231PYB101T Engineering Physics

Unit-IV

CRYSTAL PHYSICS
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• INTRODUCTION TO CRYSTAL PHYSICS
• CRYSTALLINE AND NON-CRYSTALLINE SOLIDS
• SPACE LATTICE
• CRYSTAL STRUCTURE
• LATTICE PARAMETERS
• CRYSTAL SYSTEMS
• BRAVAIS LATTICES

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INTRODUCTION TO CRYSTAL PHYSICS

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+ - -

+ +
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+ - - -

+ + +

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What is Crystal Physics
- physical properties of crystalline solids
- determination of their actual structure by using
X-rays, neutron beams and electron beams.-

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 CLASSIFICATION OF SOLIDS

SOLID MATERIALS

AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal

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 CRYSTALLINE SOLIDS

• arrangement of units of matter is regular and periodic.

• anisotropic substance.

• sharp melting point.

• possesses a regular shape

• Ex: Iron, Copper, Carbon, Germanium

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 NON CRYSTALLINE SOLIDS

• amorphous solids

• particles are randomly distributed.

• `isotropic’ substances.

• have wide range of melting point

• Examples: Glass, Plastics,

Rubber etc.,

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 POLYCRYSTALLINE SOLIDS
■ aggregate of many small single crystals

■ high degree of order over many atomic or

molecular dimensions.

■ grain boundaries.

■ grains are usually 100 nm - 100 microns in

diameter.

■ Polycrystals with grains < 10 nm in diameter are

nanocrystalline

■ Examples : Inorganic solids, Most of the metals and

Ceramics
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CRYSTALLOGRAPHIC TERMS

❖ SPACE LATTICE

❖ LATTICE POINTS

❖ LATTICE LINES

❖ LATTICE PLANES

❖ BASIS or MOTIF

❖ CRYSTAL STRUCTURE

❖ UNIT CELL

❖ LATTICE PARAMETERS
 SPACE LATTICE

• regular and periodic arrangement of points in three dimension.

• identical surroundings to that of every other point in the array.

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 BASIS
• a unit assembly of atoms or molecules identical in composition,
arrangement and orientation.

• repeatation of basis correct periodicity in all directions

• The crystal structure is real, while the lattice is imaginary.

Examples No. of atoms in Basis

Aluminim 01
Barium 01
NaCl 02
KCl 02
CaF2 03
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 CRYSTAL STRUCTURE

+ =

Lattice + Basis = Crystal structure

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 UNIT CELL
• a fundamental building block

• repeating its own dimensions in various directions gives

crystal structure

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 Lattice parameters

x, y and z are crystallographic axes

Length of the unit cell along the x, y,

and z direction are a, b, and c

Interaxial angles:

α = the angle between a and b

β = the angle between b and c

γ = the angle between c and a

a, b, c, α, β, γ are collectively known as the lattice parameters

 PRIMITIVE CELL
• A unit cell consists of only one full atom

• A primitive cell got the points or atoms

only at the corners

• If a unit cell consists more than one atom,

then it is not a primitive cell.

• Example for primitive cell :

Simple Cubic(SC)

• Examples for non-primitive cell :

BCC and FCC unit cell.
Seven crystal systems
Seven crystal systems and its lattice Parameters
BRAVAIS LATTICE
Bravais in 1948 showed that 14 types of unit cells under seven crystal systems are possible.
14 Bravais Lattices divided into 7 Crystal Systems
Crystal System Shape of UC Bravais Lattices
P I F C
1 Cubic Cube ✓ ✓ ✓
2 Tetragonal Square Prism (general height) ✓ ✓
3 Orthorhombic Rectangular Prism (general height) ✓ ✓ ✓ ✓
4 Hexagonal 120° Rhombic Prism ✓
5 Trigonal Parallopiped (Equilateral, Equiangular) ✓
6 Monoclinic Parallogramic Prism ✓ ✓
7 Triclinic Parallopiped (general) ✓

P Primitive
I Body Centred
F Face Centred
C Base- Centred 19
 Characteristics of unit cell
• Number of atoms / unit cell

• Coordination number
No. of equidistant nearest neighbouring atoms to a
particular atom

