PH5P5

MATERIALS SCIENCE
CRYSTAL STRUCTURE AND DEFECTS

III B.Sc. PHYSICS

V SEMESTER

Dr. Marimuthu Sundarrajan

Assistant Professor of Physics
SCSVMV Deemed University
 Crystalline and Amorphous solids
The materials can be classified in broad scope as
Crystalline materials
In crystalline solids the atoms are arranged in a periodic manner and the
atomic arrangement is found to be uniform through out the material.
There are single and polycrystalline materials. In polycrystalline
materials, each of the constituent crystal has uniform atomic
arrangement with in its boundary.
Examples; Quartz, Calcite, Sugar, Mica, Diamonds, table salt etc.
Non-crystalline materials or Amorphous solids
In amorphous solids , the atoms are arranged in a random manner and
there is no periodic atomic arrangement in any part of the material
Examples; Plastics, Glass, Rubber, Metallic Glass, Polymers, Gel etc.

https://www.askiitians.com/iit-jee-solid-state/amorphous-and-crystalline-solids/
 CRYSTAL STRUCTURE
A crystal structure refers to a structure in which atoms or
molecules arranged in a uniform manner. The regular
geometry of arrangement of atoms starts from a
fundamental unit and this unit is called unit cell. When this
unit cell geometry is repeated in three dimension, it results in
a crystal structure and hence a crystal

https://www.hindawi.com/journals/amse/2013/673786/fig4/
 LATTICE AND BASIS
A lattice is a two
dimensional plane which
consists of periodic
arrangement of points
where atoms or group of
atoms can be observed in
a crystal

A basis is an atom or
group of atoms that may
be present in the lattice
point of a crystal.
http://dionne.stanford.edu/MatSci202_2011/Lecture7_ppt.pdf
 SPACE LATTICE

Space lattice
It is a three
dimensional
arrangement of
lattice points in a
space where
atoms or group
of atoms are
arranged
 CRYSTAL =LATTICE + BASIS

Crystal structure is obtained when atoms or

group of atoms (basis) occupy the space
lattice points.
 UNIT CELL
FUNDAMENTAL UNIT OF CRYSTAL
Unit cell is the fundamental unit of crystal
lattice. When unit cell is repeated in a three
dimensional way, it results in space lattice and
hence crystal structure
 LATTICE PARAMETERS OF UNIT CELL
Lattice parameters define the
dimension of unit cell in terms
of axial lengths in x,y and z axes
and angles between the planes
through the x,y and z axes.

The axial lengths are called lattice

constants and angles are called
as interfacial angles. Both
lattice constants and angles are
called lattice parameters.

lattice constants, referred to as a,

b, and c and three interfacial
angles as a, b and g
Credit: CK12 Foundation - Christopher Auyeung; License: CC BY-NC 3.0.
 LATTICE CONSTANTS
AND
INTERFACIAL ANGLES

Crystallographic axes:
ox, oy, oz
Interfacial angles:
a, b, g
Lattice constant:
a, b, c
Source : http://www.brainkart.com/article/Types-of-Cubic-System_2865/
 EXAMPLES OF CRYSTALS

Large crystals
Diamonds and table salt.

Polycrystals
Polycrystal are made up
of tiny induvidual
crystals with boundaries.
Metals, rocks,
ceramics, and ice.

Source :http://dmishin.blogspot.com/2014/08/crystal-growing-table-salt-sodium.html
 CRYSTAL SYSTEMS & BRAVAIS
LATTICES
The structure of
crystals are broadly
classified in to
seven systems
based on lattice
parameters. The
following are seven
crystal systems
Cubic
triclinic
monoclinic
orthorhombic
tetragonal
trigonal
& hexagonal system
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 BRAVAIS LATTICES

In 7 crystal systems, Bravais Lattices refers to

the 14 different 3-dimensional configurations
into which atoms are arranged in crystals with
various lattice parameters.

