms in a unit cell is called
nearest neighbor distance.
If ‘r’ is the radius of an atom then ‘2r’ is the nearest neighbor distance.
2. Atomic radius:
Half the distance between centers of two nearest neighboring atoms is known as Atomic
radius.
3. Coordination number (CN):
The number of equidistant nearest neighboring atoms around an atom which are
simultaneously in contact with each other is called coordination number.
4. Atomic Packing Factor (APF):
Packing factor is the ratio of volume occupied by the effective number of atoms in a unit
cell to the volume of the unit cell. It is also called as Packing Fraction.
If ‘V’ is the volume of the unit cell and ‘v’ is the volume occupied by the effective
number of atoms in a unit cell then packing fraction is given by,
𝑍𝑣
Packing Factor= 𝑉
Where Z is the effective number of atoms per unit cell
5. Void Space: The empty space among atoms in crystal structure is called Void Space.
𝑉𝑜𝑖𝑑 𝑆𝑝𝑎𝑐𝑒 = 1 − 𝐴𝑃𝐹
6. Density of Unit cell: The ratio of mass of effective number of atoms per unit cell to that
of the volume of unit cell.
𝑍𝑀
Density 𝜌 = 𝑁 3
𝐴𝑎
Where Z= effective number of atoms per unit cell
M= Atomic weight
𝑁𝐴 =Avagadro’s Number
𝑎3 =Volume of the unit cell
Packing Factor of simple cubic (SC) structure:
Fig. (1) shows unit cell of simple cubic structure. In a unit cell, there are eight atoms at
the eight corners and each of them is a member of eight cells. So each atom is considered as 1/8th
atom. Hence the effective number of atoms per unit cell is 1/8*8 =1.i.e.,Z=1
r r
a
fig.(i): Unit cell of Simple cubic structure
In this structure every atom is surrounded by six equidistance nearest neighbors. Hence
coordination number is six. From figure 1, nearest neighbor distance = r+r=2r
Lattice constant a=2r.
Atomic radius r=a/2. ------------ (1)
Coordination number N=6.
We know that,
𝑍𝑣
Packing Factor= 𝑉 ------------------ (2)

Where,
Z=Effective Number of atoms per unit cell
v= volume occupied by the atom
V=Volume of the unit cell.
4
Volume occupied by the atom 𝑣 = 3 𝜋𝑟 3------------------ (3)
and
𝑍 = 1------------------------ (4)
Volume of the unit ell V=𝑎3 ------------------------ (5)
From equations (2), (3), (4) & (5)
4
1. 𝜋𝑟 3
3
Packing Factor APF=
𝑎3
4
𝜋𝑟 3
3
APF= --------------- (6)
𝑎3
From equations (1) & (6)
4
𝜋𝑟 3
3
APF= 8𝑟 3
𝜋
Packing Factor APF= 6
Packing Factor=0.52 (or) 52%----------------------- (7)
Hence in simple cubic crystal structure 52% of volume is occupied by atoms and 48% of volume
is left unoccupied by atoms
Void Space:
By def,
Void Space= 1- APF ----------- (8)
Void Space=1-0.52=0.48
Packing Factor of Body Centred cubic (BCC) structure:
In BCC unit cell, there are eight atoms at the eight corners and each of them is a
member of eight cells. Also, there is one atom at the centered of the body. Hence the effective
number of atoms per unit cell is (8*1/8+1) i.e two atoms per unit cell. Hence Z=2
A A A
√3𝑎 r 2r
C r C
√2𝑎
B B
Fig 2(a): unit cell of BCC Fig 2 (b) Fig 2 (c)
In this structure every atom is surrounded by eight equidistance nearest neighbors. Hence
coordination number is eight. From figures 2(b)& 2(c)

√3𝑎 = 4𝑟
4
Lattice constant a= 𝑟.
√3
√3
Atomic radius r= 4 𝑎. ------------ (1)
We know that,
𝑍𝑣
Packing Factor APF= 𝑉 ------------------ (2)
Where,
Z=Effective Number of atoms per unit cell
4
Volume occupied by the atom 𝑣 = 3 𝜋𝑟 3------------------ (3)
Volume of the unit ell V=𝑎3 ----------------------- (4)
And Z=2-------------------- (5)
From equations (2), (3), (4) & (5)
4
𝐴𝑃𝐹 = 2 × 3 𝜋𝑟 3 /𝑎3 --------------------- (6)
8 𝑟3
𝐴𝑃𝐹 = 𝜋
3 4 3
( 𝑟)
√3
√3𝜋
𝐴𝑃𝐹 =
8
Packing Factor=0.68 (or) 68%
Void Space:
By def,
Void Space= 1- APF ----------- (8)
32% of space is unutilized in BCC.
Packing Factor of Face Centred cubic (FCC) structure:
In this case each unit cell consists of eight corner atoms, each being a member of eight cells.
Moreover there exist six atoms at centers of six faces, each being a member of two cells. Thus
the effective number of atoms per unit cell is 8*1/8+6*1/2 = 4 i.e., atoms per unit cell. Hence
Z=4

r
√2𝑎 2r
r
In this structure every atom is surrounded by 12 equidistance nearest neighbors. Hence

coordination number is 12. From figure 3(b)
√2𝑎 = 4𝑟
4
Lattice constant a= 𝑟.
√2
√2
Atomic radius r= 4 𝑎. ------------ (1)
We know that,
𝑍𝑣
Packing Factor APF= 𝑉 ------------------ (2)
Where,
Z= Effective number of atoms per unit cell
4
Volume occupied by the atom= 3 𝜋𝑟 3------------------- (3)
Volume of the unit ell V=𝑎3 --------------------- (4)
and Z=4 ------------------- (5)
From equations (2), (3), (4) & (5)
4
𝐴𝑃𝐹 = 4 × 3 𝜋(𝑟)3 /𝑎3 ---------------------- (6)
4
4 × 3 𝜋(𝑟)3
𝐴𝑃𝐹 =
4 3
( 𝑟)
√2
√2𝜋
𝐴𝑃𝐹 =
6
Packing Factor APF =0.74 (or) 74% ----------------------------- (7)
Void Space:
By def,
Void Space= 1- APF ----------- (8)
In FCC structure 26% of space is unutilized

Among SC, BCC, FCC, FCC is having less void space
Hence FCC structure is strongly bonded and also called as close packed structure.
Diamond structure:
Diamond structure is the combination of two FCC sub lattices along the body diagonal by
th
¼ cube edge. Fig. 1(a) shows unit cell of diamond cubic structure. In fig. (1), one FCC sub
lattice say ‘x’ has its centre at (0,0,0) and other FCC sub lattice say ‘y’ has its origin at
(a/4,a/4,a/4).fig. 1(b) shows atomic positions in diamond cubic structure.
The points at ‘0’ & ‘1/2’ are on one sub lattice ‘x’ and the points ¼ & ¾ are on another
sub lattice ‘y’. In this structure each corner atom is surrounded by 4 equidistant nearest
neighbors. Hence coordination number is 4. In this unit cell in addition to 8 corner atoms there
are six face centered atoms and four atoms located at middle of the unit cell. Hence the number
1 1
of atoms per unit cell=8 × + × 6 + 4 = 8
8 2
1/2
0 0
3/4 1/2
1/2
y 1/2
0
x
z 1/2 3/4
1/2 0
0
Fig. 1(a) Fig. 1 (b)

y
a/4
X z
a/4 a/4
Fig 1 (c)
Miller indices:
Miller indices are the numbers which are used to designate orientation any plane in crystal
structure. These are represented by h, k, l.
Procedure to obtain miller indices:
1. Find the intercepts of desired plane on three crystallographic axes.
2. As a second step, the reciprocals of intercepts on crystal axes are calculated or taken.

3. In third step, L.C.M of reciprocals of given intercepts on crystal axes is calculated.
4. As a next step, each and every reciprocal of intercept on crystal axes is multiplied by L.C.M.
5. As a last step, the resultant numbers are represented as h, k, l, which are nothing but miller
indices. (h k l) plane represent crystal plane.
IMPORTANCE OF MILLER INDICES:

1. Miller indices represent the plane and all the planes that are parallel to it.
2. Miller indices are used to calculate the spacing ‘d’ between the planes. In cubic system,
𝑎
𝑑= 1
(ℎ2 +𝑘 2 +𝑙2 )2
3. In case of cubic system, the spacing between the planes (100), (110), (111) can be easily
calculated from experiment as
𝑎 𝑎
For simple cubic: d (100) = a, d (110) = , d (111) =
√2 √3
𝑠 𝑠 𝑠
For body centered cubic: d (100) =2, d (110) = , d (111) = 2√3
√2
𝑡 𝑡 𝑡
For face centered cubic: d (100) =2, d (110) =2√2 , d (111) =
√3
Here a, s and t are grating spaces along the principal axes for simple, body centered and face
centered cubic systems respectively.
Example:
1. Let 2, 3, 4 are intercepts on crystal axes.
1 1 1
2. Reciprocals of intercepts 2,3,4 are 2 , 3 , 4
3. The L.C.M of reciprocals of intercepts is 12.
4. Multiply the reciprocal of intercept with L.C.M we get, 6, 4, 3.
5. 6, 4, 3 represents miller indices and (6 4 3) represents crystal plane.
Directions in crystal:
In order to explain directions in crystal, let us consider figure (1). In figure (1), X,Y,Z are
crystallographic axes and a,b,c are the unit vectors along X,Y,Z axes respectively. Let ‘P’ be any
point.
By moving ‘u times ‘a’ along X-axis, ’v’ times ‘b’ along Y- axis, ‘w’ times ‘c’ along Z- axis we
can reach point ‘P’.
Y
P(u,v,w)
𝑣𝑏̅
O
𝑢𝑎̅ 𝑤𝑐̅ X

If u,v,w are the smallest integers then the direction of OP is indicated by [u v w]
Fig. 1(b) shows some important directions in crystal.
[011] [111]
[101]
Interplanar Spacing of an orthogonal crystal systems:

Y
B’
B N
M
β
O A A’
α
γ X
C
C’
Z
Let (h k l) are the miller indices of the plane ABC. Let OM=d is the normal to the plane ABC
and passing through the origin. Let 𝛼,𝛽, 𝛾 are the angles made by OM line with X,Y,Z axis
respectively.
From figure,
𝑑 𝑑 𝑑ℎ
cos 𝛼 = = =
𝑂𝐴 𝑎/ℎ 𝑎
𝑑 𝑑 𝑑𝑘
cos 𝛽 = = =
𝑂𝐵 𝑎/𝑘 𝑎
𝑑 𝑑 𝑑𝑙
cos 𝛾 = = =
𝑂𝐶 𝑎/𝑙 𝑎
We know that,
cos2 α + cos2 β + cos2 γ = 1--------- (2)
From equations (1),(2)

𝑑ℎ 2 𝑑𝑘 2 𝑑𝑙 2
( ) +( ) +( ) =1
𝑎 𝑎 𝑎
2
𝑑
(ℎ2 + 𝑘 2 + 𝑙 2 ) = 1
𝑎2
𝑎2
𝑑2 =
ℎ2 + 𝑘 2 + 𝑙 2
𝑎
𝑑= --------------- (3)
√ℎ2 +𝑘 2 +𝑙2
Equation (3) represents the distance between the plane ABC and origin.
Consider the next plane A’B’C’ at a distance ON=2d from the origin. Its intercepts are,
2𝑎 2𝑎 2𝑎
, , . Hence from equation (3) we can write,
ℎ 𝑘 𝑙
2𝑎
𝑂𝑁 = 2𝑑 = ------------------------- (4)
√ℎ2 +𝑘 2 +𝑙2
From equations (3) and (4),

𝑎
𝑀𝑁 = 𝑂𝑁 − 𝑂𝑀 = 2𝑑 − 𝑑 = ------------------- (5)
√ℎ2 +𝑘 2 +𝑙2
Equation (5) represents distance between two successive planes.
Lattice constant for cubic system:

If a is lattice constant of the cubic crystal and ρ is density of the crystal material then ‘a’
represents the side of unit cell.
Volume of the unit cell = a3
Mass of each unit cell = ρ a3 --------- (1)
𝑀
Mass of each atom =𝑁
𝐴
Here M = atomic weight , 𝑁𝐴 = Avogadro number
If n is number of atoms per unit cell then,
𝑀
Mass of each cell = n x 𝑁 ------------- (2)
𝐴
From equations (1) & (2) we have,
𝑀
ρ a3 = n x 𝑁
𝐴
3 𝑛 𝑀
a =𝜌𝑁
𝐴
𝑛 𝑀 1
a =[ 𝜌 ]3 ------------- (3)
𝑁𝐴

Equation (3) represents lattice constant for cubic crystal.
Defects in Crystals: Perfect crystal: A crystal, in which the atoms are at rest on their correct
lattice positions, is called perfect crystal.
Real crystals are never perfect. They always contain considerable density of defects and
imperfections that affect their physical, chemical, mechanical properties.
Defects: the imperfections in crystal produced due to change in size, change in shape or adding
impurities are called defects in solids.
Imperfections in crystals:
Defects in crystal can be divided into four types. They are,
1. Point defects.
2. Line defects.
3. Surface defects.
4. Volume defects.
1.Point defect: If defect occurs at a certain point then that defect is called point defect. Point
defects are point like regions. further point defects are classified into four types. They are,
I. Vacancies/Schottky defect.
II. Interstitials/Frenkel defect.
III. Compositional defects.
(i) Substitutional impurity.
(ii) Interstitial impurity.
IV. Electronic defects.
Vacancies: a Vacancy refers to an atomic site from where the atom is missing as shown in figure
1(a).
Substitutional impurity: Substitutional impurity is a point imperfection. In Substitutional
impurity, a foreign atom that substitutes for or a parent atom in the crystal as shown in figure
1(b)
Interstitial impurity: in interstitial impurity, a small sized atom occupying the void space in the
parent crystal without disturbing the parent atoms from their regular sites as shown in figure 1(c).
Vacancy parent atom Impurity atom interstitial impurity
Fig 1(a): Vacancy Fig 1(b): Substitutional impurity Fig 1(c): Interstitial impurity
Frenkel Defect:

Frenkel defect occur in ionic crystal only. In ionic crystals, an ion displaced from a
regular site to an interstitial site, is called Frenkel imperfection. Frenkel imperfection is shown in
figure 2(a)
In general, the size of anion is greater than the size of cation. Hence anions do not get displaced
as the void space is just too small for their size. Hence cations displaced to interstitial site (void
space).
Schottky defect:
Schottky defect is also occurring in ionic crystals only. A pair of cation and anion is
missing from an ionic crystal as shown in figure 2(b). Such a pair of vacant sites is called
Schottky imperfections.
Interstitial atom Vacancy Anion and cation vacant sites
Fig 2(a): Frenkel defect Fig 2 (b): 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 corresponds to the exact
stoichiometric formula.
In order to explain electronic defect, let us consider an example of ZnO. In ZnO, the
excess cations occupy interstitial void, while heating the component in Zinc vapour, two
electrons are released from each atom and stay around an interstitial cation as shown fig (3).
Zn2+ O2- Zn2+ 2+

O2- Zn2+ O2- Zn2+ O2-
Zn
O2- Zn2+ O2- Zn2+ O2- Zn2+ O2- Zn2+
Zn2+ O2- Zn2+ O2- Zn2+ O2- Zn2+ O2-
O2- Zn2+ O2- Zn2+ O2- Zn2+ O2- Zn2+
Zn2+ O2- Zn2+ O2- Zn2+ O2- Zn2+ O2-
O2- Zn2+ O2- Zn2+ O2- Zn2+ O2- Zn2+
fig 3: Electronic defect.
Energy of formation of vacancy:

