Unit I

Crystal Physics
Introduction
The matter is usually regarded to exist in solid state or fluid state. All the
materials are composed of atoms and molecules. A solid is an essentially an ordered array of atoms, bound together
by electric forces to form a very large molecule. There are three different types of solids. Crystalline, poly crystalline
and amorphous.
In a crystal, atoms are arranged into a regular periodically repeated structure that extends throughout the
whole sample. The atoms are said to have long range order. Poly crystalline material is composed of many small
crystals or grains of somewhat irregular size. In an amorphous solid a long range order is absent. (i.e.,) they have
short range order. There is no periodicity in which atoms are arranged in space. They are also regarded as super
cooled liquids.
Examples : metallic crystals : copper, silver, aluminum etc.,
Non metallic crystals: Germanium, silicon
Amorphous or non crystalline materials: glass, rubber, plastic

Difference between crystalline and amorphous material.

S.No Crystalline Amorphous

1 Regular arrangement of atoms Random arrangement of atoms does not
gives definite and geometric shape. give definite and Geometrical shape.

2 They are anisotropic They are isotropic

3 They have sharp Melting Point They do not have sharp Melting Point
4 They possess internal symmetry They do not possess internal symmetry
‘What is Crystal Physics?
Crystal Physics’ or ‘Crystallography’ is a branch of physics that deals with the study of all possible
types of crystals and the physical properties of crystalline solids by the determination of their actual
structure by using X-rays, neutron beams and electron beams.
CLASSIFICATION OF SOLIDS
Solids can broadly be classified into two types based on the
arrangement of units of matter.
The units of matter may be atoms, molecules or ions.
They are,
Crystalline solids and
Non-crystalline (or) Amorphous solids
CRYSTALLINE SOLIDS
A substance is said to be crystalline when the arrangement of units of matter is regular and
periodic.
A crystalline material has directional properties and therefore called as anisotropic substance.
A crystal has a sharp melting point.
It possesses a regular shape and if it is broken, all broken pieces have the same regular shape.
A crystalline material can either be a single (mono) crystal or a polycrystal.
A single crystal consists of only one crystal, whereas the polycrystalline material consists of
many crystals separated by well-defined boundaries.
Examples
Metallic crystals – Cu, Ag, Al, Mg etc,
Non-metallic crystals – Carbon, Silicon, Germanium,
In amorphous solids, the constituent particles t arranged in an orderly manner. They are
randomly distributed.
They do not have directional properties and so they are called as `isotropic’ substances.
They have wide range of melting point and do not possess a regular shape.
Examples: Glass, Plastics, Rubber etc.,
SPACE LATTICE
A lattice is a regular and periodic arrangement of points in three dimensions.
It is defined as an infinite array of points in three dimensions in which every point has
surroundings identical to that of every other point in the array.
The Space lattice is otherwise called the Crystal lattice
Consider the points P, Q and R.
Let us join the points P and Q by a straight line, and the point P and R by another straight line.
The line PQ is taken as X-axis and the line PR is taken as Y-axis.
The distance between any two successive lattice points in the X-direction is taken as `a’.
Similarly, the distance between any two successive lattice points along the Y-direction is taken
as ‘b’.
Here a and b are said to be lattice translational vectors. Consider a square lattice in which a=b.
Consider two sets of points A, B, C, D, E, F and A¢, B¢, C¢, D¢, E¢, F¢.
In these two sets, the surrounding environment looks symmetrical; i.e. the distances AB and
A¢B¢, AC and A¢C¢, AD and A¢D¢, AE and A¢E¢ and AF and A¢F¢ are equal.
Therefore, in the arrangement of points, if the surrounding environment looks the same when
the arrangement is viewed from different lattice points, then that arrangement is said to be a
space lattice.
BASIS:

A crystal structure is formed by associating every lattice point with an unit assembly of atoms
or molecules identical in composition, arrangement and orientation. This unit assembly is
called the `basis’.
When the basis is repeated with correct periodicity in all directions, it gives the actual crystal
structure. The crystal structure is real, while the lattice is imaginary.
CRYSTAL STRUCTURE
 UNIT CELL:
A unit cell is defined as a fundamental building block of a crystal structure, which can generate
the complete crystal by repeating its own dimensions in various directions.
CRYSTALLOGRAPHIC AXES:
Consider a unit cell consisting of three mutually perpendicular edges OA, OB and OC as shown
in figure.
Draw parallel lines along the three edges.
These lines are taken as crystallographic axes and they are denoted as X, Y and Z axes.