The smallest group of symmetrically aligned

atoms which can be repeated in an array to
make up the entire crystal is called a unit cell
7 CRYSTAL SYSTEMS AND 14 BRAVAIS
LATTICES

http://home.iitk.ac.in/~sangals/crystosim/crystaltut.html
 CUBIC SYSTEM
Assignment of Atoms / unit cell
Simple Cubic

http://www.brainkart.com/article/Types-of-Cubic-System_2865/

 Atoms are present at the corners only

 Each atom at the corner is shared equally by eight other unit cells
 Hence the contribution of each atom to the unit cell is 1/8.
 CUBIC SYSTEM
Assignment of Atoms/ unit cell
Body Centered Cubic lattice (BCC)

• Atoms are present at the corners

• The contribution of corner atom to the unit cell is 1/8.
• One full atom at the centre of the unit cell
 CUBIC SYSTEM
Assignment of Atoms/ unit cell
Face Centered Cubic lattice (FCC)

• Atoms are present at the corners

• The contribution of corner atom to the unit cell is 1/8.
• One face centred atom at the centre of all six faces
• The contribution face atoms to the unit cell is ½
 PRPOPERTIES OF UNIT CELL
Atoms per Unit cell
• This represents the content of atoms in unit cell
Atomic Radius
• It is the distance between the centers of two
neighbouring atoms in contact
Coordination number
• It is the number of nearest equidistant neighbouring
atoms to a given atom in a lattice
Atomic Packing factor (APF)
• It is the ratio of volume of atoms in a unit cell to
the volume of unit cell
APF = Volume of atoms in unit cell / Volume of unit cell
 SIMPLE CUBIC LATTICE (SC)
Number of Atoms / Unit cell
• Only corner atoms
• 8 corner atoms (1 per
corner)
• Share of each corner
atom = 1/8 of its volume
• Total no. of atoms
= 8 x 1/8 = 1 atom

https://www.coursehero.com/textbook-solutions/
 SIMPLE CUBIC LATTICE (SC)
Atomic radius

From figure

a = 2R
R = a/2

Source : https://www.slideshare.net/rpclemson/module2-71196024
 SIMPLE CUBIC LATTICE (SC)
Coordination number
The corner atom
• has 4 atoms in its
own plane
• 1 atom in lower
plane
• 1 atom in upper
plane
• All these are nearest
neighbours
Therefore
the coordination https://www.slideshare.net/rpclemson/module2-71196024
number
4+1+1 = 6
 SIMPLE CUBIC LATTICE (SC)
Atomic Packing Factor
APF = Volume of atoms in unit cell / Volume of unit cell

Source :http://www.uobabylon.edu.iq/eprints/publication_1_2901_199.pdf
 BODY CENTRED CUBIC LATTICE (BCC)
Number of atoms/ unit cell
• 8 corner atom.
• 1 full body centered
atom.
• Share of corner atom 8
x 1/8 =1
• Share of body centered
atom =1
• Total no. of atoms
per unit cell
1+1 =2 https://www.coursehero.com/textbook-solutions/
 BODY CENTRED CUBIC LATTICE (BCC)
Coordination number
The body centered
atom
• has 4 atoms in upper
plane
• 4 atoms in lower
plane
• All these are nearest
neighbours

Therefore
the coordination Source : https://www.slideshare.net/rpclemson/module2-71196024

number
4+4 = 8
 BODY CENTRED CUBIC LATTICE (BCC)
Atomic radius
From figure

3a2 = 16R2
16R2 = a2 + 2a2
R2 = 3/16 a2
R = √3/4 a
https://www.slideserve.com/mildred/unit-vii-crystal-structure
BODY CENTRED CUBIC LATTICE (BCC)
Atomic Packing Factor
APF = Volume of atoms in unit cell / Volume of unit cell

Source : http://www.uobabylon.edu.iq/eprints/publication_1_2901_199.pdf
 FACE CENTRED CUBIC LATTICE (FCC)
Number of atoms
• 8 corner atom.
• 6 face centered atoms.
• Share of corner atom
8x 1/8=1
• Share of each face
centered atom = 1/2
• Total no. of atoms
per unit cell = 1 + 6x(1/2)
1+3 = 4
https://www.coursehero.com/textbook-solutions/
 FACE CENTRED CUBIC LATTICE (FCC)
Coordination number
The face centered atom
has
• 4 corner atoms in its
own plane
• 4 face centred
atoms in upper plane
• 4 face centred atoms
in lower plane

