MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

MATERIAL SCIENCE
UNIT WISE LECTURE NOTES

K.KRAGALASKHMI M.Sc.,M.Phil.
Asst.Professor, Dept. of Physics
Sri Venkatehwaraa College of Engg & Tech
Pondicherry-605 502.

*********

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 1

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

MATERIAL SCIENCE

UNIT I - CRYSTAL STRUCTURE AND LATTICE DEFECTS

Crystal structure - Bravais Lattices , Crystal Systems - Coordination Number, Atomic Radius,
Packing Factor for FCC & HCP structures – Miller Indices- Powder X Ray Diffraction Method
Lattice defects – Qualitative ideas of point, line, surface and volume defects

UNIT II – DIELECTRIC PROPERTIES

Dielectric Polarization and Mechanism –Temperature dependence of polarization, Internal or

local Field - Clausius-Mossotti relation. Basic ideas of Dielectric loss - frequency dependence of
dielectric constant – Measurement of Dielectric constant and loss using Scherring bridge –
Elementary ideas of Piezoelectrics, Ferroelectrics and Pyroelectric materials and Applications

UNIT III – MAGNETIC PROPERTIES

Origin of atomic magnetic moment – Bohr magneton-Elementary Ideas of classification

of magnetic materials (Dia, Para, Ferro, antiferro & Ferri). – Quantum theory of Para &
Ferro Magnetism – Domain Theory of Hysteresis – Heisenberg Theory of Exchange Interaction
(without derivation) – Qualitative ideas of Anti ferromagnetic Ordering –
Structure and Properties of Ferrites – Properties of Soft & Hard Magnetic Materials –
Applications. Magnetic data storage – Magnetic tapes, Hard disks, Magneto optical
recording

UNIT IV – SEMICONDUCTORS AND SUPERCONDUCTORS

Semiconductors -Derivation of Carrier concentration in intrinsic Semiconductors –Basic

ideas of Electrical conductivity in intrinsic and extrinsic semiconductors (without derivations)
-temperature dependence of carrier concentration and electrical conductivity in semiconductors
(qualitative ideas), Hall effect in Semiconductors -Application of Hall Effect, Basic Ideas of
Compound Semiconductors (II-VI & III-V)

Superconductivity - Basic concepts – transition temperature – Meissener effect – Type I and II

superconductors – High Temperature Superconductors – 123 superconductor – Applications of
superconductors.

UNIT V – ADVANCED MATERIALS

Liquid Crystals – Types – Application as Display Devices

Metallic Glasses – preparation by melt spinning. Twin roller system, properties and
applications
Shape Memory alloys (SMA), Shape memory effect, Properties and applications of SMA
Nanomaterials- Nano materials (one, Two & three Dimensional) –Methods of synthesis
(PVD, CVD, Laser Ablation, Solgel, Ball-milling Techniques), Properties and applications
of nanomaterials. carbon nanotubes– synthesis, Properties and applications.

**********

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 2

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

CRYSTALLOGRAPHY

The study of geometric form and other physical propertes of crystalline solids by using
X-rays or neutron beams or electron beams etc are termed as crystallography.

CRYSTALLINE SOLID OR CRYSTAL

Crystalline solid are those in which the consttuent atoms or molecules arranged in an
orderly fashion throughout in a three dimensional patern.

Ex: Cu, Ag, NaCl, Si, Ge, Quatrz

TYPES OF CRYSTAL

i) Single crystal, in which the solid contains only one crystal.

ii) Poly crystal, which has aggregate of many small crystals or grains

NON CYSTALLINE SOLID OR AMORPHOUS

In amorphous solids the atoms or molecules not arranged in an orderly fashion.
Ex: Plastcs , rubber, glass..

FUNDAMENTALS OF CRYSTAL STRUCTURE

1. LATTICE
Lattice is defned as an array of points which are imaginarily kept to represent the
positon of atoms in the crystals.
2. SPACE LATTICE
It is defned as three dimensional collecton of points in space.
3. LATTICE POINT
Lattice point denote positon of the atoms or molecules in the crystal.
4. BASIS OR MOTIF
The repeatng unit assembly of atoms or molecules located at each lattice point is called
Basis.
5. CRYSTAL STRUCTURE
A crystal structure is formed by associatng a basis to every latice point in a space latice.
i.e., crystal structure = basis + space lattice.