LATTICE PARAMETERS
Consider the unit cell as shown in figure. Let OA, OB and OC are the intercepts made by the
unit cell along X, Y and Z axes respectively.
These intercepts are known as primitives. In crystallography the intercepts OA, OB and OC are
represented as a, b and c.
The angle between X and Y axes is represented as g.
Similarly the angles between Y and Z and Z and X axes are denoted by ¢a¢ and ¢b¢
respectively as shown in the above figure. These anglesa, b and g are called as interaxial
angles or interfacial angles.
To represent a lattice, the three interfacial angles and their corresponding intercepts are
essential. These six parameters are said to be lattice parameters.
PRIMITIVE CELL:
It is the smallest unit cell in volume constructed by primitives. It consists of only one full atom
A primitive cell is one, which has got the points or atoms only at the corners of the unit cell.
If a unit cell consists of more than one atom, then it is not a primitive cell.
Example for primitive cell: Simple Cubic unit cell.
Examples for non-primitive cell: BCC and FCC unit cell.
CRYSTALS SYSTEMS:
A three dimensional space lattice is generated by repeated translation of three translational
vectors a, b and c.
Crystals are grouped under seven systems on the basis of the shape of the unit cell.
The seven crystal systems are distinguished from one another by their lattice parameters.
The seven systems are,
1. Cubic 2. Tetragonal 3. Orthorhombic 4.Trigonal (rhombohedral) 5. Hexagonal 6. Monoclinic
and 7. Triclinic
The space lattices formed by unit cells are marked by the following symbols.
 Primitive lattice: P ® having lattice points only at the corners of the unit cell.
Body centred lattice: I ® having lattice points at the corners as well as at the body centre of the
unit cell.
Face centred lattice: F ® having lattice points at the corners as well as at the face centres of the
unit cell.
Base centred lattice: C ® having lattice points at the corners as well as at the top and bottom
base centres of the unit cell.
BRAVAIS LATTICES

Bravais in 1948 showed that 14 types of unit cells under seven crystal systems are possible.
They are commonly called as `Bravais lattices’.

S.No. Crystal system Axial length Interfacial angles Example

1. Cubic a=b=c  =  =  = 90° NaCl, CaF2, Au, Cu

2. Tetragonal a=bc  =  =  = 90° Ordinary white, tin,

Indium, SnO2
3. Orthorhombic abc  =  =  = 90° Sulphur, Topaz, BaSO4,
KNO3
4. Monoclinic abc  =  = 90°;  Na2So4, FeSo4, Gypsum
90°
5. Triclinic abc  90° CuSo4, K2Cr2O7
6. Rhombohedral a = b = c  =  =  90° Calcite, Sb, Bi.
7. Hexagonal a=bc  =  = 90°; Quartz, Zn, Mg.
 = 120°
MILLER INDICES: The crystal lattice may be regarded as made up of an infinite set of parallel equidistant planes
passing through the lattice points which are known as lattice planes. Miller indices are defined as the reciprocals of the
intercepts made by the plane on the three crystallographic axes. In simple terms, the planes passing through lattice points
are called ‘lattice planes’.
For a given lattice, the lattice planes can be chosen in a different number of ways.
The orientation of planes or faces in a crystal can be described in terms of their intercepts on
the three axes. Miller introduced a system to designate a plane in a crystal.
He introduced a set of three numbers to specify a plane in a crystal.
d
This set of three numbers is known as ‘Miller Indices’ of the concerned plane.
 Miller indices are set of three possible integers represented as (h, k, l) which is used to
designate plane in the crystal, is the reciprocal of the intercept made by the planes on the
crystallographic axes.

Procedure for finding Miller Indices

Step 1: Determine the intercepts of the plane along the axes X,Y and Z in terms of the lattice
constants a,b and c.
Step 2: Determine the reciprocals of these numbers.
Step 3: Find the least common denominator (lcd) and multiply each by this lcd.
Step 4: The result is written in paranthesis. This is called the `Miller Indices’ of the plane in the form
(h k l). This is called the `Miller Indices’ of the plane in the form (h k l).