Therefore
the coordination
number
4+4 +4= 12 Source : https://www.slideshare.net/rpclemson/module2-71196024
 FACE CENTRED CUBIC LATTICE (FCC)
Atomic radius

From figure
(4R)2 = a2 + a2
16R2 = 2a2
R2 = 2/16 a2
R = √2/4 a = a/2 √ 2 a
Source :http://www.uobabylon.edu.iq/eprints/publication_1_2901_199.pdf
FACE CENTRED CUBIC LATTICE (FCC)
Atomic Packing Factor
APF = Volume of atoms in unit cell / Volume of unit cell

Source :http://www.uobabylon.edu.iq/eprints/publication_1_2901_199.pdf
HEXAGONAL CLOSE PACKED STRUCTURE
,
Ex: cobalt, cadmium, zinc, beryllium, magnesium, titanium and zirconium.
HCP structure consist of three layers
In top and bottom layers,
six atoms at the corners of each
hexagon and one atom at the
centre of hexagon.
In the middle layer
three atoms.
The distance between atoms in
hexagonal plane is “a”
The distance between central
atoms of top and bottom hexagonal
planes is “c” Credit: Callister & Rethwisch 5e
HEXAGONAL CLOSE PACKED STRUCTURE (HCP)
Number of atoms
 12 corner atom.
 2 face centered atoms.
 3 central atoms
 Share of corner atom is 1/6
(upper hexagonal plane 1/3 & lower
hexagonal plane 1/3)
 Share of each face centered atom
is 1/2
 Three full atoms at the centre
 Total no. of atoms
per unit cell
12x (1/6) + 2X(1/2) + 3 = 6
Credit: Callister & Rethwisch 5e
 HEXAGONAL CLOSE PACKED STRUCTURE (HCP)
Coordination number
The face centered atom at
the centre of hexagon has
• 6 corner atoms in its own
plane
• 3 nearer central atoms in
upper plane
• 3 nearer central atoms in
lower plane

Therefore
Coordination number
6+3 +3= 12
 HEXAGONAL CLOSE PACKED STRUCTURE (HCP)
Atomic radius
In HCP structure, the corner
atoms in the hexagonal
plane touch each other
and all corner atoms touch
the face centered atom.
Therefore atomic radius
a = 2r
r = a/3
 HEXAGONAL CLOSE PACKED STRUCTURE (HCP)
CALCULATION OF c/a RATIO

Consider the figures a and b shown above.

Each top and bottom hexagonal layers of hcp structure consist of 6 corner
and 1 central atom.
The middle layer consists of three full atoms. Consider one such atom
Let C be the atom situated at the central plane of hcp structure
CALCULATION OF c/a RATIO (HCP)
CALCULATION OF c/a RATIO (HCP)
CALCULATION OF PACKING FACTOR (HCP)
CALCULATION OF PACKING FACTOR (HCP)

Since the packing density is 74%, the hcp structure is a

closely packed structure. Since FCC also has same packing
density, both HCP and FCC are called as closely packing
structures
 MILLER INDICES OF CRYSTAL PLANES

• Miller indices designate the

directions of various planes
in crystal structure.
• Miller Indices are set of three
numbers enclosed in a
parenthesis.
• In the figure the plane
intercepts at x,y and z axes
are 2,3 and 2 respectively.
• The orientation of this plane
is represented by the Miller http://www.chemohollic.com/2016/08/all-bout-
indices (3 2 3) miller-indices.html
 STEPS TO FIND MILLER INDICES