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 3

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

6. LATTICE PLANES
A set of parallel and equally spaced planes in a space lattice are called lattice planes.
7. UNIT CELL
A unit cell is defined as smallest volume of the solid from which the entre crystal can be
formed by the translatonal repettons in three dimensions.

8. LATTICE PARAMETERS OR UNIT CELL PARAMETERS

Crystallographic axes: The lines drawn parallel to the lines of
intersecton of any three faces of the unit cell which do not lie in
the same plane are called crystallographic axes (x, y, z).
Primities: The intercepts a, b, c of a unit cell along the three
coordinate axes x, y, z are called as primitves.
Interfacial (or) inter axial angles : The angle between the three axes α, β and γ are
known as interfacial angles.
Lattice parameters : The primitves (a, b and c) and interfacial angles (α, β and γ)
together
known as lattice parameters.
9. PRIMITIVE CELL
It is the simplest type of unit cell. It contains one latice point per unit cell.
Ex: Simple cubic
10. NON PRIMITIVE CELL
If there are more than one lattice point in an unit cell, it is called as non-primitve cell.
Ex: BCC, FCC,HCP
BRAVAIS LATTICE
The 14 possible ways of arranging latice points in space lattice. All the lattice points
have exactly the same surroundings. These 14 space lattices are called Bravais latices.
Unit cell
S.No Crystal System Braiais Lattice Examples
Parameters
1. a≠ b≠ c
Triclinic Simple CuSo4
α≠ β ≠γ≠90°
2. Simple a≠ b≠ c
Monoclinic FeSo4
Base-centred α= β =90°≠γ
3. Simple
Body-centred a≠ b≠ c
Orthorhombic BaSo4, MgSo4
Face-centred α= β = γ=90°
Base-centred
4. Simple
a= b≠ c NiSo4
Tetragonal Body-centred
α= β = γ=90°

5. Simple a= b≠ c
Hexagonal Tourmaline, quartz
α= β =90°γ=120°
6. Trigonal Simple a= b= c
CaSo4, Calcite
(rhombohedral) α= β = γ≠90°
7. Cubic Simple a= b= c NaCl
Body-centred α= β = γ=90°
Face-centred

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 4

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

CRYSTAL SYSTEMS AND BRAVAIS LATTICE

PARAMETERS DETERMINING THE CRYSTAL STRUCTURE OF MATERIALS

1. NUMBER OF ATOMS PER UNIT CELL

The total number of atoms present in or shared by an unit cell is known as number of
atoms per unit cell.
2. ATOMIC RADIUS
It is defned as half of the distance between the two nearest neighbouring atoms in a
crystal.
3. COORDINATION NUMBER
It is the number of nearest neighbouring atoms to a partcular atom at equal
distances in a crystal structure.
Ex: The coordinaton number for SC‐6, BCC – 8, FCC‐12,HCP‐12.

4. ATOMIC PACKING FACTOR (APF) (OR) PACKING DENSITY (OR) DENSITY OF PACKING
It is defned as the rato between the volumes occupied by the total number of
atoms per unit cell to the total volume of the unit cell.
volume occupied by thetotal number of atoms per un it cell v
APF= =
Total volume of the uni t cell V

Total number of atoms per un i t cell X Volume of one atom

APF=
Total volume of the uni t cell

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 5

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

FACE CENTERED CUBIC STRUCTURE- FCC

 The unit cell of this structure contains eight corner

atoms and six face cantered atoms.
 Each atom surrounded by 12 nearest neighbouring
atoms. All the atoms are arranged in closely packed
planes are called octahedral planes.
 It has a stacking sequence of ABC, ABC, and ABC....

i) Coordinaton No:
To calculate coordinaton number, consider corner atom as
partcular atom which is surrounded by four face centre atom in
its own plane. The plane just above the corner atom has four
face centred atom. Similarly four face centred atom in its botom
plane.
Coordinaton No: 4+4+4 = 12 atoms

ii) Atomic radius:

Let a be the side of the cube.
From ∆ ABC AC2 = AB2 + BC2
= a2 + a2
= 2a2 (AC=4r)
2 2
(4r) = 2a
16r2 = 2a2
a2 a
r 2= r=
8 2 √2
iii) Number of per unit cell:
Total no.atom per unit cell = corner atom + face centred atom
= 1/8 x 8 +1/2 x 6 = 1+3 = 4 atoms/unit cell.
ii) Atomic packing factor:
Volume occupied by the
total no.atom per unit cell v = volume of one atom X total no. atoms per unit cell.
4
v= π r 3 X 4
3
3 3 3
16 a 16 a πa
v= π ( ) ¿ π v¿
3 2√2 3 8 X 2√2 3 √2

Volume of unit cell V = a3

π a3
v π
APF= 3 √2 ¿ = 0.74 APF=74%
V ¿ 3 3 √2
a
Since the packing density is high, the FCC structure has closely (or) tghtly packed structure.