Plane ABC has intercepts of 2 units along X-axis, 3 units along Y-axis and 2 units along Z-axis.
DETERMINATION OF ‘MILLER INDICES’

Step 1: The intercepts are 2, 3 and 2 on the three axes.

Step 2: The reciprocals are 1/2, 1/3 and 1/2.
Step 3: The least common denominator is ‘6’. Multiplying each reciprocal by
lcd, we get 3, 2 and 3.
Step 4: Hence Miller indices for the plane ABC is (3 2 3)
IMPORTANT FEATURES OF MILLER INDICES
For the cubic crystal especially, the important features of Miller indices are,
A plane which is parallel to any one of the co-ordinate axes has an intercept of infinity (¥).
Therefore the Miller index for that axis is zero; i.e. for an intercept at infinity, the corresponding
index is zero.
EXAMPLE ( 1 0 0 ) plane ( Plane parallel to Y and Z axes)

In the above plane, the intercept along X axis is 1 unit.

The plane is parallel to Y and Z axes. So, the intercepts along Y and Z axes are ‘¥’.
Now the intercepts are 1, ¥ and ¥.
The reciprocals of the intercepts are = 1/1, 1/¥ and 1/¥.
Therefore the Miller indices for the above plane is (1 0 0).
MILLER INDICES OF SOME IMPORTANT PLANES

SEPARATION BETWEEN LATTICE PLANES

Consider a cubic crystal of side ‘a’, and a plane ABC.

This plane belongs to a family of planes whose Miller indices are (h k l) because Miller indices
represent a set of planes.

Let ON =d, be the perpendicular distance of the plane A B C from the origin.

Let a1, b1 and g1 (different from the interfacial anglesa, b andg) be the angles between co-
ordinate axes X, Y, Z and ON respectively.

The intercepts of the plane on the three axes are,

 From the figure, we have,
d1 d d (2)
cos 1  , cos1  1 and cos1  1
OA
From the property of direction of cosines,
OB OC

cos 2 1  cos 2 1  cos 2 1 1 (3)

Using equation 1 in 2, we get,
d1 h dk dl
cos1  , cos1  1 , and cos1  1 (4)
a a a
Substituting equation (4) in (3), we get,

2 2 2 2 2 2
 d1 h   d1 k   d1l  d1 h 2 d1 k 2 d1 l 2
 a    a    a  1  2  2 1
      a 2
a a
2
d1
2 d1
(h 2
 k 2
 l 2
) 1 2
(h 2  k 2  l 2 ) 1
a 2 a
2 a2 a
d1  2 d1  ON 
(5) (h  k 2  l2 ) h 2  k 2  l2

i.e. the perpendicular distance between the origin and the 1st plane ABC is,

Now, let us consider the next parallel plane.

Let OM=d2 be the perpendicular distance of this plane from the origin.

The intercepts of this plane along the three axes are

 Therefore, the interplanar spacing between two adjacent parallel planes of Miller indices (h k l ) is
given by, NM = OM – ON i.e.interplanar spacing

Characteristics of unit cell:

• Number of atoms per unit cell
• Coordination number
• Atomic radius
• Atomic Packing factor or Packing Density
• Number of atoms per unit cell: The number of atoms present in the unit cell.
• Coordination number: The number of equidistant nearest neighbouring atoms surrounding the
particular atom considered.
• Atomic Radius (r): It is defined as half the distance between the nearest neighbouring atoms in
a crystal.
• Atomic Packing factor or Packing Density: It is the ratio of the volume occupied by the
atoms in a unit cell (v) to the volume of the unit cell (V). It is also called packing fraction or
packing density.