When thermal energy supplied to lattice atoms, then the atoms perform elastic vibrations.
Due to these vibrations, the atoms may jump from normal to interstitial positions. This leads the

formation of vacancies and interstitial imperfections. The number of vacancies is determined by
the temperature, the total number atoms and the average energy required to create a vacancy.
Hence the number of vacancies ‘n’ is given by,
n=f(N,EV,T) --------------- (1)
Where N is the no. atoms
EV is the average energy is required to create a vacancy.
T is temperature
The total number ways in which we can pickup ‘n’ atoms from a crystal consisting of ‘N’
atoms is given by,
𝑁!
𝑤 = (𝑁−𝑛)!𝑛! -------------- (2)
By def., of entropy, increase in entropy is given by,
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 𝑤 --------------- (3)
Where KB is called Boltzmann’s constant.
Equation (3) represents Boltzmann’s law.
From equations (2) & (3), we have,
𝑁!
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛! ] --------- (4)
Change in free energy (F) due to change in entropy is given by,
𝐹 = 𝑈 − 𝑇𝑆 ------------ (5)
Where U is increase in internal energy.
If EV is the energy required to create a vacancy and ‘n’ is the total no. of vacancies then
nEV is the increase in internal energy (U) associated with ‘n’ isolated vacancies in the crystal.
𝑈 = 𝑛𝐸𝑉 --------------- (6)
From equations (4),(5)&(6),
𝑁!
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛!]
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! 𝑛!]
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! − 𝑙𝑜𝑔𝑒 𝑛!]
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − {(𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − (𝑁 − 𝑛)} − {𝑛𝑙𝑜𝑔𝑒 𝑛 − 𝑛}]
[𝑛𝑙𝑜𝑔𝑒 𝑛 − 𝑛 = 𝑙𝑜𝑔𝑒 𝑛!]
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) + (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛 + 𝑛]
𝐹 = 𝑛𝐸𝑉 − 𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛] ----------------- (7)
Free energy is constant at thermal equilibrium. Hence,
𝜕𝐹
(𝜕𝑛) 𝑇 = 0 --------------- (8)
Differentiating the equation (7) with respect to ‘n’ at constant temp.,
𝜕𝐹 −1 1
(𝜕𝑛) 𝑇 = 𝐸𝑉 − 𝑇𝐾𝐵 [−(𝑁 − 𝑛) 𝑁−𝑁 − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)(−1) − 𝑛 𝑛 − 𝑙𝑜𝑔𝑒 𝑛]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑉 − 𝑇𝐾𝐵 [1 + 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 1 − 𝑙𝑜𝑔𝑒 𝑛]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑉 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)− 𝑙𝑜𝑔𝑒 𝑛]

𝜕𝐹 (𝑁−𝑛)
(𝜕𝑛) 𝑇 = 𝐸𝑉 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ------------ (9)
𝑛
(𝑁−𝑛)
𝐸𝑉 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]=0
𝑛
(𝑁−𝑛)
𝐸𝑉 = 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ----------------- (10)
𝑛
Equation (10) represents avg. energy required to create a vacancy in the crystal.
Number vacancies at any temperature:
The average energy of a vacancy in a crystal is given by,
(𝑁−𝑛)
𝐸𝑉 = 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]
𝑛
(𝑁−𝑛) 𝐸𝑉
[𝑙𝑜𝑔𝑒 ]=
𝑛 𝑇𝐾𝐵
𝐸𝑉
(𝑁−𝑛)
= 𝑒 𝑇𝐾𝐵 ---------------- (1)
𝑛
In general, in crystal, the no. of vacancies is much smaller than the total no. of atoms. i.e.,
(𝑁−𝑛) 𝑁
n<<N. hence ≅ hence equation (1) becomes,
𝑛 𝑛
𝐸𝑉
𝑁
= 𝑒 𝑇𝐾𝐵
𝑛
𝐸
𝑛 − 𝑉
=𝑒 𝑇𝐾𝐵
𝑁
𝐸
− 𝑉
𝑛 = 𝑁𝑒 𝑇𝐾𝐵 --------------- (2)
Equation (2) represents the no. of vacancies at any temperature in elemental solids.
Equilibrium concentration of Schottky defects in ionic crystals:
In ionic crystals, Schottky defect is due to missing of a cation-anion pair from crystal. Let
’ES’ be the average energy required to create a Schottky defect and ‘n’ be the no. of Schottky
defects produced by ‘n’ number of pairs. Let ‘N’ be the total no. of cation-anion pairs.
The total number of ways to pickup ‘n’ pairs from ‘N’ pairs is given by
𝑁!
𝑤 = [(𝑁−𝑛)!𝑛!] 2 -------------- (1)
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 𝑤 --------------- (2)
Where KB is called Boltzmann’s constant.
Equation (2) represents Boltzmann’s law.
𝑁!
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛!] 2
𝑁!
𝑠 = 2𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛! ]------------------ (3)
𝐹 = 𝑈 − 𝑇𝑆 ------------ (4)
By def., internal energy,
𝑈 = 𝑛𝐸𝑆 --------------- (5)
𝑁!
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛!]
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! 𝑛!]
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! − 𝑙𝑜𝑔𝑒 𝑛!]
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − {(𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − (𝑁 − 𝑛)} − {𝑛𝑙𝑜𝑔𝑒 𝑛 − 𝑛}]
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) + (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛 + 𝑛]
𝐹 = 𝑛𝐸𝑆 − 2𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛] ----------------- (6)
𝜕𝐹
(𝜕𝑛) 𝑇 = 0 --------------- (7)
𝜕𝐹 −1 1
(𝜕𝑛) 𝑇 = 𝐸𝑆 − 2𝑇𝐾𝐵 [−(𝑁 − 𝑛) 𝑁−𝑁 − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)(−1) − 𝑛 𝑛 − 𝑙𝑜𝑔𝑒 𝑛]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑆 − 2𝑇𝐾𝐵 [1 + 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 1 − 𝑙𝑜𝑔𝑒 𝑛]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑆 − 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)− 𝑙𝑜𝑔𝑒 𝑛]
𝜕𝐹 (𝑁−𝑛)
(𝜕𝑛) 𝑇 = 𝐸𝑆 − 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ------------ (8)
𝑛
(𝑁−𝑛)
𝐸𝑆 − 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]=0
𝑛
(𝑁−𝑛)
𝐸𝑆 = 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ----------------- (9)
𝑛
Equation (9) represents avg. energy required to create a Schottky defect in the crystal.
From equation (9) we have,
(𝑁−𝑛)
𝐸𝑆 = 2𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]
𝑛
(𝑁−𝑛) 𝐸
[𝑙𝑜𝑔𝑒 ] = 2𝑇𝐾𝑆
𝑛 𝐵
𝐸𝑆
(𝑁−𝑛)
=𝑒 2𝑇𝐾𝐵
---------------- (10)
𝑛
In general, in crystal, the no. of Schottky defects is much smaller than the total no. of
(𝑁−𝑛) 𝑁
atoms. i.e., n<<N. hence ≅ hence equation (10) becomes,
𝑛 𝑛
𝐸𝑆
𝑁
=𝑒 2𝑇𝐾𝐵
𝑛
𝐸𝑆
𝑛
= 𝑒 2𝑇𝐾𝐵
𝑁
𝐸𝑆
𝑛 = 𝑁𝑒 2𝑇𝐾𝐵 --------------- (11)
Equation (11) represents no. of Schottkey defects in crystal at any temperature. Or
Equilibrium concentration of Schottkey defects in ionic crystals.

Equilibrium concentration of Frenkel defects in ionic crystals:
Let in crystal, N be the total no. of atoms,’Ni’ be the interstitial atoms, ‘n’ be the no. of
Frenkel defects, then the total no. of ways in which ‘n’ frenkel defects can be formed is,
𝑁! 𝑁𝑖!
𝑤 = [(𝑁−𝑛)!𝑛! . (𝑁𝑖−𝑛)!𝑛!] -------------- (1)
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 𝑤 --------------- (2)
Where KB is called Boltzman’s constant.
Equation (2) represents Boltzman’s law.
𝑁! 𝑁𝑖!
𝑠 = 𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛! . (𝑁𝑖−𝑛)!𝑛! ] --------- (3)
𝐹 = 𝑈 − 𝑇𝑆 ------------ (4)
By def., internal energy,
𝑈 = 𝑛𝐸𝑓 --------------- (5)
𝑁! 𝑁𝑖!
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 𝑙𝑜𝑔𝑒 [(𝑁−𝑛)!𝑛! . (𝑁𝑖−𝑛)!𝑛!]
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 {[𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! 𝑛!] + [𝑙𝑜𝑔𝑒 𝑁𝑖! − 𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)! 𝑛!]}
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 {[𝑙𝑜𝑔𝑒 𝑁! − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)! − 𝑙𝑜𝑔𝑒 𝑛!] + [𝑙𝑜𝑔𝑒 𝑁𝑖! − 𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)! − 𝑙𝑜𝑔𝑒 𝑛!]}
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 {[𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − {(𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − (𝑁 − 𝑛)} − {𝑛𝑙𝑜𝑔𝑒 𝑛 − 𝑛}] +
[𝑁𝑖𝑙𝑜𝑔𝑒 𝑁𝑖 − 𝑁𝑖 − {(𝑁𝑖 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛) − (𝑁𝑖 − 𝑛)} − {𝑛𝑙𝑜𝑔𝑒 𝑛 − 𝑛}]
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 {[𝑁𝑙𝑜𝑔𝑒 𝑁 − 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) + (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛 + 𝑛] +
[𝑁𝑖𝑙𝑜𝑔𝑒 𝑁𝑖 − 𝑁𝑖 − (𝑁𝑖 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛) + (𝑁𝑖 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛 + 𝑛]}
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 {[𝑁𝑙𝑜𝑔𝑒 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛] + [𝑁𝑖𝑙𝑜𝑔𝑒 𝑁𝑖 − (𝑁𝑖 −
𝑛)𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛) − 𝑛𝑙𝑜𝑔𝑒 𝑛]}
𝐹 = 𝑛𝐸𝑓 − 𝑇𝐾𝐵 [𝑁𝑙𝑜𝑔𝑒 𝑁 − (𝑁 − 𝑛)𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 2𝑛𝑙𝑜𝑔𝑒 𝑛 + 𝑁𝑖𝑙𝑜𝑔𝑒 𝑁𝑖 − (𝑁𝑖 −
𝑛)𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)] ------------------ (6)
𝜕𝐹
(𝜕𝑛) 𝑇 = 0 --------------- (7)
𝜕𝐹 −1 1 −1
(𝜕𝑛) 𝑇 = 𝐸𝑓 − 𝑇𝐾𝐵 [−(𝑁 − 𝑛) 𝑁−𝑁 − 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)(−1) − 2𝑛 𝑛 − 2 𝑙𝑜𝑔𝑒 𝑛 − (𝑁𝑖 − 𝑛) 𝑁𝑖−𝑁 −
𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)(−1)]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑓 − 𝑇𝐾𝐵 [1 + 𝑙𝑜𝑔𝑒 (𝑁 − 𝑛) − 2 − 2 𝑙𝑜𝑔𝑒 𝑛 + 1 + 𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)]
𝜕𝐹
(𝜕𝑛) 𝑇 = 𝐸𝑓 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)− 2𝑙𝑜𝑔𝑒 𝑛 + 𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)]

𝜕𝐹
) = 𝐸𝑓 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 (𝑁 − 𝑛)− 𝑙𝑜𝑔𝑒 𝑛2 + 𝑙𝑜𝑔𝑒 (𝑁𝑖 − 𝑛)]
(
𝜕𝑛 𝑇
𝜕𝐹 (𝑁−𝑛)(𝑁𝑖−𝑛)
(𝜕𝑛) 𝑇 = 𝐸𝑓 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ------------ (8)
𝑛2
(𝑁−𝑛)(𝑁𝑖−𝑛)
𝐸𝑓 − 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]=0
𝑛2
𝐸𝑓 = 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ] ----------------- (10)
𝑛2
Equation (10) represents avg. energy required to create a Frenkel defect in the crystal.
From equation (10) we have.
𝐸𝑓 = 𝑇𝐾𝐵 [𝑙𝑜𝑔𝑒 ]
𝑛2
(𝑁−𝑛)(𝑁𝑖−𝑛) 𝐸𝑓
𝑙𝑜𝑔𝑒 = 𝑇𝐾
𝑛2 𝐵
𝐸𝑓
= 𝑒 𝑇𝐾𝐵 ---------------- (11)
𝑛2
(𝑁−𝑛) 𝑁 (𝑁𝑖−𝑛) 𝑁𝑖
if n<<N then ≅ & ≅ hence equation (11) becomes,
𝑛 𝑛 𝑛 𝑛
𝐸𝑓
𝑁 𝑁𝑖
= 𝑒 𝑇𝐾𝐵
𝑛 𝑛
𝐸𝑓
𝑁𝑁𝑖
=𝑒 𝑇𝐾𝐵
𝑛2
𝐸𝑓
2
𝑛 = 𝑁𝑁𝑖𝑒 𝑇𝐾𝐵
𝐸𝑓
1⁄ 2𝑇𝐾
𝑛 = (𝑁𝑁𝑖) 2𝑒 𝐵
Equation (2) represents the Equilibrium concentration of Frenkel defects in ionic crystals.
2.Line defects:
If defects occurs along a line are called line defects. Line defects are one dimensional defect.
Line defects can also be called as dislocations.
A dislocation may be defined as a disturbed region between two substantially perfect parts of
a crystal. It arises due to a part - plane of atoms is displaced from its symmetrically stable
positions in the array. Line defects are classified into two types. They are,
a. Edge dislocation.
b. Screw dislocation.
a). Edge dislocation: In a perfect crystal, the atoms are arranged in both vertical and horizontal
planes parallel to the side faces as shown in figure 1(a). If one of these vertical planes does not
extend to the full length, but it ends in between, within the crystal as shown in figure 1(b). it is
called edge dislocation.

Fig 1 (a): Perfect Crystal Fig 1(b) : Crystal with Edge Dislocation
X Q Q1 Y
Fig. 1(c): +ve and –ve edge dislocations

Just above the discontinuity the atoms are squeezed and are in a state of compression.
Just below the discontinuity, the atoms are pulled apart and are in a state of tension. This type of
dislocation is called edge dislocation.
This distorted configuration extends all along the edge into the crystal. There is an extra
energy due to the distortion in the region immediately surrounding the edge of the incomplete
plane.
If one of the plane of atoms glides over another separated by integral multiples of
interatomic distance, is called slip. Slip plane is the plane in which slip has taken.
If the incomplete extra plane is above the slip plane then the edge dislocation is positive
and is represented by ‘┬’ as shown in figure 1(c)

If the incomplete extra plane is below the slip plane then the edge dislocation is negative
and is represented by ‘┴’. as shown in figure 1(c)
Burgers vector: The magnitude and direction of the displacement are measured by a vector
called the Burgers vector.
P Q P
Fig 2 (a): Perfect Crystal Fig 2(b) : Crystal with Edge Dislocation
In order to explain burgers vector, let us consider two crystals one perfect and another with edge
dislocation as shown in fig. 2(a) & 2(b) respectively. In figure 2(a), starting from point ‘P’ we
go up 6 steps. Then move towards right by 5 steps and move towards down by ‘6’ steps finally
towards left by ‘5’ steps to reach starting point ‘P’ then the Burgers circuit gets closed. When the
same operation is performed on figure 2(b), now we have to move an extra step QP-1 to return to
‘P’ in order to close 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.
b). Screw dislocation: A screw dislocation marks the boundary between spitted and un spitted
parts of the crystal. It can be produced by cutting crystal partly and shearing down one part
relative to the other by one atomic spacing line of distortion, called screw dislocation line, exists
along the edge of the cut.
C D
Fig. 2(c) :Screw Dislocation

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 as shown in figure 2(c).