HEXAGONAL CLOSELY PACKED STRUCTURE – HCP

 The unit cell of this structure contains three layers of atoms.

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 6

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

 At the botom layer, the centre atom has six nearest neighbouring atom. Further the
middle layer which is at a distance C/2 from botom layer has three atoms.
 Similarly, in third layer centre atom surrounded by six nearest corner atoms. It has a
stacking sequence of AB, AB, and AB....

i) Coordinaton No:
Consider centre atom as partcular atom
Same plane – 6 atom.
Top plane - 3 atom
botom plane - 3 atom
Coordinaton No = 6+3+3+3 = 12 atoms
ii) C/a Rato:
Let c be the height of the HCP
a be the side of the HCP
c/2 be the distance of middle layer from the botom layer.
'
AA
From ∆ AA’B, cos 30 °=
AB
'
A A = ABcos 30° { AB=a }
3 √3 }
A A' =a √ '
{ O O =a
2 2
2
AX= A A '
3
2 3 a
AX= x a √ AX=
3 2 √3
From ∆ ACX, AC2 = AX2 + CX2
2 2
a C
a 2=( )( )
√3
+
2
a2 C 2 C2 a2 C2 2 a2 C2 8
a 2= + ; =a 2− ; = ; =
3 4 4 3 4 3 a2 3

c 8 c
a √
=
3 a
iii) Number of atoms per unit cell:
=1.633

Top layer = corner atom + centre atom

= 1/6 x 6 +1/2 = 1+1/2 = 3/2 atoms
Similarily
botom layer = 3/2 atoms
middle layer = 3 atoms
Total no.atom per unit cell = Top layer + botom layer + middle layer =3/2 + 3/2 +3
= 6 atoms/unit cell.
ii) Volume occupied by total number of atoms per unit cell- i:
v = volume of one atom X total no. atoms per unit cell.
4
¿ πr3X 6
3
a
Atomic radius a=2r r =
2
K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 7
MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

3 3
4 a 6 x 4 x πx a 3
¿6 x π( ) ¿ v=π a
3 2 3 x8
i) Volume of HCP- V:
Area of ∆ ABO = ½ x base x height

= ½ x AB x OO’
'
{ O O =a
√3 }
2
3 3
¿½ x ax a √ ¿ a2 √
2 4
Area of base = 6 x Area of ∆ ABO
3 3
¿ 6 X a2 √ ¿ 3 a2 √
4 2
Volume of HCP V= Area of base x height of HCP

3
V =3 a2 √ c
2

c 8
vi) Atomic packing factor-APF: {
a
=
√
3
}

3
πa 3
v ¿ π a x2 2π a 2π 3 π
APF=
V 3
3a √ c
2
2
¿ 2
3 a √3 c
¿ ( )
3 √3 c
¿
3 √3
X
8 √ ¿
3 √2
= 0.74

APF = 74%
Since the packing density is high, the HCP structure has closely (or) tghtly packed structure.

MILLER INDICES (h k l)
Miller indices is defned as the reciprocal of the intercepts made by the plane on the
crystallographic axes which are reduced to smallest numbers.

Procedure for fnding Miller indices:

 Choose a system of three coordinate axes preferably along

crystallographic axes.
 Find the intercepts made by the plane ABC along the three axes
and express the intercepts in terms of multples of axial length.
OA:OB:OC = pa:qb:rc
 Find the coefficients of the intercepts, p:q:r
 Find the reciprocal of these numbers, 1/p:1/q:1/r
 Convert these reciprocals into whole numbers by multplying with their LCM to get
smallest numbers. This gives the miller indices of the plane (hkl).

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 8

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

INTERPLANAR DISTANCE OR PERPENICULAR DISTANCE BETWEEN TWO PARALLEL PLANES

a
OR PROVE THAT‘d’ SPACING d=
√ h +k 2+l2
2

Let us consider a cubic lattice with two planes ABC and A’B’C’.
α, β , γ be the interfacial angles.
Let ON=d1- distance between origin and frst plane ABC
OM=d2- distance between origin and second plane A’B’C’.
NM=d- distance between successive planes ABC and A’B’C’.