• Atomic Radius (r)

half the distance between the nearest neighbouring atoms

• Atomic Packing factor or Packing Density

ratio of the volume occupied by the atoms in an unit cell
(v) to the volume of the unit cell (V)

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 Simple Cubic Structure (SC)

No. of atoms/unit
a 1
cell
Atomic Radius a/2
R=0.5
Coordination No. 6
a
APF 0.52 21
 Body Centered Cubic Structure (BCC)
B

A D

No. of atoms/unit cell 2

Atomic Radius √3 a/4

Coordination No. 8

APF √3π/8 or
0.68
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 Face Centered Cubic Structure (FCC)

B
C
No. of atoms/unit
a 4r 4
cell
Atomic Radius √2a/4
A
Coordination No. 12
a D
APF π /( 3√2 ) or
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HEXAGONAL CLOSED PACKED STRUCTURE

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ATOMIC PACKING FACTOR (APF) of HCP

O
A

No. of atoms/unit cell 6

Atomic Radius a/2
Coordination No. 12
APF π /( 3√2 ) or 0.74
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 C/a Ratio
C
In the triangle AXC,
c/2 O
a
AC2 = AX2 + CX2

A
300 A’
X

O’
a

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Diamond Lattice Structure

• Formed by the combination of two

interpenetrating FCC lattices.

• The two sub-lattices , X and Y are at

(0,0,0) and (a/4, a/4, a/4).

Ex: Germanium, Silicon, Diamond

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No. of atoms/unit
8
cell
Atomic Radius √3a/8
Coordination No. 4
APF π√3 /16 or 0.34
 POLYMORPHISM & ALLOTROPHY

POLYMORPHISM - Ability of material to have more than one

structure

ALLOTROPHY - If the change in structure is reversible

Example : Cobalt at ordinary temp. -HCP and at 477°C -FCC

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 Graphite Structure

• Carbon atoms are arranged in layer or

sheet structure

• covalently bonded with other carbons

• sheets are held together by vander waals

forces

• weak bonding between sheets give

softness

• Delocalized electrons

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 Physical properties of diamond and Graphite
S.No Diamond Graphite
1 high melting point (almost 4000°C). high melting point

soft, slippery feel, and is used in

2 very hard
pencils
3 does not conduct electricity. Conducts electricity.
insoluble in water and organic insoluble in water and organic
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solvents solvents
5 Transparent Opaque
6 Crystallizes in Isometric system Crystallizes in hexagonal system

covalently bonded in same plane and

7 covalently bonded sheets are held together by Van der
waals bonds

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 MILLER INDICES

⮚ set of three possible integers represented as (h k l)

⮚ reciprocals of the intercepts made by the plane on the three

crystallographic axes

⮚ designate plane in the crystal.

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 Procedure for finding Miller Indices

▪ Step 1 : Determine the intercepts of the plane along the axes

▪ Step 2 : Determine the reciprocals of these numbers.

▪ Step 3 : Find the LCD and multiply each by this LCD

▪ Step 4 : Write it in paranthesis in the form (h k l).

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 ILLUSTRATION

Step 1 : intercepts - 2a,3b and 2c

Step 2 : reciprocals - 1/2, 1/3 and 1/2.

Step 3 : LCD is ‘6’.

Multiply each reciprocal by lcd,
we get, 3,2 and 3.

Step 4 : Miller indices for the plane

ABC is (3 2 3)

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 EXAMPLE

▪ intercepts are 1, ∞ and ∞.

▪ reciprocals of the intercepts are

1/1, 1/∞ and 1/∞.

▪ Miller indices for the plane is (1 0 0).

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MILLER INDICES OF SOME IMPORTANT PLANES

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 IMPORTANT FEATURES OF MILLER INDICES

▪ a plane parallel to the axes has an intercept of infinity (∞).

▪ a plane cuts an axis on the negative side of the origin, is

represented by a bar, as ( ͞1 0 0).