The plane ABCD is slipped area. AD is dislocation line. The name screw dislocation follows the
new character of atomic plane which are transferred. Such that as one moves around the
dislocation line in Burgers circuit.
X- Ray Diffraction
Diffraction: When light falls on obstacle or aperture whose size is comparable with wavelength
of light then light bends at corners of the obstacle or aperture. This phenomenon is called
diffraction.
Bragg’s Statement: It states that, the X – Rays reflected from atoms indifferent parallel planes
of a crystal interfere constructively when the path difference is an integral multiple of
wavelength of X - Rays.
Bragg’s law : In order to derive Bragg’s law, let us consider two successive lattice planes PQ
and RS which are separated by a distance ‘d’ as shown in fig(3). Let ‘θ’ is angle of glancing. Let
us suppose a beam of X-rays is incident on two planes. AB,DE are two rays incident on
successive planes and BC,EF are the two rays which are reflected from atomic planes PQ and RS
due to the close arrangement of atoms in a crystal. As the atoms are kept close to each other in a
crystal, X-ray diffraction is appeared as reflection.
BG, BH are the normal’s drawn from ‘B’ to DE,EF respectively. The path difference
between the two rays reflected from PQ and RS is,
From fig (3), we have
∆= GE + EH ______(1)
From Δle BGE Reflected X - Rays
Incident X - Rays
A C
D F
θ B
P Q
d G
θ θ
H
R E S
Fig. (3): Diffraction of X – Rays by crystal planes
𝐺𝐸 𝐺𝐸
Sinθ = 𝐵𝐸 = 𝑑
GE = d sinθ
From Δle BHE
𝐸𝐻 𝐸𝐻
Sin𝜃 = 𝐵𝐸 = 𝑑
EH = dsinθ
Keeping these values in equations (1) we get,

∆= dsinθ + dsinθ
∆= 2dsinθ _____(2)
But the condition for maximum is
diffraction path ∆ = nλ _______ (3)
From equations (2) & (3) we get,
2dsinθ = nλ _______ (4)
Equation (4) represents Bragg’s law.
From Bragg’s law we can write,
.λ=2d100 sinθ1=2d110 sinθ2=2d111 sinθ3
1 1 1
: : = sin θ1 : sin θ2 : sin θ2 ___________ (5)
𝑑100 𝑑110 𝑑111
1 1 1
The ratios 𝑑 :𝑑 :𝑑 for different cubic lattice are given below.
100 110 111
1 1 1
: :
𝑑100 𝑑110 𝑑111
Simple cubic √1 : √2 : √3
1
Body centred cubic √1 :√2 : √3
√3
Face centred cubic √1 : √2 : 2
X-ray diffraction by Laue’s method :

Laue’s method is used to study the crystal structure of single crystal. The experimental
arrangement of Laue’s method is shown in fig.(1).
Single
crystal
Collimator
D
Diffraction pattern due to transmission method
Diffraction pattern due to back reflection method

fig.(1)
This method is used to study the crystal orientation and to verify the crystal symmetry.

This method is applicable for stationary single crystal in this we use white x-ray
radiation.
In this method a beam of white x-radiation is collimated through collimator(c).The white
x-rays fall on the stationary crystal. The Bragg’s angle θ is therefore fixed for every set of planes
in crystal. Now, each set of planes selects and diffracts a particular wavelength that satisfies the
Bragg’s law for particular values of dhkl and θ. Therefore we get a diffracted beam each
corresponding to one set of planes for a particular wavelength. The diffracted pattern caught on
the photographic film.
Laue pattern can be obtained either in transmission or back reflection method. In
both ways diffracted beams gives a series of spots on the film. The spots are obseved on the
curves.
In transmission Laue pattern, these curves are either Ellipses or Hyperbolas and for
back reflection method these are Hyperbolas.
𝑟
The Bragg angle for any transmission laue spot is given by the relation Tan2θ = 𝐷1.
Where r1-Distance between centre of film and diffraction spot,
D-Distance between specimen and film.
Laue spots near the centre of the film correspond to the first order reflections from planes
inclined at very small angles to incident light. In this case only lower wavelengths can satisfy
Bragg’s condition. As we moves towards the centre of the laue pattern, the corresponding values
of θ decreases at the same time the indices of planes hkl increases and dhkl decreases.
In the case of back reflection pattern the bragg’s angle for any spot may be obtained by,
𝑟
Tan (180-2θ) = 𝐷2.
X-ray diffraction – Powder method(Debye-Scherrer method):
The powder method is used to study crystal structure of crystalline powder or to a very
fine grained polycrystalline specimen. This method is used to determine the lattice parameters of
crystals of known structure. The powder specimen is kept inside a small capillary tube. A narrow
pencil of monochromatic X – Rays is diffracted from the powder and recorded by photographic
film as a series of lines of varying curvature.
The camera used in this method is Debye Scherrer camera. It consists of cylindrical
cassette. A strip of photographic film is positioned around the circular periphery of cassette. The
powder specimen is placed at the center. The X – Ray beam enters through a small hole in the
camera and falls on the powder specimen. Some part of the beam is diffracted by the powder
while remaining passes through the exit port.
In the powder, large number of crystals are randomly oriented. Hence set of planes which
make an angle ‘θ’ with incident beam can have a number of possible orientations. Hence
reflected radiations lies on the surface of the cone. If all the crystal planes of interplanar spacing
‘d’ reflects at the same angle ‘θ’, all reflections from a family lie on the same cone. Hence ‘d’
can have different combinations and accordingly different θ values satisfy Bragg’s law. Let us
take n=1 in Bragg’s equation. Hence many cones of reflection are emitted by powder specimen.

In the powder camera a part of each reflected cone is recorded by the film strip in cylindrical
cassette. The recorded lines from any cone are a pair of arcs that form part of the circle of
intersection. The full opening angle of the diffracted cone is 4θ is determine by measuring the
distance ‘S’ between two corresponding arcs on the powder photographs.
The distance S on the film between two diffraction lines corresponding to particular
𝑆
plane related to Bragg’s angle is given by 4𝜃 = 𝑅 radians. R is radius of the camera
Exit beam
film
incident beam Specimen
fig.(1)
Fig. (2):
Applications of X- ray diffraction:
1. Laue diffraction method:
Laue method is used for mounting the single crystals in a known orientation. It is very
much useful for study of crystal symmetry.
2. Powder diffraction method:
Powder diffraction method is used to find the interplanar distance between the layers in
crystal.
3. Study of mixtures:
If a mixture is used for the study, measuring the relative intensities of non overlapping
lines the relative concentration of each component can be obtained.
4. Study of alloys:
If an alloy is used for the study, for uniform composition a typical powder diffraction
pattern is produced. If one of the components precipitates, separate lines corresponding to
that component is observed.
5. Stress determination in metals:
If there is a stress in a metal, it changes the d- spacing. This results in change of angle of
diffraction core. By measuring this change, accurate measurements of stress is possible.
6. Determination of particle size:
When the size of the crystallite decreases, the angular speed of X- ray diffraction
increases. Hence width of the observed diffraction pattern also increase. By measuring
the full width at half maximum, the mean particle size of the sample can be measured.
7. Rotating crystal method is generally used to align the crystals and measure lattice
parameters and determine the crystal structure.
UNIT – II
DIELECTRIC PROPERTIES
 Introduction:
Dielectrics are insulating materials. In dielectrics all the electrons are bound to their molecules
and there are no free charges. Even with normal voltage or thermal energy electrons are not
released. Dielectrics are non- metallic materials of high specific resistance and have negative
temperature coefficient of resistance.
 Some Important Definitions:
Electric Dipole: Two equal and opposite charges separated by a distance constitute a electric
dipole as shown in figure.
Fig: Electric dipole

Dipole Moment: (  ): The product of charge and distance between two charges is called dipole
moment.
i.e.  =qd.
Units: Coulomb-meter ( or ) Debye
Dielectric Constant: ( r )
The dielectric characteristics of a material are determined by the dielectric constant or relative
permittivity ‘ r ’ of that material. Dielectric constant is the ratio between the permittivity of the
medium and the permittivity of free space.
 C
i.e. r   .
0 C0
Units: - No Units
Where  is permittivity of the medium, 0 is permittivity of the free space

C is capacitance of a capacitor with dielectric and
C0 is capacitance of a capacitor without dielectric.
Polarizability: ( ' ' )

When the strength of the electric field ‘E’ is increased the strength of the induced dipole  also
increases. Thus the induced dipole moment is proportional to the intensity of the electric field.
i.e.    E .
α = µ/E
Where ' ' the constant of proportionality is called Polarizability. It can be defined as induced
dipole moment per unit electric field.
Electric Susceptibility:  xe 
The polarization vector ‘P’ proportional to the total electric flux density D and is in the same
direction of E.
The polarization vector can be written as
P 0 xe E.
Where the constant xe is the electric susceptibility
xe  r 1
Displacement vector or Electric displacement:
The electric flux density or electric displacement D at a point in a material is given by
 
D=  E  r  
 0 
D= r 0 E
When ‘E’ is the electric field strength, 0 is the dielectric constant or permittivity of free space
and r is the relative dielectric constant or relative permittivity of the material
D= 0 E  p
Since D= r 0 E
r 0 E = 0 E  p  P 0 r 1 E
Polarization Vector ( p ) :
The dipole moment per unit volume of the dielectric material is called polarization vector p . If
 is the average dipole moment per molecule and ‘N’ is the number of molecules per unit
volume.
The polarization vector ( p ) = N  .
Electric Polarization:
The process of producing electric dipoles by an electric field is called polarization in dielectrics.
When an electric field is applied to a crystal or a glass containing positive and negative charges
the positive charges are displaced in the direction of the field, where the negative charges are
displaced in the opposite direction. This displacement produces local dipoles throughout the
solid.
 Measurement of Relative Dielectric Constant:
The polarization or the relative dielectric constant can be measured using parallel plate capacitor.
When a voltage ‘V’ is applied to the capacitor, with the plates separated by vacuum, charge
develops on the plates.
The capacitance of the capacitor without dielectric.

 A
C 0
d
Where ‘A’ is the area of the parallel plates.
‘d’ is the distance between the two plates.
If a dielectric material is inserted between the plates, the charge on the plates increases due to
polarization in the material
The capacitance of the capacitor with a dielectric material is given by
 A
C1  0 r
d
The relative dielectric constant can be found by taking the ratio C1 to C
Hence Ɛr = C1/C
 Polarization Processes:
Polarization occurs due to several atomic mechanisms. When the specimen is placed inside a d.c.
electric field, polarization is due to 4 types of processes.
a) Electronic Polarization
b) Ionic Polarization
c) Orientation Polarization
d) Space charge Polarization.
a) Electronic Polarization:
The displacement of the positively charged nucleus and the negative electrons of an atom in
opposite directions under the action of an electric field is called electronic polarization. On
applying the electric field, the electron cloud around the nucleus shift towards the positive end of
the field. Then the nucleus and centre of electron cloud are separated by a certain distance. As a
result, a dipole moment is created in each atom. The number of dipoles generated is proportional
to applied electric field.
 e E
e   e E .
Where  e is the electronic Polarizability. It is independent of temperature.
A simplified classical model of an atom is shown in below fig (a). Here the nucleus of charge Ze
is surrounded by an electron cloud of charge -Ze distributed in a sphere of radius ‘R’

Fig: Electric polarization
The charge density ‘  ’ is given by (charge per volume )
 Ze

4 3
R
3
−3𝑍𝑒
=
4𝜋𝑅 3
When the system is subjected to an external applied field of intensity E, the nucleus and electron
experience Lorentz forces of magnitude F=ZeE in opposite directions Therefore the nucleus and
electron cloud are pulled apart as shown in fig (a) when they are separated a coulomb force
develops between them, which tends to oppose the displacements. When these forces namely
Lorentz force and Coulomb force are equal and opposite, an equilibrium is reached.
Let us assume the displacement be ‘x’
Lorentz force = -ZeE
𝐶ℎ𝑎𝑟𝑔𝑒 𝑒𝑛𝑐𝑙𝑜𝑠𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑠𝑝ℎ𝑒𝑟𝑒 𝑜𝑓 𝑟𝑎𝑑𝑖𝑢𝑠 𝑥
Coulomb force = Ze X 4𝜋 𝜀0 𝑥 2
4
Charge enclosed is   x 3 
3
4 3  3  ze  
=  x   3 
3  4   R 
 zex3
= .
R3
ze   zex3 
4 0 x 2  R3 
Hence Coulomb force is =
 z 2e2 x
=
4 0 R3
In the equilibrium position
 z 2e2 x
 zeE  E
4 0 R3

zex
E= .
4 0 R 3
4 0 R3
X= E.
ze
Thus the displacements of the electron cloud are proportional to the applied field. Thus the two
electric charges +Ze and –Ze are separated by a distance ‘x’ under the action of the applied field
thus constituting induced electric dipoles.
Induced electric dipole moment e  zex
4 0 R3
= ze E
Ze
e  4 0 R 3 E
 e   e E .
Where  e  4 0 R 3 is called electronic Polarizability. The dipole moment per unit volume is
called polarization.
Pe  N e  Ne E.
Where ‘N’ is number of atoms/m3.
P  N e E
e
We know the Pe 0 (r 1) E

N e
N e E 0 r 1 E r 1  .
0
r 1 0
Hence  e  .
N
(b) Ionic Polarization:
The Ionic Polarization is due to the displacement of cations and anions in opposite directions and
occurs in an ionic solid as shown in figure (b). Suppose an electric field is applied in the +ve X-
direction. The positive ions moved to the right by x1 and the negative ions move to the left by x2.
Assuming that each unit cell has one cation and one anion, the resultant dipole moment per unit
cell due to ionic displacement is given by
  e( x1  x2 ).
If 1 and  2 are restoring force constants of cation and anion and F Newton’s is the force due to
the applied field.
F= 1 x1   2 x2
F
Hence x1 
1

Fig: Ionic Polarization
Restoring force constants depend upon the mass of the ion and angular frequency of the
molecule in which ions are present.
eE
Then x1 
m02
eE
x2 
M 02
Where ‘M’ is the mass of the anion
eE  1 1 
 x1  x2  2   
w0  M m 
And   e  x1  x2 
 eE  1 1 
  
e w02  M m 
e2 E  1 1 
  2   
w0  M m 
We know that the dipole moment per unit electric field is called Polarizability
 e2  1 1 
i   
E w02  M m 
Thus the ionic Polarizability is inversely proportional to the square of the natural frequency of
1
 1 1
the ionic molecule and to its reduced mass which is equal to   
M m
(c) Orientation polarization:
Orientation polarization occurs in polar dielectrics i.e. in molecules with permanent dipole
moment. In methane molecule, the centre of the –ve and +ve charges coincide, so that there is no
permanent dipole moment. On the other hand, in certain molecules such as CH3Cl, the positive
and negative charges do not coincide.
In this molecule Cl atom pulls the bonding electrons to itself more strongly than hydrogen. In the
absence of an electric field, this molecule carries a dipole moment. When an electric field is
applied on such molecules which possess permanent dipole moment, they tend to align
themselves in the direction of applied field as shown in fig©.