To fnd d1
Let OA,OB and OC be the intercepts made by the plane ABC on the three axis.
a a a
OA= OB= OC=
h k l
ON d 1 d 1 h
c os α = = =
From ∆ OAN, OA a a
h
ON d 1 d 1 k
c os β= = =
OB a a
k
ON d 1 d 1 l
c os γ= = =
OC a a
l
From the law of directon of cosines c os 2 α +c os2 β+ c os 2 γ =1
d1h 2 d1k 2 d1l 2
( ) +( ) +( ) =1
a a a

d 12 h2 d 12 k 2 d 12 l 2
+ 2 + 2 =1
a2 a a
d 12 ( h2+ k 2 +l 2)
=1
a2
2
a a
d 12= 2 2 2 d 1= 2 2 2
(h + k +l ) √ h + k +l

To fnd d2
Let OA’,OB’ and OC’ be the intercepts made by the plane ABC on the
three axis.
2a 2a 2a
OA ' = OB '= OC ' =
h k l
ON d 2 d 2 h
c os α = = =
From ∆ OAN, OA ' 2a 2a
h
ON d 2 d 2 k
c os β= = =
OB ' 2 a 2a
k

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 9

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

ON d 2 d 2l
c os γ= = =
OC ' 2 a 2 a
l
From the law of directon of cosines c os 2 α +c os2 β+ c os 2 γ =1
d2h 2 d2k 2 d2l 2
( ) +( ) +( ) =1
2a 2a 2a

d 22 ( h2+ k 2 +l 2)
=1
4 a2
2
4a 2a
d 22= 2 2 2 d 2=
(h + k + l ) √ h + k 2 +l2
2

Interplanar distance d
Interplanar distance is the distance between two successive planes in a crystal.
NM= OM-ON
d = d2-d1
2a a a
d= 2 2 2 − 2 2 2 d= 2 2 2
√ h +k +l √ h + k +l √ h +k +l
RELATION BETWEEN LATTICE CONSTANT AND DENSITY OF CRYSTAL
Let us consider cubic crystal of following parameters
Let a-be the lattice constant
n- Number of atoms per unit cell
M- atomic weight of crystal
N- Avogadro’s number
ρ- density of crystal
M
Mass of each molecule ¿
N
M
Mass of n molecules ¿ n Volume of the unit cell=a 3
N
mass of an unit cell
Density of the unit cell is ρ=
volume of an unit cell

M
n 3 Mn
N Mn a=
ρ= 3 = Nρ
a N a3
1/ 3
atomic weight x Number of atoms per unit cell
lattice constant a= [
Avogadro ’ s number x Density of theunit cell ]
POWDER X-RAY DIFFRACTION METHOD OR DEBYE SCHERRER METHOD OF CRYSTAL
STRUCTURE DETERMINATION.

Principle
This technique is based on the principle of Bragg’s refecton. When a monochromatc
beam of X- rays made to fall on millions of tny crystals having diferent orientatons, all
possible planes will be available for Bragg’s refecton.

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 10

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

Powder difractometer- Debye- Scherrer Camera

The monochromatc beam of X- rays emerging from an X-ray tube is passed through the
lead slits S1 and S2. The slits produce fne beam of X-rays. This beam is made to fall on a thin
walled capillary tube, in which the given sample is taken in the form of powder. The
photographic flm is mounted in a circular frame.
The incident X-ray beams are refected by the diferent crystal planes. The refected rays
will form a cone of X-rays with Bragg’s angle of 4θ, whose axis lies along the directon of the
incident beam. The exposed flm is found to have concentric rings.

In the concentric rings,

D- distance between two difracton lines corresponding to a partcular plane.

R- distance between the specimen and flm.
4θ = D/R radians
The interplanar distance d is then determined using Bragg’s equaton,
2d sinθ = nλ
The calculaton of inter atomic distance and the miller indices for a cubic crystal is given
below.
a
d= 2 2 2
√ h + k +l
Substtutng the values of d in Bragg’s equaton, we get
2a
sinθ = nλ
√ h + k 2 +l2
2

Squaring and rearranging, we get

2 2
2 n λ 2 2 2
Sin θ = 2 (h +k +l )
4a

Sin2 θ = K2 (h2 +k 2+l 2 )

2 n2 λ2
Where K is a constant and is equal to
4 a2
The constant K2 is determined by fnding the values of Sin2 θ for all the concentric rings. By
measuring the radius of the camera and the diameter of circular rings, the values of θ is
determined.
The constant K2 is used to fnd the lattice constant a. The cell constant a is given by the
nλ
relaton a=
2K

Adiantages
 There is no need of single crystals
K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 11
MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

 It is used to fnd the miller indices

 The lattice parameters are accurately determined.