Simple cubic structure

Body centred cubic structure
Face centered cubic structure
Hexagonal closed packed structure
DIAMOND CUBIC STRUCTURE
From le XAZ

XZ2 = XA2+AZ2 Graphite:

= (a2/16) +( a2/16)

= (a2/8)

From le XYZ

XY2 = XZ2+YZ2

= (a2/8) +( a2/16)

= (3a2/16)

XY = √3a /4

Atomic Radius 2r=XY=√3a /4

r = √3a /8

No. of atoms/unit cell 8

Atomic Radius √3a /8
Coordination No. 4
APF Π√3/16 or 0.34
  Carbon atoms are arranged in layer or sheet structure

 Each carbon atoms are covalently bonded with three other carbons

 The sheets are held together by van der waals forces

 Weak bonding between sheets give softness

 Fourth bonding electron of carbon is delocalized

 Delocalized electrons are mobile and contribute conduction

POLYMORPHISM -Ability of material having more than one structure

ALLOTROPHY - If the change in structure is reversible

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

Physical properties of diamond and Graphite

S.No Diamond

1 High melting point (almost 4000°C).

2 very hard
Does not conduct electricity.
All the electrons are used up in bonding
3
(held tightly between) the atoms, and
are not mobile

4 insoluble in water and organic solvents

5 Transparent

6 Crystallizes in Isometric system

7 Carbon atoms are covalently bonded

Miller Indices of Planes

S.NO x y z

1 intercept of plane on axis a ∞ ∞

2 Reciprocal 1/a 1/∞ 1/∞

3 Convert to the smallest integers 1 0 0

4 Miller Indices (hkl) (1 0 0)

Crystal growth

Solidification and Crystallization Solidification is the transformation of material from liquid to solid state on
cooling.

When the liquid solidifies, the energy of each atom is reduced. This energy is given out as latent heat during the
solidification process. For a pure metal, it occurs at a fixed temperature, Ts (Fig). During solidification, the
disordered structure of the liquid (constituents of material in liquid state have more velocity, more

Collisions and hence have random position) transforms to the orderly arrangement depending upon the time of
solidification.

This solidification process greatly influences the crystal growth.

CRYSTAL GROWTH TECHNIQUES

The crystal growth technique is classified into 6 types.

They are
(i) Melt growth

(ii) Low temperature solution growth

(iii) High temperature solution growth (Flux growth)

(iv) Hydrothermal growth

(v) Gel growth

(vi) Vapour phase growth

Melt growth Melt growth is the process of crystallization by fusion and resolidification of the starting
materials from the melt.

CZOCHRALSKI TECHNIQUE

Principle
It is a crystal pulling technique of growth of crystal by a gradual layer by layer condensation of melt. It is
based on liquid - solid phase transition initiated by a seed crystal.

Characteristics:

• Charge and seed are separated at start.

• No material is added or removed (conservative process)

• charge is held at temperature slightly above melting point

• crystal grows as atoms from the melt adhere to the seed

Czochralski method
Advantages:
• Growth from free surface (stress free)
• crystal can be observed during the growth process
 • Forced convection easy to impose
• Large crystals can be obtained
• High crystalline perfection can be achieved
Drawbacks:
• delicate start (seeding, necking) and sophisticated further control
• delicate mechanics (the crystal has to be rotated; rotation of the crucible is desirable)
• cannot grow materials with high vapor pressure
• batch process (axial segregation, limited productivity
Bridgman method:
Characteristics:
• charge and seed are placed into the crucible
• no material is added or removed (conservative process)
• axial temperature gradient along the crucible

Advantages:

• The shape of the crystal is defined by the container

• No radial temperature gradients are needed to control the crystal shape.

• low thermal stresses result in low level of stress-induced dislocations.

• crystals may be grown in sealed ampules (easy control of stoichiometry)

• easy control and maintenance

Drawbacks:

• confined growth (crucible may induce stresses during cooling)

• difficult to observe seeding and growing processes

• delicate crucible and seed preparation, sealing, etc.

CHEMICAL VAPOUR DEPOSITION

CVD is the formation of a non-volatile solid film on a substrate by the reaction of vapor phase chemicals
(reactants) that contain the required constituents.

The reactant gases are introduced into a reaction chamber and are decomposed and reacted at a heated surface to
form the thin film.

CVD APPARATUS

 Gas delivery system – For the supply of precursors to the reactor chamber

 Reactor chamber – Chamber within which deposition takes place

 Substrate loading mechanism – A system for introducing and removing substrates, mandrels etc.

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

 Vacuum system – A system for removal of all other gaseous species other than those required for the
reaction/deposition.

 Exhaust system – System for removal of volatile by-products from the reaction chamber.