 Find the intercepts of the plane on

three axes in terms of lattice
constants
2a, 3b, 2c
 Take the coefficients of intercepts
2, 3, 2
 Take the ratio of reciprocals
1 / 2 : 1/3, 1 /2
 Convert these reciprocals in to
whole number by multiplying with
LCM
323
 Enclose in parenthesis
( 3 2 3)
 The Miller indices of the given
plane is (3 2 3)
MILLER INDICES OF VARIOUS PLANES

http://www.chemohollic.com/2016/08/all-bout-miller-indices.html

http://www.chemohollic.com/2016/08/all-bout-miller-indices.html
MILLER INDICES OF VARIOUS PLANES

http://www.chemohollic.com/2016/08/all-bout-miller-indices.html
INTERPLANAR DISTANCE
INTERPLANAR DISTANCE
INTERPLANAR DISTANCE
INTERPLANAR DISTANCE
INTERPLANAR DISTANCE
INTERPLANAR DISTANCE
 X Ray Diffraction (XRD)

Useful for the findings on;

• Crystal structure of materials
• Orientation of single crystal grain
• Size and shape of small crystalline regions in
polycrystalline materials
• Average spacing between layers of atoms
 X Ray Diffraction
 Diffraction will occur when the size of the obstacle is of the
order of wavelength of the incident radiation.
 The evaluation of material structure is obtained from
diffraction of incident radiation over the material atoms.
 In material structure atoms are the obstacles and they diffract
the incident radiation when the radiation wavelength is of the
order of size of atoms.
 In the case of X-rays this condition is met and hence X-ray
diffraction is used to analyse material (crystal) structure.
 The arrangement of atoms in the cleavage planes of a space
lattice act as three dimensional grating and hence diffraction
occurs.
 Bragg’s law
• W.L Bragg discovered the
reflection of X-rays in the
cleavage plans of the crystal,
when X-rays incident at some
glancing angle, known as Bragg’s
angle.
• The condition for the constructive
interference between the
reflected X-rays was given by the
Bragg’s law.
 Powder X Ray Diffraction
This method is suitable to
powder crystalline material or
finely grained polycrystalline
material

Also called as Debye-

Scherrer method

Used in the findings;

Lattice parameters of crystals

of known structure

Identification of elements
https://docplayer.net/11027738-X-ray-diffraction-xrd.html
 Powder X Ray Diffraction
Powder specimen is taken in a small
capillary tube
 Pencil beam of X rays are diffracted by
the powder
Diffracted rays are recorded by a
photogrphic film as a series of varying
curves
The distane S between two
corresponding arcs in photographic
plate measures full opening angle 4θ of
diffraction cone
4θ = S / R radians, where
R – Specimen to film distance
Using the S values of S , values
of θ can be tabulated

Using the values of θ and λ ,

interplanar spacing “d” can be
determined

Using the “d” values between

the planes, indexing for
reflection and unit cell
parameters can be obtained.
 Lattice defects – Qualitative ideas of
point, line, surface and volume defects
Crystal defects (or)
Imperfections
Minor deviation from the periodicity
of arrangement of atoms at the
surface or inside a crystal is
called defect or imperfection.
Many crystal properties are defect
centric.
Various crystalline imperfections
 Point Imperfection
 Line imperfection
 Surface imperfection
 Volume imperfection
 Point Imperfections
 These are also called as
zero dimensional
imperfections

 Imperfections are point

like regions at the Size of
one or two atom size

 Unnecessary presence or
absence of atoms result in
imperfections

https://www.askiitians.com/iit-jee-solid-state/imperfections-in-solids-and-defects-in-crystals/
 Types of Point Imperfections
Vacancy
Refers to the missing of an atom from its
actual place in lattice

Substitutional Impurity
Refers to a foreign atom that replaces a
parent atom in the crystal lattice
Ex: doping of pentavalent or trivalent
atoms in semiconductor