Disadiantages
 This method is not suitable for the determinaton of structure of crystals because of
multplicity factor and the difficulty in indexing.

CRYSTAL DEFECTS OR IMPERFECTIONS

Defniton
Any deviaton from stoichiometric, chemically pure, perfect crystal is called as an
imperfecton
Classifcaton of Defects
I . Point defects (zero dimensional)
a) Stoichiometric
i) Frenkel defect ii) schotky defect

b) Non Stoichiometric
1 ) Metal ion excess defect
1. Due to vacancy 2.Due to extra ion
2) Metal ion defciency defect
1. Due to missing ion 2. Due to presence of impurity ion
II) Line defect (one dimensional)
a. Edge dislocaton b. Screw dislocaton
III) Plane defect (one dimensional)
a. Grain boundaries
b. Tilt boundaries
c. Twist boundaries
d. Twin boundaries
e. stacking fault.
IV) Volume defect (Three dimensional)

I)Point Defect
a) Stoichiometric
Frenkel defect : This defect arises when an ion is dislodged from
its original site and occupies an intersttal site in an ionic crystal.
Ex. AgX, CaF2.

Schottky defect : When a pair of one caton and one anion missing
from an ionic crystal lattice.
Ex . Nacl, Cscl

b) Non Stoichiometric
I ) Metal ion excess defect

1. Due to iacancy : It is arises due to absence of negatve ions in

the crystal lattice which is occupied by Free electrons. These sites
are called F centres.

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 12

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

2.Due to extra ion : This defect arises due to due to presence of additonal metal ions which
occupy intersttal sites. Ex. Zno

II) Metal ion defciency defect:

1. Due to missing caton: This defect arises when one or more

catons are missing from the crystal lattice. Ex.: FeO

2. Due to the presence of impurity ion. In this solid soluton

sites of Ag+ are occupied by Cd++. But for neutrality,
neighbouring Ag+ ions in the adjacent positon is removed.Ex.
AgCL/ Cd Cl2

II Line defects (one dimensional)

1. Edge dislocaton defect: It is a defect caused due to inserton of an atomic plane which
ends abruptly in the crystal. If the edge dislocaton is on the upper side. It is positve (I)
dislocaton and if it is on the lower side, it is negatve (T) dislocaton.

2. Screw dislocaton defect: When the crystal

is sheared parallel to the cut with the extent
of only one inter atomic distance, a screw
dislocaton takes place.

Burger iector (or) Dislocaton line (b):‐

The vector which indicates the directon and magnitude of the shif of the latice (edge &
screw dislocaton) on the slip plane is called Burger vector. (or) Dislocaton line.

III Plane defects (Two dimensional)

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 13

MATERIAL SCIENCE UNIT-I- CRYSTAL STRUCTURE AND LATTICE DEFECTS

1. Grain boundaries: Usually all crystal lattices are polycrystalline containing a large number
of crystallites or grains. When the three dimensional lattice periodicity is terminated abruptly
at the surface.

2. Tilt boundaries: They consist of a series of edge dislocatons lying

a
one above other. The angle of inclinaton is small and given by θ =
h

3. Twist boundaries: They are formed when two sets of screw

dislocatons interest each other. The angle of inclinaton is very
a
small, given by α=
h

4. Twin boundaries: In these, the arrangement of atoms on

one side of the boundary is mirror image of the atomic
arrangement of the other side.

5. Stacking faults: Arrangement of atomic planes in a specifc sequence

in the process of crystal lattice formaton is called as stacking. When any
one atomic plane stacks out of sequence on another plane, a fault is
created.

iii. Volume defect ( Three dimensional )

This defect occurs due to the inclusions of foreign partcles, voids and non crystalline
regions of few angstroms. The crack that arises due to a small electrostatc dissimilarity
between the stacking sequences is also called Volume imperfecton.

********************

K.KRAGALAKSHMI, AP/PHYSICS PUDUCHERRY. 14