▪ a plane passing through the origin have non zero intercepts

▪ All equally spaced parallel planes have same Miller indices

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 INTERPLANAR DISTANCE or d-Spacing

Z
▪ Two planes ABC and A’B’C’
C’

▪ Interfacial angles α, β,γ and α’, β’, γ’

C
▪ Intercepts of the plane ABC M
γ N
d d2
’ 1
α’ β
O
’

A B

A’ B’
X 38
Y
From the property of direction of cosines,

Similarly , for the plane A’B’C’

Interplanar spacing

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 METHODS OF CRYSTAL GROWTH

❖ Solid Growth - Solid-to-Solid phase transformation

❖ Liquid Growth - Liquid to Solid phase transformation

❖ Vapour Growth - Vapour to Solid phase transformation

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 GROWTH FROM MELT

• All materials can be grown in single crystal form from the melt.

• Depending on the thermal characteristics, the following

techniques are employed.
1. Bridgman technique
2. Czochralski technique
3. Kyropoulos technique
4. Zone melting technique
5. Verneuil technique
 Bridgman method

• charge and seed are placed into the crucible

• axial temperature gradient along the

crucible

• rates of movement for such processes range

from about 1 – 30 mm/hr.

•Crystallization begins at the tip and continues

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usually by growth from the first formed
Advantages: Drawbacks:
• shape of the crystal is defined • confined growth (crucible
by the container may induce stresses during
cooling)
• No radial temperature
gradients are needed to control • difficult to observe seeding
the crystal shape. and growing processes

• low thermal stresses result in • delicate crucible and seed

low level of stress-induced preparation, sealing, etc.
dislocations.

• crystals may be grown in sealed

ampules Crystals grown:
GaAs, ZnS, CdSe…
• easy control and maintenance
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 Czochralski method

• By controlling the furnace

temperature, the material is
melted.

• A seed crystal is lowered to

touch the molten charge.

• the molten charge in contact

with the seed solidifies.

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Advantages: Drawbacks:
• Growth from free surface • delicate start (seeding,
(stress free) necking) and sophisticated
further control
• crystal can be observed during
the growth process • delicate mechanics (the
crystal has to be rotated;
• Large crystals can be obtained rotation of the crucible is
desirable)
• High crystalline perfection can
be achieved • cannot grow materials with
high vapour pressure

Crystals grown:

Semiconductormaterials, dielectric materials, jewellery crystals. 52

Puller rod with
seed crystal

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 CHEMICAL VAPOUR DEPOSITION
• formation of a non-volatile solid film on a substrate by the
reaction of vapor phase chemicals (reactants)

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⮚ Gas delivery system – supply of precursors to the reactor chamber

⮚ Reactor chamber – Chamber within which deposition takes place

⮚ Substrate loading mechanism – for introducing and removing substrates.

⮚ Energy source – Provide the energy/heat that is required to get the precursors to
react/decompose.

⮚ Vacuum system – for removal of all unwanted gaseous species 55

Advantages:

⮚ High growth rates possible

⮚ Can deposit materials which are hard to evaporate
⮚ Good reproducibility
⮚ Can grow epitaxial films

Disadvantages

⮚ high temperatures
⮚ complex processes
⮚ toxic and corrosive gases 56
 APPLICATION
⮚ Coatings

⮚ Semiconductors and related devices

⮚ Dense structural parts

⮚ Optical Fibers

⮚ Composites

⮚ Catalysts

⮚ Nano machines
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 Physical Vapour Deposition (PVD)

⮚ a vaporization coating technique

⮚ involving transfer of material on an atomic level

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• Working Concept
- involved four steps:
1.
Evaporation
2.
Transportation
3. Reaction
4. Deposition

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 Importance of PVD Coatings

⮚ Improved hardness and wear resistance

⮚ Reduced friction

⮚ Improved Oxidation resistance

⮚ Improving efficiency and longer component life.

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 DISADVANTAGES

⮚ extremely difficult to coat undercuts and similar surface

features

⮚ High capital cost

⮚ operate at high vacuums and temperatures requiring skilled

operators

⮚ require appropriate cooling systems

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Applications

⮚used to improve Hardness, Wear Resistance And Oxidation

Resistance.

⮚such coatings use in a wide range of applications such as:

▪ Aerospace
▪ Automotive
▪ Surgical/Medical
▪ Dies and moulds for all manner of material processing
▪ Cutting tools
▪ Fire arms

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