Fig: Orientation Polarization
The polarization due to such alignment is called orientation polarization and is dependent on
temperature. When the temperature is increases the thermal energy tends to randomize the
alignment.
Orientation polarization can be represented as Po  N 
2E
=N
3KT
=N  o E
P0 2
o  
NE 3KT
Thus the orientation Polarizability is inversely proportional to temperature of the material.
 Internal Fields in Solids (Lorentz Method): or Local field in dielectrics

Let a dielectric be placed between the plates of a parallel plate capacitor and let there be an
imaginary spherical cavity around the atom ‘A’ inside the dielectric as shown in figure. It is also
assumed that the radius of the cavity is large compared to the radius of the atom.
The internal field at the atom site A can be considered to be made up of the following four
components namely E1 , E2 , E3andE4 .
Fig: Calculation of internal field for a cubic structure

FIELD E1:
E1 is the field intensity at A due to the charge density on the plates
D
E1 
0
We know that D  P  0 E
P  0 E p
 E1   E       (1)
0 0
FIELD E2:
E2 is the field intensity at A due to the charge density induced on the two surfaces of the
dielectric.
P
E2  ---------(2)
0
FIELD E3:
E3 is the field intensity at A due to other atoms contains in the cavity. We are assuming a cubic
structure, so E3=0 because of symmetry.
FIELD E4:
E4 is the field intensity due to polarization charges on the surface of the cavity and was calculated
by Lorentz as shown in the figure.
Fig: Cavity enlarged

In the above figure, If dA is the surface area of the sphere of radius ‘r’ lying between  and
θ + dθ where θ is the angle with reference to the direction of applied force.
Then dA = 2  PQ  QR 
But S in  =PQ/ r PQ = r S in 
QR  rd .
 dA  2 r 2 sin  d .

The charge dq on the surface dA is equal to the normal component of the polarization multiplied
by the surface area.
 dq  dA.P cos 
dq = p( 2 r 2 sin  cos  d )
The field due to this charge at A denoted by dE4 in the direction  =0 is
dq  1 cos 
dE4=
4 0 r 2
P cos  2 r 2 sin  cos  d
=
4 0 r 2
p
= cos 2  sin  d
2 0
Thus the total field E4 due to the charges on the surface of the entire cavity is obtained by
integrating

P
 dE4  
2 0 0
cos 2  sin  d
1
P
E4   x  dx 
2
2 0 1
3 1
P x 

2 0  3 
P 1 1  P  2  P
=-
2 0  3  3   2   3   3 
0 0
 E  E1  E2  E3  E4 .
Substitute E1 , E2 , E3 & E4 values we get the Local field
This equation is known as Lorentz relation or local field or internal field. And it should
observe that the local field is greater them the applied electric field.

 Clausius – Mosotti Equation:
Consider the elemental dielectrics which have cubic structures since there are no ions and
permanent dipoles in these materials.
i  0  0
Where  i  ionic Polarizability
 0  Orientation Polarizability
Hence polarization
 N e 
P 1    N e E
 3 0 
N e E
P=    (1)
N e
1
3 0
N e N e E
1  .
3 0 P
We know that
D  P  0 E
P  D  0 E
P
  0
E
P
0r  0 0 r 1
E
 P  E 0 0 1      (2)
From (1) & (2) Equations.

N e E
 E 0 r 1
N e
1
3 0
N e N e
1 
3 0 0 r 1
 
N e  1 
1 1  
3 0  r 1 
 3 
N e  3 
1 1  
3 0  r 1 
N e  1
i.e.  r
1
3 r 2
r 1
  1  N e
Thus  r 
 r 2  3 0
Where ‘N’ is the number of molecules per unit volume. The above relation is known as Clausius
– Mosotti equation.
 Piezo – Electricity:
The materials which have the property of becoming electrically polarized when mechanical
stress is applied are called piezoelectricity. Piezoelectricity refers to the creation of opposite
kinds of charges at one pair of opposite faces of the piezo electric crystal. Thus it reflects to the
development of e.m.f. through dielectric polarization by the application of mechanical force.
It has an inverse. According to inverse piezo electricity when an electric voltage is applied, the
material become strained. The strain is directly proportional to applied p.d. All ferroelectric
crystals exhibit the piezo electricity but all piezo electric materials need not exhibit
ferroelectricity.
 Piezo electric materials are very important to the conversion of the mechanical energy into
electrical energy and vice-versa.
Ex:-Quartz, lithium Niobate and BaTiO3
Applications:-
 Single crystal of quartz is very widely used for filter, resonator and delay line
applications.
 Rochelle salt is used as transducer in graphite pick-ups, ear phones, hearing aids,
microphones etc.
 The commercial ceramic materials are based on barium titanate, lead zirconate. They are
used for high voltage generation transducers.
 Piezo electric semiconductors such as GaS, ZnO are finding applications as amplifiers of
ultrasonic waves.
 Pyro- electricity:
Pyroelectric effect is the change in spontaneous polarization when the temperature of the
specimen is changed. The Pyroelectric coefficient λ is defined as the change in polarization per
unit temperature change of the specimen.
λ = dP / dT
Change in polarization results in change in external field and hence charge on the surface. As it
is possible to detect a charge of 10-16 coulomb with a suitable electrometer, temperature changes
as small as 10-6 oC can be measured using the Pyroelectric effect.
Applications:
 The Pyroelectric materials such as BaTiO3, LiNbO3 etc are used to make very good
infrared detectors which can operate at room temperatures.
 Materials such as TGS, NaNO2 and PZT ceramics are used in the construction of
Pyroelectric image tubes.
 Ferro– Electricity:
The dielectric materials which are having spontaneous polarization in the absence of electric
field are called ferroelectric materials. And the phenomenon of possessing spontaneous
polarization in the absence of electric field is called ferroelecricity
Eg: - Rochelle salt (NaKc4H4O6, 4H2O), Barium titanate (BaTiO3-) etc.,
Properties:
1. All ferroelectric materials possess spontaneous polarizations below a certain temperature.
2. As temperature increases the spontaneous polarization decreases and at a particular
temperature, the spontaneous polarization vanishes. This temperature is known as Curie
temperature.
3. At which temp the ferroelectric materials converts into paraelectric materials that temp is
called Curie temperature.
4. Above Curie temperature, dielectric constant varies with temperature according to curie-
weiss law .
𝐶
𝜀𝑟 =
𝑇 − 𝑇𝑐
5. All ferroelectric materials exhibit the property piezo-electricity and Pyroelectricity.

6. Hysteresis:-
When electric field is applied on a ferroelectric material then polarization takes place .This
polarization always lags behind the applied electric field. This phenomenon is known as
hysteresis of a ferroelectric material. The hysteresis loop between polarization and electric field
is as shown in figure

7. The hysteresis loop area represents the dielectric loss that occurs in dielectric materials.
8. The spontaneous polarization of the ferroelectric material depends upon
(i) Shape of the hysteresis loop
(ii) The thermal and electrical properties of the crystal.
(iii) Temperature
Applications:
The ferroelectric materials are used as high permeability materials in
 Magnetic amplifiers and dielectric amplifiers
 Magnetic information storage devices.
 Magnetostrictive transducers.
 Used in the construction of memory devices used in computers.
 The ferroelectric materials show piezoelectric property, so they are used in produce and
detect sound waves.
 They shows piezoelectric property, so they are used to detect infrared radiation
UNIT III
MAGNETIC PROPERTIES
 Introduction:
Magnetic materials play an important role in industrial and scientific research fields. The
magnetism of materials is mainly due to the interactions of uncompensated magnetic
moments of the constituent atoms or molecules.
Many of our modern technological devices rely on the behavior of magnetic materials, such
devices include electric motors, electrical power generators, transformers, radio, television,
telephones, computers, components of audio and video recording and reproduction systems.
These are mainly used in information storage devices.
 Some Important Definitions:
Magnetism:
The attracting property exhibited by the magnet is known as magnetism.
Magnetic dipole:
A magnet consists of north and south poles. Any two opposite poles of a magnet separated by
a finite distance constitute a magnetic dipole.
Magnetic moment:
If m is the magnetic pole strength and 2l is the length of the magnet then

i.e. µm = 2lm ampere-m2
Where m is the pole strength and ‘2l’ is the distance between North Pole and South Pole of the
magnet.
( or )
When an electric current (I) flows through a circuit wire of one turn having an area of cross
section A. it is said to have a magnetic moment
i.e. µm = I.A Ampere-meter2
it is a vector quantity.
Magnetic induction (B): or magnetic flux density
It is defined as the number of lines of magnetic lines of forces passing through an unit area of
cross section of material
𝜙
B=𝐴 where 𝛟 magnetic flux
A area of cross section
2
Units are Weber/m or Tesla or Gauss
1 Tesla = 104 Gauss
( or )
It is the force experienced by unit north pole placed at a given point in a magnetic field.
𝐹
B=𝑚 units Newton/ A.m
Intensity of magnetization (M):
When a material is magnetized, it develops a net magnetic moment then the developed magnetic
moment per unit volume is given as intensity of magnetization.
M = Magnetic moment/volume
µm
M= 𝑉
Units:- ampere/m
Magnetic field intensity or magnetic field strength (H):
It is defined as the ratio between the magnetic induction and the permeability of the medium in
which the magnetic field exists at any point in a magnetic field is the force acting on unit north
pole placed at that point.
B 𝐹
H= = µm

Units: Ampere/ meter.
Magnetic Permeability:
It is defined as the ratio of the magnetic field induction to the applied magnetic field strength
B
=
H
i.e B =  H
B = µ0H
Where 0 is the permeability of free space

The permeability of free space value is 4 107 henry/m
Instead in vacuum,
if the field is applied in a medium, the magnetization in the solid is given by
B= H
Where  is the permeability of the solid material
B
=
H
Hence the magnetic permeability of any material is the ratio of the magnetic induction in the
sample to the applied magnetic field intensity
Relative permeability (µr):
The ratio of permeability of a material to the permeability of free space.

r 
0
No units.
Magnetic susceptibility: (χm)
The magnetic susceptibility (  ) of a material is the ratio of the intensity of magnetization
produced in the sample to the magnetic field intensity. It has no units.
𝑀
i.e χm= 𝐻
Relation between B, H and M :
We know that B   H
µoµrH
B = µoµrH + µoH - µoH
B= µoH + µoH (µr-1)
B = µoH + µoM
Where the magnetization M is equal to H ( r  1)
i.e. B = µo (H+M)
Where 0 is the permeability of free space.
 Relation between  r and χ
Now B =  H
This equation can be written in other way as
B = 0 (M+H)
Where 0 is the permeability of free space.

The relative permeability  r 
0
µr = (B/H) / (B/(M+H))
µr = (M+H)/H =1+M/H
µr =1+ χ =
Where  is the magnetic susceptibility. µr is the relative permeability.
 Origin of magnetic moment (or) Magnetism due to electron motion:
In atoms, the permanent magnetic moments can arise due to the following
1. The orbital magnetic moment of the electrons

2. The spin magnetic moment of the electrons
3. The spin magnetic moment of the nucleus.
1. The orbital magnetic moment of the electrons:
When a magnetic moment is obtained through the motion of electrons in various orbits of an
atom, then it is called “orbital magnetic moment”
Bohr magneton:(µB)
The magnitude of spin moment contributed by single electron is known as Bohr magneton.
e
1 Bohr magneton,  B 
2m
Let us consider an electron of charge e which is revolving around the nucleus in the stationary
orbit of radius ‘r’ with a liner velocity ‘v’ as shown in figure 1. Hence, the current produced by
the electrons.
i=charge of the electron/time
e
i= ------(1)
T
2
Where T is time taken by the electron to make one revolution around the nucleus. i.e. T =

Where  is angular velocity of the electron.
electron
Fig. 1 current loop
But the relation between linear velocity and angular velocity can be written as
ν = rω
ω=ν/r
2𝜋𝑟
there fore T = 𝜈
Substitute (2) in (1)

i = -e/(2πr/ν) = -eν/2πr
From the definition of dipole moment   iA
Where i is current produced by the orbital motion of the electron and A is area covered by the
orbital.
−𝑒𝜈
Therefore µ = 2𝜋𝑟 (πr2)
µ = -eνr/2
Dividing and multiplying the above equation by the mass of the electron(m)
e(mvr )

2m
ml h
Since, the angular momentum L=mvr =
2
Where ml is the magnetic quantum number. its values are 0,1,2,3….n-1
e  ml h 
  
2m  2 
e
 ml
2m
    B ml
e
Hence  B   9.27 1024 ampere-m2 is called as Bohr magneton.
2m
Spin magnetic moment of the Electron:
Besides the orbital motion of an electron, electron rotates about its own axis. Magnetic moment
associated with spinning of an electron is called spin magnetic moment and the electronic spin
dipole moment is given by
𝑒ђ
M spin of e- =- [2𝑚] 𝑚𝑠
Where ms is spin quantum number i.e ms= ±1/2
Nucleus spin magnetic moment:

Nucleus magnetic moment arises due to the spinning of nucleus (protons) and is given by
𝑒ђ
M nucleus = - [2𝑀𝑝]
Where Mp is the mass of the proton.
But it is very less compared with e- spin magnetic moment. So it can be neglected.
 Classification of magnetic materials:

The magnetic materials have been classified into 5 types based on the influence of external field
on them. They are
1. Diamagnetic material
2. Para magnetic material

3. Ferromagnetic material
4. Anti Ferro magnetic material
5. Ferri magnetic material
1. Diamagnetic material:
The diamagnetism is the phenomenon by which the induced magnetic moment is always in the
opposite direction to the applied magnetic field. An electron moving around the nucleus results
in magnetic moment, due to different orientations of various orbits of an atom , the net magnetic
moment is zero in dia magnetic materials. Therefore in Dia magnetic material posses no
permanent magnetic moment or magnetic moment in each atom is zero.
When an external magnetic field is applied the motion of electrons in their orbits changes
resulting in induced magnetic moment in a direction opposite to the direction of the applied field.
Properties:
 Diamagnetic material possesses no permanent dipole moment.
 Diamagnetic materials repel magnetic lines of force.
 There is an induced magnetism opposite to the applied field.
 In the presence of magnetic field, the magnetic lines of force are pulled out from the
material. Hence, magnetic field induction is greater outside the material than inside
i.e. Bout  Bin
 Magnetic susceptibility is independent of applied magnetic field strength and

temperature.
 No spin alignment is present.
 The permeability for diamagnetic substances is <1
 The susceptibility for diamagnetic substances is Negative.
 E.g.: wood, H2O, silver, Zn , Bi, organic materials, paper etc….
2. Paramagnetic substances:
Each electron in an orbit has an orbital magnetic moment and spin magnetic moment. When
shells are unfilled there is no net magnetic moment. In the absence of external magnetic field the
net moments of the atoms are arranged in random directions.
These substances which when placed in magnetic field acquired weak magnetism in a direction
parallel to the applied magnetic field are known as paramagnetic substances.

