Crystal Structure

23CHY109
Engineering Chemistry
Dr. Mohan Kumar T. M.
1
 23CHY109
Engineering Chemistry
Unit I
Solid state- Fundamentals of crystalline structures – unit cell, lattice parameters, Bravais lattices and types of
crystals; Xray diffraction - Bragg’s equation and experimental methods (powder method and rotating crystal
technique); Elements of symmetry in crystal systems, defects in crystals – stoichiometric, non-stoichiometric,
extrinsic and intrinsic defects. Vesta – for visualization of crystal structures. Solar energy - introduction,
utilization and conversion, photovoltaic cells - design, construction and working, panels and arrays. Advantages
and disadvantages of PV cells. DSSC (elementary treatment).

2
Solid state
• Fundamentals of crystalline structures – unit cell, lattice parameters,
Bravais lattices and types of crystals

3
4
Solids

• Rigid

• Incompressible

• Have definite mass

• Constituent particles will have fixed positions

• Strong intermolecular forces

• Short intermolecular distances

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Crystal: term comes from Greek term crystallon meaning cold drop or frozen drop

• is a substance in which the atoms, ions or molecules are arranged in a

definite, repeating pattern in three dimension across its whole volume.
(orderness for long range).

• Even at infinite length scales, each atom is related to every other

equivalent atom in the structure.

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➢Polycrystal is a material made up of an aggregate of many small single
crystals (also called crystallites or grains) .

• The grains are usually 100 nm - 100 microns in diameter.

➢If the grain diameter is < 100 nm, they are called nano-crystalline
solids.

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 Amorphous Crystalline
I. Pseudo solids I. True solids
II. Do not have regular arrangement II. Regular 3D arrangement of
of particles for long distance particles
III. Do not have well defined position III. Have well defined geometrical
for particles for long distance shape
IV. Short range ordering IV. Long range ordering
V. Do not have sharp melting point V. Sharp M.P.
VI. Do not have fixed heat of fusion VI. High and fixed heat of fusion
VII. ISOTROPIC in nature VII. ANISOTROPIC

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The heat of fusion is the amount of energy required to convert one mole of solid into liquid.
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Isotropic materials: Amorphous
• have the same or similar properties throughout the material.
• They show the same properties in all directions
• This is due to their uniform composition throughout.

Anisotropic materials: Crystalline

• have varying properties in different orientations of the mineral surface.
• The differences in properties are due to the compositional differences.

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 Isotropic Anisotropic
Amorphous Crystalline

Properties Direction independent Direction-dependent

Refractive index Only one More than one
Velocity of light Same in all directions Different
Chemical bonding Consistent Uncertain

Example Glass, wood Any crystalline solid

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 Why should study crystals?
• Structure-Property Relationship: properties of materials are closely linked to their crystal structure.

• Eg: hardness of diamond and the conductivity of metals are determined by their crystal lattices.

• Crystals exhibit anisotropy, which is crucial for designing materials with specific characteristics.

• Crystals like quartz and calcite are used in lenses, lasers, and optical fibers.

• Metallurgy: crystal defects and grain boundaries influences the conductivity, strength and durability of metals,
alloys, semiconductors etc.

• Crystals are key to developing new materials like superconductors, ferroelectrics, and nanomaterials.

• Helps in understanding biological molecules, leading to drug discovery and disease research.

• Study of crystal structures reveals information about the Earth's composition and the formation of minerals.

• Crystals found in meteorites provide clues about the origins of the universe.
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For better understanding of crystal structure, we must
know the following technical terms of crystals like…..

➢ Lattice
➢ Space Lattice
➢ Basis
➢ Unit cell
➢ Lattice parameters
➢ Lattice constant
➢ Atomic packing factor ( APF )
➢ Co-ordination number…….

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Lattice /Crystal lattice & Unit cell

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 Space lattice
An imaginary point in space

or

A three dimensional translational periodic arrangement of

imaginary points in space is called a lattice.

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 Basis (or) Motif

An atom or a group of atoms associated with each

lattice point is called as basis or motif.

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Crystal = Space Lattice + Motif (basis)

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 Cell / Unit cell
➢A cell is a parallelogram (2D) or a parallelopiped (3D) with
lattice points at their corners.
1-D Lattice

∞ ∞
2-D Lattice 3-D Lattice
∞

∞
∞ ∞
∞

∞ 19
 Lattice parameters
a, b, & c --- the primitives of the unit cell. Y
AND
α, β, & γ --- the interfacial angles.

b
These lattice parameters decide
the actual size and shape of the
α γ a
X
unit cell.
c β

Z
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 BRAVAIS LATTICE
In 1850, M. A. Bravais showed that identical points
can be arranged is space to produce 14 types of
regular patterns.
M. A. Bravais
These 14 space lattices are known as ‘Bravais lattices’.