 Exhaust treatment systems – In some instances, exhaust gases may not be suitable for release into the
atmosphere and may require treatment or conversion to safe/harmless compounds.

 Process control equipment – Gauges, controls etc.. to monitor process parameters such as pressure,
temperature and time. Alarms and safety devices would also be included in this category.

 Steps involved in a CVD process (schematic)

1. Transport of reactants by forced convection to the deposition region.

2. Transport of reactants by diffusion from the main gas stream through the boundary layer to the wafer surface.

3. Adsorption of reactants on the wafer surface.

4. Surface processes, including chemical decomposition or reaction, surface migration to attachment sites (such as
atomic-level ledges and kinks), site incorporation, and other surface reactions.

5. Desorption of byproducts from the surface.

6. Transport of byproducts by diffusion through the boundary layer and back to the main gas stream.

7. Transport of byproducts by forced convection away from the deposition region.

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

APPLICATIONS

 Coatings –

 Such as wear resistance,

 Corrosion resistance,

 High temperature protection,

 Erosion protection and

 Combinations thereof.

 Semiconductors and related devices –

 Integrated circuits,

 Sensors and

 Optoelectronic devices

 Dense structural parts – CVD can be used to produce components that are difficult or uneconomical to
produce using conventional fabrication techniques.

Dense parts produced via CVD are generally thin walled and maybe deposited onto a mandrel or former.

 Optical Fibers – For telecommunications.

 Physical Vapour Déposition(PVD)
 Physical vapour deposition (PVD) is fundamentally a vaporization coating technique, involving transfer of
material on an atomic level.
 It is an alternative process to electroplating
 The process is similar to chemical vapour deposition (CVD) except that the raw materials/precursors,
 i.e. the material that is going to be deposited starts out in solid form, whereas in CVD, the precursors are
introduced to the reaction chamber in the gaseous state.
 Working Concept
PVD processes are carried out under vacuum conditions. The process involved four steps:
1.Evaporation
2.Transportation
3.Reaction
4.Deposition

 Evaporation
During this stage, a target, consisting of the material to be is bombarded by a high energy source such as a
beam of electrons or ions. This dislodges atoms from the surface of the target, ‘vaporizing’ them.
 Transport
This process simply consists of the movement of ‘vaporized’ atoms from the target to the substrate to be
coated and will generally be a straight line affair.
 Reaction
In some cases coatings will consist of metal oxides, nitrides, carbides and other such materials.

In these cases, the target will consist of the metal.

The atoms of metal will then react with the appropriate gas during the transport stage.

For the above examples, the reactive gases may be oxygen, nitrogen and methane.
In instances where the coating consists of the target material alone, this step would not be part of the process.

Deposition

This is the process of coating build up on the substrate surface.

Depending on the actual process, some reactions between target materials and the reactive gases may also
 take place at the substrate surface simultaneously with the deposition process.
The component that is to be coated is placed in a vacuum chamber. The coating material is evaporated by
intense heat from, for example, a tungsten filament.
An alternative method is to evaporate the coating material by a complex ion bombardment technique.
The coating is then formed by atoms of the coating material being deposited onto the surface of the
component being treated.

Evaporative Deposition

In which the material to be deposited is heated to a high vapor pressure by electrically resistive heating in
"high" vacuum

Importance of PVD Coatings

 PVD coatings are deposited for numerous reasons. Some of the main ones are:

 Improved hardness and wear resistance

 Reduced friction

 Improved Oxidation resistance

 The use of such coatings is aimed at improving efficiency through improved performance and longer
component life.

 They may also allow coated components to operate in environments that the uncoated component would
not otherwise have been able to perform.

Advantages

 Materials can be deposited with improved properties compared to the substrate material

 Almost any type of inorganic material can be used as well as some kinds of organic materials

 The process is more environmentally friendly than processes such as electroplating.

Disadvantages

 It is a line of sight technique meaning that it is extremely difficult to coat undercuts and similar surface
features
 High capital cost

 Some processes operate at high vacuums and temperatures requiring skilled operators

 Processes requiring large amounts of heat require appropriate cooling systems

 The rate of coating deposition is usually quite slow

Applications

 PVD coatings are generally used to improve Hardness, Wear Resistance and Oxidation Resistance.

 Thus, 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