Paramagnetic materials possess permanent dipole moment in each atom. The induced magnetic
moment produced by the external field increases the magnetic induction present in the material.
Properties:
 These posses permanent dipole moment

 There is an induced magnetism in the direction of the field.
 Net magnetic moment exists in the direction of the field.
 All spins or magnetic moment are randomly oriented in the absence of magnetic field
 In the presence of magnetic field the magnetic lines of force are attracted towards the
centre of the material and hence the magnetic induction inside the material is greater than
the outside Bin  Bout
 Paramagnetic susceptibility is dependent on temperature.
 Susceptibility is Positive.
 Permeability of paramagnetic substances greater than 1
 Ex Al, Pt, Mn etc….
C
 Susceptibility is inversely proportional to the temperature. i.e.   where C is Curie’s
T
constant.
3. Ferromagnetic substances:
The substances which when placed in a magnetic field the substances are strongly attracted by
the magnet. Such substances are known as ferromagnetic substances. Ferromagnetic materials
have a strong magnetic moment in the absence of external magnetic field. This is called
spontaneous magnetization. The large magnetization is due to spontaneous magnetization. There

is a special form of interaction called exchange coupling between adjacent atoms, coupling their
magnetic moments together in rigid parallelism.
At normal state all the domains are random in order. When this is kept in the external magnetic
field, all the domains are arranged in direction of field.
Properties:
 They are strongly attracted by the magnets

 These posses enormous permanent magnetic moment
 Large net magnetic moment exists in the direction of applied magnetic field.
 All the magnetic moments are orderly oriented in the absence of magnetic field.
 When placed in a magnetic field, it attracts the magnetic lines of forces very strongly i.e.
Bin  Bout
 Susceptibility is always positive and large and it depends upon temperature in a complex
manner. This is shown in below
𝐶
Χ=𝑇−𝜃
c

T 
 When the temperature of the material is greater than its curie temperature θ or Tc then it
converts into paramagnetic material
 These ferro magnetic materials exhibit hysteresis
 These materials consists of small region which are spontaneously magnetized called
“domains “
 Spin alignment is parallel in manner.
 Ex:-Fe, Ni, Co etc

 Depending up on the spin orientation of the electrons, ferromagnetic materials are
classified into two types. They are

(a) Anti ferro magnetic materials
(b) Ferri magnetic materials
4. Anti ferromagnetic materials:
(1) These are the ferro magnetic materials in which equal number of opposite spins with same
magnitudes such that the orientation of neighbouring spins is in anti parallel manner are
present
(2) Susceptibility is small and +ve for these materials

(3) The temperature at which anti ferromagnetic materials converts into paramagnetic material is
known as Neel’s temperature. (θ or TN )
(4) Susceptibility is inversely proportional to the temperature, the variation of susceptibility with
temperature is shown in figure
C

T 
(5) Ex:- FeO, MnO, etc
Neel’s temperature
O
Tc T
5. Ferri magnetic materials:
1. These are the ferromagnetic materials in which equal number of opposite spins with different
magnitudes are available such that the orientation of neighboring spins is in anti parallel
manner are present. Hence Ferri magnetic materials posses a net magnetic moment.
2. Susceptibility is positive and very large for these materials

3. The magnetization of ferromagnetic materials is intermediate to that of ferromagnetic and
anti ferromagnetic materials
4. Susceptibility is inversely proportional to temperature. The variation of susceptibility with
temperature is shown in figure.
C

T 
Where θ or TN are called Neel’s temperature.
5. Ferrites are the best examples of Ferri magnetic materials

6. Ex:-ZnFe2O4,Nickel ferrite, Manganese ferrite…
 Domain Theory of Ferromagnetism:

According to Weiss, a virgin specimen of ferromagnetic material consists of a number of
regions or domains which are spontaneously magnetized. In each domain spontaneous
magnetization is due to parallel alignment of all magnetic dipoles. The direction of
spontaneous magnetization varies from domain to domain. The resultant magnetization may
hence be zero or nearly zero. When an external field is applied there are two possible ways of
alignment of a random domain.
i) By motion of domain walls : the volume of the domains that are favorably oriented with
respect to the magnetizing field increases at the cost of those that are unfavorably oriented as
shown in fig. b.
fig. a shows domain arrangement in a virgin specimen when no magnetic field is applied.
ii) By rotation of domains: As shown in fig. c when the applied magnetic field is strong,
rotation of the direction of magnetization occurs in the direction of the field.
Fig (a) Fig. (b) Fig.(c)

 Hysteresis curve:
The hysteresis of ferromagnetic materials represents the phenomenon of lagging of
magnetization behind the applied magnetic field. The loop also refers to the hysteresis loss.
Fig: Typical Magnetization Curve of the virgin Specimen

(1) When the magnetic field is applied on a ferromagnetic materials. The magnetization
increases rapidly with applied field up to a value and after that it remains constant. This
magnetization is known as saturation of magnetization.
(2) If magnetic field on the material is reduced back to zero magnetization will not travel in
that initial path , creates a new path and it reaches to a point called residual
magnetization. It is also called as retentivity
(3) To reduce residual of magnetization to zero, negative field has to be applied when sufficient
negative field is applied, then the residual magnetization becomes zero and the field is known
as coercive field(HC)
(4) Further if negative magnetic field is applied then it increases that magnetization in negative
direction. This maximum magnetization in negative direction is called negative saturation of
magnetization
(5) If negative field is decreased back to zero the negative saturation of magnetization will not be
travel in the initial path, crates a new path and reaches to a point called negative residual
magnetization. It is also called as retentivity
(6) To decrease the negative residual magnetization to zero some positive fields has to be
applied. The amount of magnetic field required to bring residual magnetization to zero is
known as coercive field(HC)
(7) The positive magnetic field increases the magnetization reaches again to positive saturation.
And it is cyclic process. The hysteresis curve is as shown in the figure.
(8) The area of hysteresis loop refers to the hysteresis loss. If the loop area of a ferromagnetic
material is large then more loss occurs during each cycle of hysteresis.

(9) Depending on the hysteresis loss values, the ferromagnetic materials are classified into two
categories they are
(i) Soft magnetic materials.
(ii) Hard magnetic materials.
Soft magnetic materials:

The magnetic materials which can be easily magnetized and demagnetized are known as soft
magnetic materials. The features of the soft magnetic materials are
(i) Hysteresis loop is narrow, hence hysteresis loss small as shown in fig.
(ii) Permeability and susceptibility are large
(iii) Eddy current loss is high due to its high resistivity.
(iv) Coercivity and retentivity are small
(v) Magneto static energy is very small
(vi) it is used in electro –magnetic machineries and transformers
(vii) Ex Ferrites, granites, iron-silicon alloy etc.
Fig: Soft Magnetic Material
Hard magnetic materials:

The magnetic materials which cannot be easily magnetized and demagnetized are known as hard
magnetic materials. The salient features of hard magnetic materials are
(1) Hysteresis loop is wide, hence hysteresis loss is more as shown in fig
(2) Permeability and susceptibility are small
(3) Eddy current loss is low due to its smaller resistivity. This losses can be minimized by
increasing the resistivity
(4) Coersitivity and retentivity are large
(5) Magnetostatic energy is large
(6) It is used in making permanent magnets, magnetic detectors, microphones etc
(7) Ex: plane carbon steel, cobalt steel, Al-Ni-co alloys, etc

Fig: Hard magnetic Material
Applications of magnetic materials:

Some important applications of magnetic materials are mentioned in the following sub sections.
Magnetic recording and readout:
Magnetic materials can be used for recording information as well as for reading out the recorded
information. The recording head example (a tape recorders recording head) consists of a
laminated electromagnet, fabricated using permanently or a soft ferrite with an air gap. A wire
coil is bound around the magnetic material core. As a magnetic tape or disc is passed around an
electro magnet, the electrical signal fed to the coil generates a magnetic field with in the gap. The
magnetization of this portion of the tape is proportional to the current passing through the coil.
The magnetic material coated on the tape is such that magnetization is retained even after the
removal of the field. The signal thus gets stored in the tape. The moving tape induces an emf in
the wire coil. To read the tape, the induced alternating emf is amplified through a suitable
amplifier and fed into an output device.
Applications of ferrites:
 They are used in thermal sensing switches used refrigerators, air conditions, microwaves
 In producing ultrasonic waves
 These materials are used in digital data storage devices
 Ferrites can be used in transformer cores for frequencies up to micro waves
 Soft ferrites are used in the magnetic floppy disks, magnetic tapes & memory devices
 They are also used as radio frequency transformer core materials
 Ferrite rods are used in radio receiver to increase sensitivity and selectivity
 They are also used in digital computers and data processing circuits
Basic concepts of super conductivity:
 The phenomenon of attaining zero resistivity or infinite conductivity at low temperatures
is known as super conductivity. The material becomes a super conductors and it will be in
super conducting state.
 The temperature at which the material undergoes a transition from normal state to super
conducting state is known as “ critical temperature “ or transition temperature Tc
 Different materials have different Tc values
Ex: Mercury Tc=4.2K

Lead Tc = 7.2K
General properties of super conductors:
1. Super conductivity is a low temperature phenomenon.
2. Different materials will have different Tc values.
3. Zero electrical resistivity.
The transition from normal state to super conductivity state occurs below the Tc.
4. The current once set up in a super conductors persists for a long time due to zero resistivity.
5. Concept of Perfect Diamagnetism:(Meissner Effect)
When a superconductor is placed in a weak magnetic field below its transition temp, the
magnetic lines of induction ‘B’ inside the superconductor are expelled as shown in fig.
The phenomenon of expulsion of magnetic flux from a superconducting specimen is known as
“Meissner effect”.
The diamagnetic behavior of a superconductor is as shown in figure.
The meissner effect is a reversible phenomenon i.e. when the temp is raised above Tc. The flux
suddenly starts penetrating; as a result the specimen returns back to the normal state. In this state
the magnetic induction inside the specimen is given by
B = 0 (H+M)
Where H=external applied magnetic field
M=magnetization inside the specimen
Since B=0 inside the superconductor
0 (H+M)= 0  H+M=0
 H=-M
The susceptibility is given by  =M/H = -H/H = -1
  = -1
Which is true for a perfect diamagnetic.
Therefore superconductors are diamagnetic materials.
Thus materials can behave as a super conductor only when resistivity of material is zero and flux
should be equal to zero when it is placed in uniform magnetic field.

Both these conditions are independent to each other and to get superconducting states, these two
conditions should be satisfied simultaneously.
6. Effect of magnetic field:
When a magnetic field is applied to a super conductor then for a particular value of applied field
looses super conductivity and becomes a normal conductor.
The magnetic field(H) at which a super conductor looses its super conductivity and becomes
normal conductor is known as critical magnetic field Hc
The value of critical field Hc depends on the temperature and differs from material to material. It
is given by
Hc=H0[1-(T/Tc)2]
Where Hc --------critical field
H0------------critical field at zero Kelvin
T--------temperature of super conductors.
Tc-------- critical temperature of super conductors.
For T=Tc Hc=0
T=0K Hc=H0
7. Effect of pressure:
By applying very high pressures it is possible to bring super conducting trasition temperature Tc
of a material near to room temperature. i.e. Tc α pressure.
8.Isotope effect:
The Tc values are inversely proportional to square root of the atomic weights of the isotopes of
Superconductor.
Tcα1/M0.5 where M→atomic weight of isotope of Superconductor.
Ex: atomic weights of isotopes of Hg are 199.5- 203.5 amu
For Hg 199.5-------------- Tc=4.185K
Hg203.4------------------- Tc=4.146K
9. Effect of heavy current:
The super conductivity properties of the super conductors disappear when sufficiently heavy
current is passed through them. When the large current flows through super conductor it will
produce the magnetic field which can destroy the super conductivity state.
It is given by Ic=2 ᴨ rHc
Here Ic= critical current
Hc= critical magnetic field
r = radius of conductor wire
2𝐻𝑐
Critical current density=Ic/A= 2 ᴨ rHc/ ᴨ r2 = 𝑟
Where A= area of cross section of the conductor wire

Type I and Type II superconductors:
In the presence of critical field Hc , a super conductors converts into a normal conductor, based
on the conversion process or based on dia magnetic response super conductors are classified into
two types.
1. Type I superconductors ( Soft Superconductors )

2. Type II superconductors ( Hard Superconductors )
Differences between type I and type II super conductors
Type I super conductors Type II super conductors
H<Hc1Superconducting State (S.S)

H<HcSuperconducting State(S.S)
Hc1<H<Hc2 mixed state
H>Hc Normal State( N.S)
H>Hc2Normal State( N.S)
 In this type, when the applied field is
 In this type, when applied field reaches
equal to critical field , then
lower critical field (Hc1) conversion
immediately it converts into normal
starts and it is completed slowly at upper
conductor
critical field (Hc2)
 It has two critical field values i.e Hc1 and
 It has a single critical field Hc
Hc2
 Ther is no mixed state
 There is a mixed state
 They are hard super conductors.
 They are soft super conductors.
 Material with impurities are of type II
 Material with pure form of are type I
super conductors.
super conductors.
 Ex: Nb3Ge, Nb3
 Ex: Hg, Nb etc..
BCS theory:
BCS theory is named as the Bardeen, Cooper and Schrieffer who proposed it in 1957.
Its basic assumption is the existence of electron pairs in a super conductor. The two electrons in
such a pair are bound to each other and move together.
They have opposite wave vectors and spins, hence denoted by K↑ and -K↓.

In a super conducting state one particle orbital’s are occupied or vacant in pairs. If an orbital
with K↑ is occupied, then the orbital with -K↓ is also occupied, otherwise both are vacant, such
electron pairs or orbital pairs are called cooper pair.
The super conductivity phenomenon is treated quantum mechanically by describing the two
electrons of a cooper pair with a common wave function ѱ. This procedure has been introduced
for explaining fluxons. It also represents the derivation of London equations which explain
Meissner effect etc.
In normal materials electrons repel each other. But it is assumed that, in a super conductor,
electron pairs exists due to an electron – lattice – electron interaction.
This could happen when one electron interacts with a lattice and deforms it while a second
suitable electron interacts with such a deformed lattice.
The net result is an attraction, instead of repulsion between the two electrons.
It can be seen that the cooper pairs have zero spin, hence they can be regarded as a charged
boson gas.
 Applications of Superconductors:
Applications of super conductors- science and technology:
1. Electric Generators:
Superconducting generators are very small in size and less weight when compared with
conventional generators. Motors with very high power as large as 2500 kW could be constructed
at very low voltage as low as 450 V. This is the basis of new generation of energy saving power
system.
2. Low loss Transmission lines and transformers:
Since the resistance is almost zero at superconducting state, the power loss during transmission is
negligible. Hence electric bulbs are designed with superconducting wires. If superconductors are
used for winding of a transformer the power losses will be very less.
3. Generation of High magnetic fields.
4. Fast electrical switching.
5. Logic and storage functions in computers.
6. SQUIDS (Superconducting Quantum Interference Devices):
Squid is double junction quantum interferometer. The squids are based on the flux quantization
in a superconducting ring. These are used to study tiny magnetic signals from the brain and heart.
Squid magnetometers are used to detect the paramagnetic response in the liver. This gives
information about the amount of iron held in the liver.

Magnetic Levitation:
 Magnetic Levitation:
Diamagnetic property of a superconductor, namely, rejection of magnetic flux lines is the basis
of magnetic levitation.
If a super conducting material is placed in magnetic field , electric currents are set up at its
surface, screening out an external magnetic field. this results in zero magnetic field inside the
material. Thus a super conducting material displays a perfect dia magnetism. This property
ensures that the magnet brought near a super conductor is repelled. This repulsion effect can be
used to float a magnet above a super conductor. This phenomenon is called magnetic levitation.
Magnetic levitation (maglev) is used to operate levitated trains. These trains do not move on rails
like the conventional trains., but flout on an air cushion over strongly magnetized tracks. Super
conducting coils in the train result in magnetic repulsion that enables levitation. The absence of
any mechanical friction allows the achievement of extremely high speeds. Speeds as high
as500Km/h have been achieved.
The following are some applications where this phenomenon is used
 A super conducting supercollider (SSC) other than maglev trains is particle accelerator
that uses strong magnetic fields generated by super conducting magnets. Energy in the
range of tens of TeV can be generated and used for interactions.
 Large super conducting magnets also find applications in Magnetic Resonance Imaging
(MRI) systems used in medicine.
Memory Devices:
Magnetic data can be stored in storage devices such as tapes, floppies and magnetic discs.
Magnetic materials used for information storage must have a square shaped hysteresis loop and a
low coercive field. This permits a rapid transmission of information. Magnetic tapes for audio or
video applications are fabricated by plating, sputtering, or evaporating magnetic materials such
as Fe2O3 or CrO2 on a polyester tape. Magnetic oxide materials are dispersed in a binder to
ensure strong bonding. The oxide particles are needle like, with a size of around 0.1 to .5 mm2.
Coercivity of Fe2O3 is around 20 to 28 kA/m. the elongated particles are aligned using a field
during manufacturing so that the long axes become parallel to the length of the tape or the track.
Floppy discs and hard discs used in computer data storage or also fabricated in a similar manner.
Magnetic particles used in a hard disc, for example are, embedded in a polymer film on a flat
substrate of aluminum. The domains can rotate very fast in a magnetic field due to the presence
of small particles in the polymer matrix.