Interstitial Impurity
Refers to a small foreign atom which
occupies the interstitial space in the
lattice without affecting the parent
atoms from the their regular place
https://www.askiitians.com/iit-jee-solid-state/imperfections-in-solids-and-defects-in-crystals/
http://studytronics.weebly.com/crystal-structure--defects.html
 Interstitial Impurity
 Frenkel effect
• Occurs in ionic crystals
• Due to displacement of
cations from their regular
sites to interstitial sites
• Since cations are smaller,
does not affect the lattice
 Schottkey effect
• Occurs due to the missing
of a pair of anion and
cation from their regular
place in a lattice
https://www.askiitians.com/iit-jee-solid-state/imperfections-in-solids-and-defects-in-crystals/
 Line Imperfections
One dimensional
imperfections
Also called as dislocations
Types
Edge dislocation
Screw dislocation

Edge dislocation
Consider a crystal space lattice as shown
in fig.1.
The image at the bottom of fig.1
represents the front side atomic
arrangement.
The arrangement shows the periodic Fig.1
arrangement of atoms in all vertical lines of
lattice
 Line Imperfections
Edge dislocation
 In fig.2 there is a discontinuity in
atomic ordering in one of the line.
This type of missing of atoms in a
line is called line imperfection
Above the imperfection the atoms
are compressed and below the
imperfection the atoms are dragged
out and in a state of tension.
This distorted configuration extends
up to the edge of the crystal as shown
Fig.2
in fig.2
 Line Imperfections
Edge dislocation
Positive and negative edge
dislocations

When the incomplete plane starts

from the top of crystal it is positive
edge location

If it is from bottom of crystal it is

negative edge dislocation
 Line Imperfections
Edge dislocation
Burgers Vector
The magnitude and direction of
displacement is called Burger vector.
Fig.3 shows a perfect crystal
A vector line is drawn from P.
It travels through 6 atoms top
Then travels through 5 atoms right
Then travels through 5 atoms
down
Then travel through 6 atoms left
Fig.3 Fig.4
and reaches the point P.
Burger circuit is closed
 Line Imperfections
Edge dislocation
Burgers Vector
Fig.4 shows a crystal with edge
dislocation
When the above operation is
repeated, the vector ends up in Q
instead of P
To reach P , we have toreturn
through QP
The vector QP is the Burger vector
Fig.3 Fig.4
Burger Vector BV = QP = b
 Line Imperfections
Screw dislocation
Fig.5 shows a crystal with screw
dislocation
It is due to the displacement of
atoms in one part of a crystal
relative to the other part.
This creates a spiral ramp at the
line of dislocation
 b is the burger vector at the edge
Fig.5
dislocation
Burger circuit is drawn as shown
in the fig5.
 Surface Imperfections
Distortions at the crystal
surface of few atomic diameter
thickness
Occurs due to the termination
of atomic bonds at the surface
Also occurs inside the crystal
during recrystallization process
In recrysatallization, the grains
of crystal grow in different
orientations as shown in fig.6 Fig. 6
 Surface Imperfections
One grain compress the another
one and atoms at boundary
displaced to equilibrium due to
varying forces at the boundary
The regions are called grain
boundaries
They have thickness of few atomic
diameter
The misalignment of grains result
in a sharp change of crystal
orientation at the boundary as Fig.6

shown in fig.6
 Surface Imperfections
High angle and Low angle boundaries

High angle boundaries

If the orientation difference
between the grains (crystals) is
greater than 10 degrees (Fig.6)
Low angle tilt boundaries
The orientation difference is less
than 10 degrees. The tilt boudary is
shown in Fig.7

Fig.7
 Surface Imperfections
Stacking Faults
Planar surface
imperfection
Occurs due to the fault
in the stacking sequence of
atomic planes in crystals

Twin Boundaries
Planar surface
imperfection
Atomic arrangements in
one side of boundary is the
Fig.8
mirror image of other side of
boundary
The intermediate region is
called twinned region (Fig.8)
 Volume Imperfections

Cracks in a crystal is a volume defect

Cracks may occur during growth
Cracks can occur due to the electrostatic dissimilarity produced between
layers of crystal during growth
Cracks may occur when crystal is subjected to an external stimulus
Missing a cluster of atoms inside the crystal
Large void in the crystal is also a volume defect
When the crystal is grown, chances are there for the setting up of non
crystalline regions of considerable size inside the crystal.