Lattices are classified on the basis of their symmetry

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Bravais: a French physicist
 14 types of space lattices can be classified
into 7 different crystal systems/classes.

Cubic 3
Tetragonal 2
Orthorhombic 4
07 Monoclinic 2
Triclinic 1
Rhombohedral/ Trigonal 1
Hexagonal 1
Total= 14
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Why are there only 7 crystal systems?

In 3D, it's impossible to have more than 7 !

Because mathematically, it's impossible to have more

crystal systems in 3D space.

"Other" crystal systems can be cut down (simplified) to one

of the seven!

There are seven crystal systems, with 14 Bravais-types, 32

crystallographic point-groups and 230 space groups. 23
1. Cubic Systems
a = b = c ; 𝛂 = 𝞫 = 𝝲 = 90o
3 possible types

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2. Tetragonal Systems
a=b≠c ; 𝛂 = 𝞫 = 𝝲 = 90o
2 possible types

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3. Orthorhombic Systems
a ≠ b ≠ c ; 𝛂 = 𝞫 = 𝝲 = 90o
4 possible types

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4. Monoclinic Systems
a ≠ b ≠ c ; 𝛂 ≠ 90o and 𝞫 = 𝝲 = 90o
2 possible types

Base Centered
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5. Triclinic Systems
a≠b≠c ; 𝛂 ≠ 𝞫 ≠ 𝝲 ≠ 90o
1 possible types

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6. Rhombohedral / Trigonal Systems
a = b = c ; 𝛂 = 𝞫 = 𝝲 ≠ 90o
1 possible types

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7. Hexagonal Systems
a = b ≠ c ; 𝛂 = 𝞫 = 90o and 𝝲 = 120o
1 possible types

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31
 NAME OF THE No. OF PRIMITIVES INTERFACIAL
TYPES EXAMPLE
CRYSTAL LATTICES (a, b, c) (α,β,γ)

3 S, B, F CsCl, NaCl
Cubic a=b=c α = β = γ = 900

2 S, B TiO2 (Rutile), SnO2

Tetragonal a=b≠c α = β = γ = 900
(Cassiterite)
4 S, B, F, C KNO3,
Orthorhombic a≠b≠c α = β = γ = 900
BaSO4 (Baryte)
1 S α = β = γ <1200
Rhombohedral
a=b=c ≠900 Ice, Al2O3
(Trigonal)

1 S α = β = 900 ;
Hexagonal a=b≠c Mg, Zn, PbI2
γ= 1200
2 S, C α =γ = 900 ; Monoclinic Sulphur,
Monoclinic a≠b≠c
β ≠ 900 Na2SO4.10H2O
1 S
Triclinic a≠b≠c α ≠ β ≠ γ ≠ 900 CuSO4.5H2O

S: Simple cubic B: Body centered

F: Face centered C: base Centered 32
 MILLER INDICES
• The set of three integers used to describe the William Hallowes Miller
orientation of a crystal planes are called Miller Indices.

• General form for Miller Indices of a plane is (h k l)

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 Procedure for finding Miller Indices

Step: 1 Find the intercepts of the plane along

the 3 axes a, b & c .

Step: 2 Take reciprocals of the intercepts.

Step: 3 Convert into smallest integers in the same ratio.

(Taking its LCM)
Step: 4 Enclose in parentheses .

NOTE: The reciprocal procedure avoids the intercept of infinity for

a plane parallel to an axis by making it to zero. 34
Some Miller planes

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001 Plane 110 Planes

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111 Planes

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Example:
Step: 1 Intercepts are 2,1,2 1
2
2
Step: 2 Take the reciprocals
of the intercepts
2,1,2 as 1/2, 1,1/2

Step: 3 Convert into smallest

integers as 1,2,1

Step: 4 Enclose in the parentheses as (1 2 1).

Gives the Miller Indices for the above plane. 39
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011 Plane

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 Xray diffraction
• X-ray diffraction (XRD) is used to study the crystal structure.

• Measure the average spacings between layers or rows of atoms.

• Measure the size, shape and internal stress of small crystalline regions

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 How X-ray crystallography done?
1. Take a purified sample of a molecule, a crystal or amorphous.

2. Above sample is exposed to an X-ray beam.

3. The X-rays interact with the electron clouds of the atoms in the crystal/amorphous.

4. The resulting pattern of diffracted X-rays is recorded by a detector (CCD: Charge

coupled device) as spots.

5. Computer program is used to visualize the molecular structure.

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X-rays are produced in X-ray tubes

1. Electrons are produced: A current is applied to a cathode filament, which heats up and
releases electrons.

2. Electrons are accelerated: The electrons are accelerated towards a positive anode by a
voltage applied across the tube.