UNIT IV
OPTICS AND LASERS
Optics is a branch of Physics which deals with the study of light phenomena like
interference, diffraction and polarization. Optics becomes an extremely important because of its
applications in many diverse areas. The phenomena such as interference, diffraction and
polarization are used for scientific applications such as calibration and precision measurements,
optical information processing, optical computing etc.
Interference:
Thomas Young demonstrated the concept of interference of light in 1802. When two or more
waves travel simultaneously in medium, the resultant displacement at any point is due to the
algebraic sum of the displacements due to individual waves.
Let at any point y1 be the displacement due to one wave at any instant in the absence of the other
wave and y2 be the displacement of the other wave at the same instant in the absence of the first
wave.
Then the resultant displacement due to the presence of both the waves is given by
y = y1±y2
+ve sign has to be taken when both the displacements y1 and y2 are in the same direction; -ve
sign has to be taken when they are in the opposite direction.
To obtain interference pattern we need two sources emitting waves of same amplitude, same
wavelength with constant (or zero) phase difference. These types of sources are called as
“coherent sources” of light.
Interference in Thin Films (Reflected light)
In a thin film, interference is due to superposition of light reflected from the top and bottom
surfaces of the film. In both reflected as well as transmitted light one can observe interference.
Let us consider a thin film of thickness “t” bound by two plane surfaces XY and X′Y′ and let µ
be the refractive index of the material of the film.
A ray of light AB incident on the surface XY at an angle “i” is partly reflected along BC and
partly refracted along BD. Let the angle of refraction be “r”.
On the surface X′Y′, the refracted ray is partly reflected along DE and partly refracted
(transmitted) along DK. Similar reflection and refraction occur at E and G also as shown in
figure.

The rays BC and EF constitute reflected system. To find the path difference between these
reflected rays a perpendicular EP is drawn to BC.
Path difference = (BD+DE) µ - BP
𝐷𝑄 𝑡
In ΔBDQ, cos r = =
𝐵𝐷 𝐵𝐷
𝑡
Or BD =
cos 𝑟
𝑡
Similarly from ΔDQE, DE =
cos 𝑟
2𝑡
So BD +DE =
cos 𝑟
2µ𝑡
Hence path difference = – BP -------------------(1)
cos 𝑟
𝐵𝑃
In ΔBPE, sin i =
𝐵𝐸
Or BP = BE sin i = (BQ + QE) sin i
𝐵𝑄
In ΔBDQ, tan r =
𝐷𝑄
Or BQ = t tan r = QE
Or BP = 2t tan r sin i
sin 𝑟 sin 𝑖
= 2t µ sin r (because µ = ) --------(2)
cos 𝑟 𝑠𝑖𝑛 𝑟
Substituting Eq. (2) in Eq. (1)
2µ𝑡 𝑠𝑖𝑛2 𝑟
Path difference = - 2µt
cos 𝑟 cos 𝑟
(1−𝑠𝑖𝑛2 𝑟 ) 2µ𝑡 𝑐𝑜𝑠 2 𝑟
= 2µt =
cos 𝑟 cos 𝑟
= 2µt cos r
Since the ray BC is reflected at the air-medium (rarer-denser) interface, it undergoes a
phase change of π or path increase of λ/2. Hence the path difference between the ray BC and EP
is
𝜆
= 2µt cos r - ---------------(3)
2
i) Condition for bright band
The film will appear bright if the path difference is equal to integral multiple of wavelength λ.
𝝀
2µt cos r - = n λ ----------------------------(4)
𝟐
Where n = 0,1,2,3,-------etc.,
𝜆
Or 2µt cos r = (2n+1)
2
Where n = 1,2,3,-------etc.,
ii) Condition for dark band
The film will appear dark if the path difference is equal to odd multiple of half wavelength λ.
𝝀 𝝀
2µt cos r - = (2n+1) ---------------------(5)
𝟐 𝟐
i.e. 2µt cos r = (n+1) λ
where n = 0,1,2,3,-------etc.,
or 2µt cos r = n λ
where n = 1,2,3,---------etc.,
iii) If the film thickness is extremely small when compared to λ, then 2µt cos r can be neglected
in Eq. (3) and then the net path difference is λ/2. Hence destructive interference will occur and
the film will appear dark.
Newton’s Rings
Interference pattern can also observed by placing a plano-convex lens of long focal length on the
top of a flat glass plate. With this arrangement a thin film of air is enclosed between the lower
surface of the lens and the upper surface of the glass plate. At the point of contact where the lens
touches the glass plate the thickness of the air film is zero and when moved radially towards the
edge of the lens, the thickness of the air film increases. When the lens is illuminated with
normally incident light rays from a monochromatic light source and observed concentric rings
pattern is seen. These circular rings were first observed by Newton and hence are called
Newton’s rings.

Newton’s rings by reflected light
Let R be the radius of curvature of the Plano convex lens and let us choose a point P at a distance
“r” from O and let “t” be the thickness of air film at that point.
The path difference between the light reflected at P and Q is “2t = mλ” ( As the path difference is
2µt cosr = mλ, for normal incidence rays cosr = 1, for air medium µ =1)
Radii of Dark rings:
Let us consider the curved surface of the lens as an arc of a circle whose centre is at “c”.
From the figure.,
By apply equation of chords in circles, we can write as
HE X EP = OE X EO′
i.e., r2 = t (OO′ – EO) (As HE = EP = r, OE = t and EO′ = OO′ – OE = 2R - t)
= t(2R – t)
= 2Rt – t2
But we have 2t = mλ
= 2Rt (approximately)
r = mλR
2
Or rm = √𝑚𝑅𝜆 where m = 1,2,3,--------etc.,

Dm = 2 rm = 2√𝑚𝑅𝜆
Or Dm2 = 4mλR

Determination of wavelength of sodium light using Newton’s rings:
Let “R” be the radius of curvature of the Plano convex lens in contact with the glass plate and
“λ” the wavelength of light used.
As we know the radius of nth dark ring is, rn = √𝑛𝑅𝜆
The diameter of the nth dark ring is, Dn = 2rn = 2√𝑛𝑅𝜆 = √4𝑛𝑅𝜆
Hence D2n = 4nRλ -------------------(1)
Similarly the diameter of the (n+m)th dark rings is
Dn+m = 2rn+m = √4(𝑛 + 𝑚)𝑅𝜆
Hence D2n+m = 4(n+m)Rλ -----------(2)
Subtracting equation (6) from equation (7) we get
D2n+m – D2n = 4mRλ
2
𝐷𝑛+𝑚 −𝐷𝑛2
or λ= ------------------(3)
4𝑚𝑅
Hence by measuring the diameters of rings of different orders and knowing the radius of
curvature of the lens “R”, we can determine the wavelength “λ” of the given monochromatic
source of light.
Diffraction
The phenomenon of bending of light round the corners of obstacles and spreading of light waves
into the geometrical shadow region of an obstacle placed in the path of light is called diffraction.
It can be explained by taking Huygen’s wave theory that every point on the primary wavefront
acts as second source of disturbance and secondary waves are generated from those points.
Let primary wavefront XY from point source S of monochromatic light reach the aperture MN
placed in its path. The light passing through the aperture has to cause brightness inside AB on the
screen and regions beyond A and B have to be dark i.e. regions of geometrical shadow. But due
to diffraction property every point on the wavefront reaching the aperture MN acts as secondary
waves enter into the geometrical shadow region.

The diffraction phenomenon is divided into two types:
i) Fresnel Diffraction
ii) Fraunhofer Diffraction
Comparison between these two types of diffraction

S No Fresnel Diffraction Fraunhofer Diffraction
1. Either a point source or an illuminated Extended source at infinite distance is used.
narrow slit is used. The width between fringes is never equal.
2. The wavefront undergoing diffraction is The wavefront undergoing diffraction is a
either spherical or cylindrical. plane wavefront.
3. The source and the screen are finite The source and the screen are at infinite
distances from the obstacle producing distances from the obstacle producing
diffraction. diffraction.
4. No lens is used to focus the rays Converging lens is used to focus parallel rays.
Difference between interference and diffraction

S No Interference Diffraction
1. Superposition is due to two separate Superposition is due to secondary wavelets
wavefronts originating from two originating from different parts of the same
coherent sources. wavefront.
2. The fringes normally have equal widths. The width between fringes is never equal.
3. All the bright fringes have the same The intensity of bright fringes usually
intensity. decreases with increase of order.
4. All the dark fringes have zero intensity. The intensity of dark fringes is not zero.
Fraunhofer diffraction at single slit

Let “S” be a point source of monochromatic light. L1 is the collimating lens of focal length “f” at
a distance “f” from the source so that the lens renders parallel rays.
AB is the single slit of width “a”.
The light passing through this slit is collected by lens L2 which forms the final image on the
screen XY.
Let us consider a plane wavefront incident normally on the slit AB. Each and every point on the
wavefront will act as secondary source of light and wave from such sources travel after AOB in
all possible directions.
Let us consider the waves travelling along OPo. i.e., the waves from A, O and B, travel straight
and focus at Po. Since all these waves have travelled the same optical distance, there is no path
difference between them and hence they produce constructive interference and hence point Po is
bright with maximum intensity.

Now let us consider the secondary waves travelling along AR at an angle “θ” with respect to AD.
All secondary waves from the incident wavefront AOB travel along this direction to reach P 1 on
the screen.
To know whether P1 will have maximum or minimum intensity, it depends on the path difference
between secondary waves from various points on the wavefront AOB reaching P1.
To calculate this let us draw BL perpendicular to AR. Let that cut OP1 at MO after BML all the
waves travel same distance to reach P1.
From the figure it is clear that the secondary waves starting from various points on BOA have
varying path difference to reach P1. This path difference varies from minimum value of zero at B
to maximum value of AL at A. Let AL = δ.
𝐴𝐿 𝛿
In ΔABL sin θ = =
𝐴𝐵 𝑎
Or δ = a sin θ
Where “a” is the width of the slit, “θ” is the angle of diffraction and “δ” is the path difference
between the secondary waves originating from A and B.
If this path difference is λ, 2 λ, 3 λ ---------etc., P1 will be a point of minimum intensity.
Hence in general the condition for minimum intensity can be written as
a sin θn = nλ
Where n = 1,2,3,-----etc., n is an integer. θn corresponds to the direction of nth minima.
When the path difference is odd multiple of λ/2 , secondary maxima is obtained.
i.e., a sin θn = (2n+1)λ/2 where n = 1,2,3,-----etc.
Fraunhofer diffraction due to N-Slits (Diffraction grating)
Diffraction grating: It Consist of very large number of narrow slits side by side separated by
opaque spaces of equal width “b”. The incident light is transmitted through the slits of equal
width “a” and blocked by opaque spaces. In general a plane transmission grating is a plane sheet
of transparent material on which opaque rulings are made with a diamond point. The rulings are
opaque and are of equal width. The combined width of a ruling and a slit is called grating
element (a+b). Points on successive slits separated by a distance equal to the grating element are
called corresponding points i.e. (a+b) = c.
Theory of plane transmission grating

Let ABCDEF shown in figure represent the section of grating normal to the plane of the paper.
AB, CD, EF etc., represent the slits of width “a” each while BC, DE, etc., represent opaque
rulings of width “b” each.
Let a plane wavefront be incident normally on the grating. The points in the slits AB, CD, EF
etc, act as secondary sources of light giving rise to secondary waves. These waves spread in all
direction on the other side of the grating. The secondary waves travelling in the same direction as
that of the incident wave are focused at Po on the screen. Since all these secondary waves have
travelled equal distance to reach Po, they reinforce constructively and hence the point Po is the
position of central bright maximum as shown in figure (a).
Let us consider the secondary diffracted waves proceeding in a direction which makes an angle
“θ” with respect to the normal to the grating as shown in figure (b).
AMM1 is drawn normal to the diffracted light. Let us consider the waves diffracted at the
corresponding points A and C. The path difference between the waves on reaching P 1 is CM
since they travel equal path beyond AM.

𝐶𝑀
In Δ ACM sin θ =
𝐴𝐶
or CM = AC sin θ
= (a+b) sin θ
The superposition of these waves at P1 causes interference. P1 will be bright when
(a+b) sin θm = mλ -----------------------------(1)
Where m = 0,1,2,3, --------etc., and angles θ1, θ2, θ3--------etc., correspond to the directions of the
principal maxima.
Hence
𝑚𝜆
Sin θm =
(𝑎+𝑏)
= mNλ
1
Where = N is the number of grating elements or lines per unit width of the grating.
(𝑎+𝑏)
Grating spectrum
In Eq. (1), for m = 1
(a+b) sin θ1 = λ
In a direction inclined at an angle θ1 to the incident direction, first order image is obtained.
Similarly the second order bright images is obtained when θ = θ2. i.e., m = 2.
(a+b) sin θ2 = 2λ
Thus different order bright images are obtained on both sides of the direct ray.
Instead of monochromatic source of light such as sodium vapour lamp, if white light source such
as mercury lamp is used, in the each diffracted order different colours are diffracted at different
angles.

LASER
It is a device to produce a highly intense monochromatic narrow beam of light in which
the waves are convergent. Laser is an acronym for light amplification by stimulated emission of
radiation. The light emitted from the conventional light source (eg: sodium lamp, candle) is said
to be incoherent. Because the radiation emitted from different atom do not have any definite phase
relationship with each other. Lasers are much important because the light sources having high
monochromaticity, high intensity, high directionality and high coherence.
Laser principle now a days is extended up to - rays hence Gamma ray lasers are called Grazers.
The first two successful lasers developed during 1960 were Ruby laser and He- Ne lasers. Some
lasers emit light is pulses while others emit as a continuous wave.
Characteristics of laser radiation:
The four characteristics of a laser radiation over conventional light sources are
(1) Laser is highly monochromatic
(2) Laser is highly directional
(3) Laser is highly coherent
(4) The intensity of laser is very high
1. Highly monochromatic:
0
The band width of ordinary light is about 1000A . The band width of laser light is about 10Ao.
The narrow band width of a laser light is called as high monochromaticity.
Band width: The spread of the wavelength (frequency) about the wavelength of maximum
intensity is band width. Laser light is more monochromatic than that of a conventional light
source. Because of this monochromaticity large energy can be concentrated in to an extremely
small band width.
The degree of monochromaticity of light from any source can be defined in terms of line width
(spectral width) of the source. The frequency spread Δν of spectral line is related to the wavelength
spread Δλ as
𝑐
Δλ = ( 2 )𝛥𝜈
𝜈
For a white light source Δλ = 300nm whereas for a gas discharge line Δλ = 0.01nm.

2. High directionality:
The conventional light sources like lamp, torch light, sodium lamp emits light in all directions.
This is called divergence. Laser in the other hand emits light only in one direction. This is called
directionality of laser light. Light from ordinary light spreads in about few kilometers. Light from
laser spreads to a diameter less than 1 cm for many kilometers of travel. The directionality of laser
beam is given by (or) expressed in divergence.
The divergence ∆ = (r2 -r1) /d2-d1
Where r2, , r1 are the radius of laser beam spots and d2 , d1 are distances respectively from the laser
source. Hence for getting a high directionality there should be low divergence.
3. Highly coherent:
Laser has high degree of ordering than other common sources. Due to its coherence only it is
12
possible to create high power (10 watts) in space with laser beam of 1µm diameter. There are two
independent concepts of coherence.
i) Spatial coherence ii) Temporal coherence
i. Spatial coherence: The two light fields at different point in space maintain a constant phase
difference over any time (t) they are said to be spatial coherence or transverse coherence. When we
choose two spatial points P1 and P2 on the cross section of the output beam, if they are in phase
with one another or maintain same phase differences then they are spatially coherent.
In He- Ne gas laser the coherence length ( lc ) is about 600km.It means over the distance the
phase difference is maintained over any time .For sodium light it is about 3cm.
ii. Temporal coherence: The correlation of amplitude and phase between any two points on a
wave train over a period of time is called temporal coherence or longitudinal coherence. If the two
points P1 and P2 which are on the same wave train caries same phase and amplitude then it is said
to be temporal coherence.

-3 -10
For He- Ne laser it is a about 10 second , for sodium it is about 10 second only.
4. High intensity:
Lasers are bright and intense light sources because of coherence and directionality. Intensity of a
wave is the energy per unit time flowing through a unit area. The light from an ordinary source
spreads out uniformly in all directions and form spherical wave fronts around it.
Ex:- If we look a 100W bulb from a distance of 30cm the power entering the eye is 1 / 1000 of
watt. But in case of a laser light, energy is in small region of space and in a small wavelength and
hence is said to be of great intensity.
-3 9
The power range of laser is about 10 W for gas laser and 10 W for solid state laser.
Spontaneous and stimulated emission of radiation:
Light is emitted or absorbed by atoms during their transitions from one energy state to another.
The process of transferring a atom from ground state to higher energy state is called excitation.
Then the atom is said to be excited and the process is called induced absorption or absorption.
The atom in the excited state can remain for a short interval of time known as life time. The life
time is of the order of 10-8 sec, in the excited states in which the life time is much greater than
10-8 sec are called metastable states. The life time of the atom in the metastable state is of the
order 10-6 sec to 10-3sec.
The probability of transition to the ground state with emission of radiation is made up of two
factors one is constant and the other variable.
The constant factor of probability is known as spontaneous emission and the variable factor is
known as stimulated emission.
Spontaneous emission: The emission of atoms from higher energy state to lower energy state
spontaneously by emitting a photon of energy “h” is known as "spontaneous emission".

Stimulated emission: The emission of a atom from higher state to lower state by stimulating it
with another photon having energy equal to the energy difference between transition energy
levels is called stimulated emission.
Difference between Spontaneous emission & Stimulated emission:

S No Spontaneous emission Stimulated emission
1 Incoherent radiation coherent radiation
2 Less Intensity high intensity
3 Polychromatic monochromatic
4 One photon released two photons released
5 Less directionality high directionality
6 More angular spread during propagation less angular spread during propagation
Ex:-Light from sodium lamp, Mercury light from a laser source: Ruby laser, He-Ne
7
vapour lamp gas laser.
Einstein’s equations (or) Einstein’s Coefficients:

Based on Einstein's theory of radiation we can derive an expression for probability for stimulated
emission of radiation to the probability for spontaneous emission of radiation under thermal
equilibrium.
Let E1, E2 be the energy states and N1, N2 be the no of atoms per unit volume

Upward transition: If ()d is the radiation energy per unit volume between the frequency
range of  and +d. Then the number of atoms after absorption of energy undergoing upward
transition per unit volume per second from level
E1 to E2 = N1 ( )B12 ------ 1
B12 represents probability of absorption per unit time.
Stimulated emission: When an atom makes transition from E2 toE1 in the presence of external
photon whose energy equal to (E2-E1) stimulated emission takes place thus the number of
stimulated emission per unit volume per second from levels
E2 to E1 = N2 () B21 ------ 2
B21 is represents probability of stimulated emission per unit time.
Spontaneous emission: An atom in the level E2 can also make a spontaneous emission by
jumping into lower energy level E1.
E2 to E1=N2A21 -----------3
A21 represents probability of spontaneous emission per unit time.
Under steady state (dN / dt) = 0
Number of atoms undergoing absorption per second = Number of atoms undergoing emission
per second
i.e. 1 =2+3
N1 ( )B12 = N2 ( )B21 + N2 A21
N2 A21 = N1 ( )B12 - N2 ( )B21
= ( )(N1B12 - N2B21)
 () = N2 A21 / (N1B12 - N2B21)
= A21 / [(N1 / N2 )B12 - B21)] -------- 4
From Boltzmann distribution Law, we know that
−𝐸𝑖
Ni = gi No exp [ ] --------------------5
𝑘𝑇
Where Ni is the population density of the energy level Ei, No is the population density of
the ground state at temperature T, gi is the degeneracy of the ith level and k is the Boltzmann
constant ( = 1.38X10-23 joul/K).
Hence N1 = g1 No exp (– E1 / kT)
N2 = g2 No exp (– E2 / kT)
𝑁1 𝑔1 (𝐸2− 𝐸1 )
= exp --------------6
𝑁2 𝑔2 𝑘𝑇
𝑁1 𝑔1 ℎ𝜈
= exp[ ] ---------------7
𝑁2 𝑔2 𝑘𝑇
Substituting Eq. (7) in Eq. (4)

𝐴21 /𝐵21
 () = 𝑔1 𝐵12 ℎ𝜈 -----------8
exp[ ]−1
𝑔2 𝐵21 𝑘𝑇
From Plank’s law of black body radiation, the radiation density is given by
8𝜋ℎ𝜈3 1
 () = [ ℎ𝜈 ] ---------9
𝑐3 exp( )−1
𝑘𝑇
Comparing Eqs. (8) and (9)
𝑔1 𝐵12
=1
𝑔2 𝐵21
g1B12 = g2B21 ------------------------------10
𝐴21 8𝜋ℎ𝜈3
and = --------------------------11
𝐵21 𝑐3
Eq.s (10) and (11) are referred to as the Einstein relations.
Population inversion:
The number of atoms in higher energy level is more than the number of atoms in lowest energy
level i.e. N2˃N1. The process of making of higher population in higher energy level than the
population in lower energy level is known as population inversion.
Population inversion is achieved by pumping the atoms from the ground level to the higher energy
level.
The population inversion is easily achieved at the metastable state, where the life time of the
atoms is higher than that in other higher energy levels.
The states of system, in which the population of higher energy state is more in comparison with
the population of lower energy state, are called "Negative temperature state".
A system in which population inversion is achieved is called as an active system. The method of
raising the particles from lower energy state to higher energy state is called "Pumping".
There are four different methods of pumping the energy to create population inversion. They are
1. Optical pumping
2. Electrical discharge
3. Chemical reaction
4. Injection current etc.
Different types of laser:
1. Solid state laser - Ruby laser, Nd-YAG laser
2. Gas laser - He-Ne laser, CO2 laser
3. Semi conductor laser - GaAs laser
RUBY LASER:
Ruby laser is a three level solid state laser having very high power of hundreds of mega watt in a
single pulse. It is a pulsed laser.
The system consists of mainly three parts
1) Active material: Ruby crystal in the form of rod.
2) Resonant cavity: A fully reflecting plate at the left end of the ruby crystal and partially
reflecting end at the right side of the ruby crystal both the surfaces are optically flat and exactly
parallel to each other.
3) Exciting system: A helical xenon flash tube with power supply source.
Construction: In ruby laser, ruby rod is a mixture of Al2O3+Cr2O3. When an Aluminum rod is
dipped in Chromium solution, some of surface Al3+ ions are replaced by Cr3+ ions which are
3+
involved in lasing action. Typical Cr ion concentration is about 0.05% by weight then the colour
of rod becomes pink. The emission wave length is 0.6943µm or 694.3nm i.e. 6943Ao.
The length of the ruby rod is 4cm and diameter 5mm and both the ends of the ruby rod are
silvered such that one end is fully reflecting and the other end is partially reflecting. The ruby rod
3+
is surrounded by helical Xenon flash lamp tube which provides the optical pumping to raise Cr
ions to upper energy level. The chromium atom has been excited to an upper energy level by
absorbing blue and green portions of the visible spectrum emitted by the Xenon flash lamp (i.e.
photons of wave length 5600A0). Initially the chromium ions (Cr3+) are excited from E1 to E3. The
population in E3 increases. Since the life time of E3 level is very less (10-8 Sec) the chromium ions
drop to (E2 energy level) lower-lying metastable energy states of life time 10-3Sec. These states are
the upper levels of the two ruby laser transitions. The transition from E3 to E2 is non radiative.

Since the life time of metastable state is much longer, the no of ions in this state goes on increasing
hence population inversion achieved between the metastable state E2 and the ground state E1.
When an excited ion passes spontaneously from the metastable state E2 to the ground state E1, i.e
from first metastable state emits a photon of wave length 692.7nm (6927Ao) and from second
metastable state emits a photon of wave length 694.3nm (6943Ao) respectively. Stimulated emission
at the 694.3nm line usually dominates. This photon travel through the ruby rod and it is reflected
back and forth by the silver ends until it stimulates an excited ion in E2. The emitted photon and
stimulated photon are in phase and the process is repeated again and again finally the photon beam
becomes intense; it emerges out through partially reflecting surface. Since the emitted photon and
stimulating photon in phase, and have same frequency and are traveling in the same direction, the
laser beam has directionality along with spatial and temporal coherence.
Importance of resonator cavity: To make the beams parallel to each other curved mirrors are
used in the resonator cavity. Resonator mirrors are coated with multi layer dielectric materials to
reduce the absorption loss in the mirrors. Resonators act as frequency selectors and also give rise to
directionality to the output beam. The resonator mirror provides partial feedback of the protons.
He – Ne laser:
Construction: He - Ne gas laser consists of a gas discharge tube of length 80cm and diameter of
1cm. The tube is made up of quartz and is filled with a mixture of Neon under a pressure of
0.1mm of Hg and Helium under the pressure of 1mm of Hg. The ratio of He-Ne mixture of about
10:1, hence the no of helium atoms are greater than neon atoms. The mixtures is enclosed
between a set of parallel mirrors forming a resonating cavity, one of the mirror is completely
reflecting and the other is partially reflecting in order to amplify the output laser beam.
Working: When an electric discharge is passed through the gaseous mixture electrons are
accelerated down the tube, these accelerated electrons collide with the helium atoms and excite
them to higher energy levels since the levels are meta stable energy levels He atoms spend
sufficiently long time and collide with Neon atoms in the ground level E 1 . Then Neon atoms are
excited to the higher energy levels E4 & E6 and helium atoms are de excited to the ground energy
level E1.

Since E6 & E4 of Ne atom are metastable states, population inversion takes place at these levels.
The stimulated emission takes place between E6 to E3 gives a laser light of wavelength 632.8nm
(6328A0) and the stimulated emission between E6 and E5 gives a laser light of wave length
3.39µm. Another stimulated emission between E4 to E3 gives a laser light of wave length
1.15µm. The Neon atoms undergo spontaneous emission from E3 toE2 and E5 to E2. Finally the
Neon atoms are returned to the ground state E1 from E2 by non-radeative diffusion and collision
process. After arriving at the ground state, once again the Neon atoms are raised to E6 & E4 by
excited Helium atoms thus we can get continuous output from He-Ne laser.
Semiconductor laser (Gallium Arsenide Diode Laser or Homojunction laser):
Semiconductor laser is also known as diode laser.
Principle: In the case of direct band gap semiconductors there is a large possibility for direct
recombination of hole and electron emitting a photon. GaAs is a direct band gap semiconductor and
hence it is used to make lasers and light emitting diodes. The wave lengths of the emitted light
depend on the band gap of the material.
Constructions: A p-n junction provides the active medium. To obtain laser action population
inversion is to be created by providing optical feedback. Optical feedback is provided by the end
faces of the junction. As the thickness of the P-N junction layer is very narrow at the junction and
the sides are well polished and parallel to each other. Since the refractive index of GaAs is high the
reflectance at the material air interface is sufficiently large so that the external mirrors are not
necessary to produce multiple reflections. To obtain stimulated emission, there must be a region in
the device where there are many excited electrons and holes present together. This is achieved by
forming a homojunction from very heavily doped n and p materials. In such n-type material, the
Fermi level lies within the conduction band. Similarly, for the p-type material Fermi level lies in the
valence band.

When the junction is forward biased, the electrons and holes are injected across the junction in
sufficient numbers to create a population inversion in a narrow zone called the active region.
Working: When the junction is forward biased with a voltage that is nearly equal to the energy gap
voltage (Eg/e), a large current of order104 amp/cm2 is passed through the narrow junction to provide
excitation. Thus the electrons and holes injected from N side and P side respectively. The
continuous injection of charge carries the population inversion of minority carriers in N and P sides
respectively.
The excess minority electrons in the conduction band of P - layers recombine with the majority
holes in the valence band of P-layer emitting light photons similarly the excess minority holes in the
valence band of N- layers recombine with the majority electrons in the conduction band of N- layer
emitting light photons.
The emitted photons increase the rate of recombination of injected electrons from the N- region and
holes in P- region. Thus more number of photons are produced hence the stimulated emission take
place, light is amplified.

The wave length of emitted radiation depends upon the concentration of donor and acceptor atoms.
The GaAs laser emits light at 900nm (infrared) while a GaAsP laser radiates at 650nm (visible red
region). The efficiency of laser emission increases, when we cool the GaAs diode.
Drawbacks:-
1. Only pulsed laser output is obtained
2. Laser output has large divergence
3. Poor coherence
Application of lasers:
Lasers in scientific research:
1) Lasers are used to clean delicate pieces of art, develop hidden finger prints.
2) Laser is used in the fields of 3D photography called holography.
3) Using lasers the internal structure of micro organisms and cells are studied very accurately
4) Lasers are used to produce certain chemical reactions.
Laser in Medicine:
1) The heating action of a laser beam used to remove diseased body tissue.
2) Lasers are used for elimination of moles and tumours, which are developing in the skin tissue.
3) Lasers are also used for the treatment of liver and lungs.
4) Laser beam is used to correct the retinal detachment by eye specialist.
Laser in Communication:
1) More amounts of data can be sent due to the large band width of semiconductor lasers.
2) More channels can be simultaneously transmitted.
3) Signals cannot be tapped.
4) Atmospheric pollutants concentration, ozone concentration and water vapour concentration can
be measured.
Lasers in Industry: Lasers are used:
1) To blast holes in diamonds and hard steel
2) To cut, drill, welding and remove metal from surfaces
3) To measure distance to making maps by surveyors
4) For cutting and drilling of metals and non metals such a ceramics plastics glass

UNIT V
NANO SCIENCE
In 1959, Richard Feynman made a statement 'there is plenty of room at the bottom'. Based on his
study he manipulated smaller units of matter. He proposed that "we can arrange the atoms the
way we want, the very atoms, all the way down". The term 'nanotechnology' was coined by
Norio Taniguchi at the University of Tokyo. Nano means 10-9. A nano meter is one thousand
millionth of a meter (i.e. 10-9 m).
Nanomaterials could be defined as those materials which have structured components with size
less than 100nm at least in one dimension. Any bulk material we take, its size can be expressed
in 3-dimensions. Any planer material, its area can be expressed in 2-dimension. Any linear
material, its length can be expressed in 1-dimension.
Materials that are nano scale in 1-dimension or layers, such as thin films or surface coatings.
Materials that are nano scale in 2-dimensions include nanowires and nanotubes.
Materials that are nano scale in 3-dimensions are particles like precipitates, colloids and quantum
dots.
Nanoscience: it can be defined as the study of the phenomena and manipulation of materials at
atomic, molecular and macromolecular scales, where properties differ significantly from those at
a bulk scale.
Nanotechnology: It can be defined as the design, characterization, production and application of
structures, devices and systems by controlling shape and size at the nano meter scale. It is also
defined as "A branch that deals with the design and manufacture of extremely small electronic
circuits and mechanical devices built at molecular level of matter. Now nanotechnology crosses
and unites academic fields such as Physics, Chemistry, Computer science and biotechnology.
Classification of Nanomaterials:
Nanomaterials generally fall into two categories: fullerenes and inorganic nanoparticles.
Fullerene:
The fullerenes are a class of allotropes of carbon which are graphene sheets rolled into tubes or
hollow spheres. Spherical fullerenes are also called buckyballs, and cylindrical one are called

carbon nanotubes or buckytubes. Fullerenes are similar in structure to graphite, but they may
contain pentagonal rings.
The first fullerene discovered was buckminsterfullerene C60 in 1985.
Carbon nanotubes (CNTs) are allotropes of carbon with a cylindrical nanostructure. Nanotubes
are members of the fullerene structural family. Nanotubes are categorized as single-walled
nanotubes (SWNTs) and multi-walled nanotubes (MWNTs) as shown in figure (a) and (b).
These cylindrical carbon molecules have novel properties. They exhibit extraordinary strength
and unique electrical properties.
Properties of nano particles:

The properties of nano scale materials are very much different from those at a larger scale. Two
principal factors that cause the properties to differ significantly are increased relative surface
area to volume ratio and quantum confinement effects. These can enhance or change properties
such as reactivity, strength and electrical characteristics.
1. Increase in surface area to volume ratio:
Nano materials have relatively larger surface area when compared to the volume of the bulk
material.
Therefore, when the given volume is divided into smaller pieces, the surface area increases.
To show this, let us consider a sphere of radius “r”,
Its surface area = 4πr2
Its volume = (4/3) πr3
Surface area to volume ratio = (3/r)
Thus when the radius of the sphere decreases, its surface area to volume ratio increases.
The same can be explained for the cube of side 1m. The surface area of the cube is 6m2 and the
volume of the cube is 1m3. Therefore the surface area to volume ratio is 6/1.