3. Electrons hit the target Anode: The electrons hit the target matal, such as tungsten,
molybdenum, cobalt etc, and slow down.

4. X-rays are released: As the electrons slow down, they release X-rays. 49
• Crystal is bombarded with X-rays of a fixed wavelength (similar to inter planar
distance ‘d’ )
X-ray sources with different wavelength () for doing XRD studies

When an electron falls (cascades)

from L-shell to the K-shell = x-ray emitted is called a
K-alpha x-ray.
from M-shell to K-shell, the x-ray emitted is called a
K-beta x-ray.

• In crystals the typical interatomic spacing ~ 1–3 Å so the suitable radiation is X-rays.

• Hence, X-rays can be used for the study of crystal structures

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• X-rays are either transmitted through the crystal, reflected off the surface, or diffracted by the crystal
lattice.

• A beam stop is located on the opposite side to block transmitted rays.

• Reflected rays are not picked up by the detector due to the angles involved.

• Diffracted rays at the correct orientation for the configuration are then collected by the detector.

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• Crystals will have periodic array of atoms called the crystallographic planes.

• When the x-ray strikes the crystal, x-ray will enters into the crystal.

• Each plane of the crystal reflect a portion of the X-ray.

• When the X-ray falls on the atom, it interact with the electron of that atom and get
diffracted as x-ray.

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• Physicists Sir W.H. Bragg and
his son Sir W.L. Bragg
developed the relationship

Bragg’s Law

n  = 2d sinq

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• when the difference in the travel path of AOA’ and BOB’ is equal to integral
multiple of the wavelength (n λ) of the incident X-ray, then constructive interference
will occur.

• [ when ‘λ’ and ‘d’ matches i.e., when ‘d = n λ’ , constructive interference happens ]

• a diffracted beam of X-rays will leave the crystal at an angle equal to that of the
incident beam i.e., ‘θ’ with constructive interference. [ λ , d and θ matches ]

• the diffracted X-rays will interfere constructively to produce an intense beam of X-rays
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Bragg's Law: When x-rays are scattered from a crystal lattice, peaks/spots of
scattered intensity are observed which correspond to the following conditions:

The angle of incidence = angle of scattering.

The path length difference = an integer number of wavelength.

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• Θ = Braggs angle
• d = inter planar distance

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 λ Ɵ= Braggs angle
λ= angle of incidence
d= distance between planes
n is an integer

When a crystal is bombarded with X-rays of a fixed wavelength (similar to

spacing of the atomic-scale crystal lattice planes) and at certain incident angles,
intense reflected X-rays are produced when the wavelengths of the scattered X-
rays interfere constructively.

Bragg's Law, expressed as: n λ = 2d sinΘ

where n (an integer) is the "order" of
reflection, λ is the wavelength of the incident
X-rays, d is the interplanar spacing of the
crystal and Θ is the angle of incidence.
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Rotating crystal method

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 Solids
• 1) Single crystal- Single crystal XRD

• 2) Powder XRD- Polycrystalline XRD

a) Poly crystal
b) Micro crystal
c) Nao-crystal
d) Amorphous

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 Single crystal method / Laue Method (Max
von Laue, in 1912)

• A single crystal is mounted on a rotating shaft.

• Shaft is rotated to rotate the crystal.

• A cylindrical photographic film/sensor is placed around the crystal.

• With its axis perpendicular to the incident beam.

• X-ray with particular λ is focused, and the incident angle is varied.

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 Single crystal XRD

• Crystals consist of planes of atoms (atomic planes) that are spaced by a distance ‘d’ apart,

• Each plane with a different d spacing ( eg: d1, d2, d3, ….. ).

• Different planes, with different spacing.

• To satisfy Bragg’s law, θ has to change as d changes.

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 Diffraction pattern for ZnS in 1912 by von Laue

• When the Bragg’s eqn is satisfied

• i.e., when the ‘λ’ and the interplanar spacing ‘d’ matches (when d = n λ) , and the diffracted
beam of X-ray leave the crystal at an angle equal to that of the incident beam, θ.

• A constructive interference happens, and a spot will be generated on the photo film/sensor.

• Each plane in the crystal will give one spot.

• Diffraction from different planes of atoms produces a diffraction pattern, which contains
information about the atomic arrangement within the crystal.
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• Intensity and position of the spot determines the specific set of lattice
planes in the crystal, described by Miller indices (h k l ).

• Positions of the diffraction spots will determine the lattice parameters.

• Software tools like VESTA, CRYSTALS, Olex2 etc, are used for
processing and refinement. 65
Solids
• 1) Single crystal- Single crystal XRD

• 2) Powder XRD- Polycrystalline XRD

a) Poly crystal
b) Micro crystal
c) Nao-crystal
d) Amorphous

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Powder XRD --1

is used for microcrystalline or amorphous

powder samples.