When the volume of the cube is divided into 8 pieces, the side of each cube will be (½)m. Then
its surface area = (1/2)*(1/2)*6*8= 12m2. Therefore the surface area to volume ratio = 12/1.
When the same volume is divided into eight pieces its surface area becomes 18m2.
Thus we find that when the given volume is divided into smaller pieces, the surface area
increases. Hence as particle size decreases, greater proportions of atoms are found at the surface
compared to those inside. Thus nano particles have much greater surface to volume ratio. It
makes material more chemically reactive. As growth and catalytic chemical reaction occur at
surfaces, then given mass of material in nano particulate form will be much more reactive than
the same mass of bulk material. This affects their strength or electrical properties.
2. Quantum confinement effects
When atoms are isolated, energy levels are discrete or discontinuous. When very large number of
atoms is closely packed to form a solid, the energy levels split and form bands. Nano materials
represent intermediate stage. When dimensions of potential well and potential box are of the
order of de-Broglie wave length of electrons or mean free path of electrons, then energy levels of
electrons changes. This effect is called Quantum confinement effect.
When the material is in sufficiently small size, organization of energy levels into which electrons
can climb or fall changes. Specifically, the phenomenon results from electrons and holes being
squeezed into a dimension that approaches a critical quantum measurement called the exciton
Bohr radius. These can affect the optical, electrical and magnetic behaviour of materials.
Synthesis of Nanomaterials:
Material can be produced that are nanoscale in one dimension like thin surface coatings in two
dimensions like nanowires and nanotubes or in 3 dimensions like nanoparticles
Nano materials can be synthesized by' top down' techniques producing very small structures
from larger pieces of material. One way is to do mechanical crushing of solid into fine nano
powder by ball milling.
Nanomaterials may also be synthesized by 'bottom up' techniques, atom by atom or molecule by
molecule. One way of doing this is to allow the atoms or molecules arranges themselves into a
structure due to their natural properties
Ex: - Crystals growth
Preparation or Synthesis methods:
There are many methods in Bottom-up fabrication to produce nanomaterials. They are
1. Chemical vapour deposition
2. Sol-Gel method
3. Physical vapour deposition, etc
1. Sol - Gel:
• The sol gel process is a wet-chemical technique.
• The starting material from a chemical solution leads to formation of colloidal suspensions
known as sol.
• Then the sol evolves towards the formation of an inorganic network containing a liquid
phase called the gel.
• The removal of liquid phase from the sol yields the gel.
• Particle size and shape are controlled by the sol to gel transitions.
• The starting material is processed with water in a alkaline solvent.
• The material undergoes a hydrolysis and polycondensation reaction which leads to the
formation of collide.
• The colloid system composed of solid particles is dispersed in a solvent containing
particle size from 1nm to 1µm.
• The sol is then evolved to from an inorganic network containing a liquid phase(gel).

• Drying of the gel, by thermal evaporation is to form xerogel, and if the solvent is
extracted under super critical conditions form a Aero gel.
• The sol can be further processed to obtain the substrate in the form of a film either by
dipping (or) spinning by calcinations.
The rate of hydrolysis and condensation reactions are governed by various factors such as PH,
temperature, H2O/Si molar ratio, nature and concentration of catalyst and process of drying.
Under proper conditions spherical nanoparticles are produced.
2. Physical Vapor Deposition (PVD)
It is a collective set of processes used to deposit thin layers of material, typically in the range of
few nanometers to several micrometers. This technique consist of three fundamental steps as
shown in the figure,

1. Vaporization of the material from a solid source assisted by high temperature vacuum or
gaseous plasma.
2. Transportation of the vapor in vacuum or partial vacuum to the substrate surface.
3. Condensation onto the substrate to generate thin films.
Different PVD technologies utilize the same three fundamental steps but differ in the methods
used to generate and deposit material. The two most common PVD processes are thermal
evaporation and sputtering.
Thermal evaporation is a deposition technique that relies on vaporization of source material by

heating the material using appropriate methods in vacuum.
Sputtering is a plasma-assisted technique that creates a vapor from the source target through
bombardment with accelerated gaseous ions (typically Argon).
In both evaporation and sputtering, the resulting vapor phase is subsequently deposited onto the
desired substrate through a condensation mechanism.
PVD is used in a variety of applications, including fabrication of microelectronic devices, Inter-

connects, battery and fuel cell electrodes, diffusion barriers, optical and conductive coatings, and
surface modifications.
3. BALL MILLING (MECHANICAL CRUSHING): (TOP-DOWN METHOD)

In this method, small balls are allowed to rotate around the inside of a drum and then fall on a
solid with gravity force and crush the solid into nanocrystallites. Ball milling can be used to
prepare a wide range of elemental and oxide powders. Ball milling is the preferred method for
preparing metal oxides. For example, Iron with grain sizes of 10-30nm can be formed. Other
crystallites, such as iron nitrites, can be made using ammonia gas.
Fig: Ball milling-very heavy small balls inside the rotating drum crush the solid into
nanopowder.

Variations of properties of nano materials
The physical, electronic, magnetic and chemical properties of materials depend on size. Small
particles behave differently from those of individual atoms or bulk.
1. Physical properties: The effect of reducing the bulk into particle size is to create more surface
sites i.e. to increase the surface to volume ratio. This changes the surface pressure and results in a
change in the inter particle spacing. Thus the inter atomic spacing decreases with size.
The change in the inter particle spacing and the large surface to volume ratio in particle have a
combined effect on material properties. Variation in the surface free energy changes the chemical
potential. This affects the thermodynamic properties like melting point. The melting point
decreases with size and at very small sizes the decrease is faster.
2. Chemical properties: the large surface to volume ratio, the variations in geometry and
electronic structure has a strong effect on catalytic properties. The reactivity of small clusters
increases rapidly even when the magnitude of the cluster size is changed only by a few atoms.
Another important application is hydrogen storage in metals. Most metals do not absorb,
hydrogen is typically absorbed dissociatively on surfaces with hydrogen- to- metal atom ratio of
one. This limit is significantly enhanced in small sizes. The small positively charged clusters of
Ni, Pd and Pt and containing between 2 and 60 atoms decreases with increasing cluster size. This
shows that small particles may be very useful in hydrogen storage devices in metals.
3. Electrical properties: The ionization potential at small sizes is higher than that for the bulk
and show marked fluctuations as function of size. Due to quantum confinement the electronic
bands in metals become narrower. The delocalized electronic states are transformed to more
localized molecular bands and these bands can be altered by the passage of current through these
materials or by the application of an electric field.
In nano ceramics and magnetic nano composites the electrical conductivity increases with
reduction in particle size whereas in metals, electrical conductivity decreases.

4. Optical properties: Depending on the particle size, different colours are seen. Gold nano
spheres of 100nm appear orange in colour while 50nm nano spheres appear green in colour. If
semiconductor particles are made small enough, quantum effects come into play, which limits
the energies at which electrons and holes can exist in the particles. As energy is related to
wavelength or colour, the optical properties of the particles can be finely tuned depending on its
size. Thus particles can be made to emit or absorb specific wavelength of light, merely by
controlling their size.
An electro chromic device consists of materials in which an optical absorption band can be
introduced or existing band can be altered by the passage of current through the materials, or by
the application of an electric field. They are similar to liquid crystal displays (LCD) commonly
used in calculator and watches. The resolution, brightness and contrast of these devices depend
on tungstic acid gel's grain size.
5. Magnetic properties: The strength of a magnet is measured in terms of coercivity and
saturation magnetization values. These values increase with a decrease in the grain size and an
increase in the specific surface area (surface area per unit volume) of the grains.
Fig: Deviation from the bulk magnetic moment in (a) Fe, (b) Co, and (c) Ni as a function of
nearest neighbor coordination (in various structures)
In small particles a large number or fraction of the atoms reside at the surface. These atoms have
lower coordination number than the interior atoms. As the coordination number decreases, the
moment increases towards the atomic value there is small particles are more magnetic than the
bulk material.
Nano particle of even non magnetic solids are found to be magnetic. It has been found
theoretically and experimentally that the magnetism special to small sizes and disappears in
clusters. At small sizes, the clusters become spontaneously magnetic.

6. Mechanical properties: If the grains are nano scale in size, the interface area within the
material greatly increases, which enhances its strength. Because of the nano size many
mechanical properties like hardness, elastic modulus, fracture toughness, scratch resistance,
fatigue strength are modified.
The presence of extrinsic defects such as pores and cracks may be responsible for low values of
E (Young's modulus) in nano crystalline materials. The intrinsic elastic modulli of nano
structured materials are essentially the same as those for conventional grain size material until
the grain size becomes very small. At lower grain size, the no. of atoms associated with the grain
boundaries and triple junctions become very large. The hardness, strength and deformation
behaviour of nano crystalline materials is unique and not yet well understood.
Superplasticity is the capability of some polycrystalline materials to exhibit very large texture
deformations without fracture. Superplasticity has been observed somewhat low temperatures
and at higher strain rates in nano crystalline material.
Fig: Ratio of young’s modulus (E) of nanocrystalline materials to (Eo) of conventional grain size
materials as a function of grain size.
Characterization of Nanoparticles:
Nanoparticles can be characterized by both X-ray diffraction (XRD) and Transmission Electron
Microscopy (TEM) techniques.
Transmission Electron Microscope (TEM):

A schematic representation of a TEM is shown below. Each component/part is labeled and their
functions are briefed below.
• The electron gun produces a stream of monochromatic electrons.
• This stream is focused to a small coherent beam by the first and second condenser lenses.
• The condenser aperture knocks off high angle electrons.
• The beam strikes the specimen.
• The transmitted portion is focused by the objective lens into an image.
• Objective aperture enhances the contrast by blocking out high angle diffracted electrons.
• The electron gun produces a stream of monochromatic electrons.
• This stream is focused to a small coherent beam by the first and second condenser lenses.
• The condenser aperture knocks off high angle electrons.
• The beam strikes the specimen.
• The transmitted portion is focused by the objective lens into an image.
• Objective aperture enhances the contrast by blocking out high angle diffracted electrons.
Thin specimen interactions used in TEM

Unscattered electron:
These are electrons transmitted through a thin specimen without any interactions occurring inside
the specimen. The intensity of transmitted unscattered electrons is inversely proportional to the
thickness of the specimen. Hence thicker areas of the specimen appear darker than the thinner
areas.

Elastically scattered electrons:
These are electrons that are scattered [deflected from their original path] by atoms in the
specimen without loss of energy. These scattered electrons are then transmitted through the
remaining portions of the specimen. The scattered electrons follow Braggs law;
2dsinθ=nλ
hence by collecting the scattered electrons at different angles, one can get information about the
orientation , atomic arrangements and phases present.
In elastically scattered electrons:
These are electrons that interact with specimen atoms in an inelastic manner, loosing energy.
Then they are transmitted through the remaining portions of the specimen. The inelastic loss of
energy is characteristic of the elements that have interacted with the specimen. Hence these
energies are unique to bonding state of each element. Hence this can be used to interact both
compositional and bonding information.
TEM Analysis:
A TEM image of the silver nano particles studied using XRD in section. The “Ag” nano particles
are spherical in shape with a smooth surface morphology. The diameter of the nano particles is
found to be approximately 15nm.TEM image also shows that the produced nano particles are
more or less uniform in size and shape.

Applications:
TEM gives the following useful information’s:
1. Morphology: The size and arrangement of the particles as well as their relationship to one
another on the scale of atomic diameter.
2. Crystallographic information: The arrangement of atoms in the specimen and their degree
of order , detection of atomic scale defects a few nanometers in diameter.
3. Compositional information: The elements and compounds the sample is composed of and
their relative ratios.
APPLICATION OF NANOMATERIALS:
1. Engineering: i).Wear protection for tools and machines (anti blocking coatings, scratch
resistant coatings on plastic parts). ii) Lubricant - free bearings.
2. Electronic industry: Data memory (MRAM, GMR-HD), Displays (OLED, FED), Laser
diodes, Glass fibers.
3. Automotive industry: Light weight construction, Painting (fillers, base coat, clear coat),
Sensors, Coating for wind screen and car bodies.
4. Construction: Construction materials, Thermal insulation, Flame retardants.
5. Chemical industry: Fillers for painting systems, Coating systems based on nano composites.
Impregnation of papers, Magnetic Fluids.
6. Medicine: Drug delivery systems, Agents in cancer therapy, Anti microbial agents and
coatings, Medical rapid tests Active agents.
7. Energy: Fuel cells, Solar cells, batteries, Capacitors.
8. Cosmetics: Sun protection, Skin creams, Tooth paste, Lipsticks.

Engineering Physics Complete Notes

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UNIT – I

CRYSTALLOGRAPHY AND X-RAY DIFFRACTION

(a) Lattice (b) Basis (c) Crystal structure

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Seven crystal systems:

1. Cubic crystal system :

2. Tetragonal crystal system :

3. Orthorhombic crystal system :

4. Monoclinic crystal system :

7. Hexagonal crystal system :

2 Tetragonal a=b ≠c NiSO4, SnC2

5 Triclinic a≠b≠c α CuSO4,K2SO4

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(i). Simple Tetragonal (ii) Body centred Tetragonal

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(i). Simple Monoclinic (ii). Base centred Monoclinic

5. Triclinic crystals: 6. Trigonal crystals: 7. Hexagonal crystals:

(i). Simple Triclinic (i). Simple Trigonoal (i). Simple Hexagonal

Unit cell Parameters:

1. Nearest neighbor distance:

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In this structure every atom is surrounded by 12 equidistance nearest neighbors. Hence

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Fig. 1(a) Fig. 1 (b)

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IMPORTANCE OF MILLER INDICES:

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Interplanar Spacing of an orthogonal crystal systems:

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From equations (3) and (4),

Equation (5) represents distance between two successive planes.

Lattice constant for cubic system:

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Vacancy parent atom Impurity atom interstitial impurity

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Fig 2(a): Frenkel defect Fig 2 (b): Schottky defect

Zn2+ O2- Zn2+ 2+

fig 3: Electronic defect.

Energy of formation of vacancy:

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Fig. 1(c): +ve and –ve edge dislocations

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Fig. 2(c) :Screw Dislocation

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X-ray diffraction by Laue’s method :

Diffraction pattern due to transmission method

Diffraction pattern due to back reflection method

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Fig: Electric dipole

Where  is permittivity of the medium, 0 is permittivity of the free space

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The capacitance of the capacitor without dielectric.

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We know the Pe 0 (r 1) E