It is difficult to grow high-quality single crystals of sufficient size to perform

single crystal XRD measurements for many materials.

Sample preparation is easy,

but it require more quantity of powder sample.
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Powder XRD --2

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Powder XRD --3

A powder X-ray diffractometer consists of

an X-ray source & a way to vary the incident angle θ,

a sample stage and

a detector

• X-ray is focused on to the sample at an angle θ.

• The incident angle ‘θ’ is changed continuously.

• A circle of film is used to record the diffraction pattern as shown.

• or the detector is made to moves in a circle around the sample.

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Powder XRD --4
• Powdered sample contain thousands of microcrystals oriented in random
directions.

• A particular plane for example:(101) of a crystal will diffract forming 1 spot.

• Similarly, (101) plane of each of the crystal will diffract the X-ray when the
sample is rotated.

• So, the diffracted beams will form a continuous cone for (101) plane.

• Each cone / ring corresponds to one set of identical planes within the
powder sample.

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Powder XRD --5

• Each cone / circle corresponds to one plane, gives rise to a peak.

• Detector position is recorded as the angle 2theta (2θ).

• X-ray intensity is recorded as “counts per second”.

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Powder XRD --6

Powder X-ray
diffraction pattern

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Powder XRD --7
X-ray diffraction of SiO2

• All the 3 are SiO2

1. Silica glass - Amorphous

2. Quartz – SiO2 - crystalline

3. Cristobalite – SiO2 - crystalline

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74
Single crystal Diffraction Pattern Powder XRD: Circular Diffraction Pattern.

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 Single crystal XRD Powder XRD
1. Non destructive 1. Non destructive
2. Single crystal is required 2. Polycrystalline, microcrystalline or
amorphous solid sample is possible.
3. One very small crystal is enough.
3. More quantity of sample is required.
4. Ultimate structure of the substance will be
established. 4. Composition can be established.
5. No separate standard is required to 5. A reference standard is required to confirm
establish the structure. the composition.
6. Sample analysis require few hours. 6. Sample analysis completes in few minutes.
7. Possible for 100% pure substance. 7. % quantity of composition (purity) can be
determined.
8. Difficult to grow high-quality single crystals
8. Sample preparation is easy.
9. Diffraction produces periodic dots.
9. Diffraction produces concentric rings.

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Strengths of Single-crystal XRD
• Non-destructive

• No separate standards required

• Detailed crystal structure, including unit cell dimensions, bond-

lengths, bond-angles etc.

• Structures of high pressure and temperature phases can be

determined (alpha, beta phase)

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Limitations of Single-crystal XRD
• Must have a single, robust (stable) sample,
generally between 0.1 – 0.5 mm in size.

• Optically clear sample is required.

• Data collection requires few hours.

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There are four types of crystals

1. Ionic

2. Metallic

3. Covalent and

4. Molecular crystals

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Ionic Crystals
• Consists of alternate +ve cations and –ve anions.

• The ions may either be monatomic or polyatomic.

• Monoatomic: NaCl, CaO. polyatomic: CaCO3, Co(NO2)3.
• Generally, ionic crystals form by the combination of
Group-1 or 2 metals and Group-16 or 17 nonmetals
or nonmetallic polyatomic ions.

• Ionic compounds do not conduct electricity as

solids, but do conduct when molten or in aqueous
solution., Eg: NaCl, NaOH
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• Ionic crystals are hard and brittle and have high melting points.

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Metallic Crystals
• Consist of metal cations surrounded by a “sea”
of mobile valence electrons.

• These electrons, also referred to as delocalized

electrons, do not belong to any one atom, but
are capable of moving through the entire crystal.
•
• As a result, metals are good conductors of
electricity.

• The melting points of metallic crystals display a

wide range.

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Factors like atomic size, electron delocalization, and lattice structure complexity contribute to the variation in the M.P. of metals.
 Covalent Network Crystals
• Consists of atoms at the lattice points of the crystal,
with each atom being covalently bonded to its nearest
neighbor atoms.

• The covalently bonded network is three-dimensional.

• These are hard and brittle, with extremely high

melting and boiling points. Being composed of atoms
rather than ions, they do not conduct electricity in any
state.

• Eg: diamond, quartz, many metalloids, and oxides of

transition metals and metalloids.
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Molecular Crystals
• Consist of molecules at the lattice points of the
crystal, held together by relatively weak
intermolecular forces.
• The intermolecular forces may be dispersion forces in
the case of nonpolar crystals, or dipole-dipole forces
in the case of polar crystals.
• Some molecular crystals, such as ice, have molecules
held together by hydrogen bonds.
• As a result, the melting and boiling points of
molecular crystals are much lower.
• Lacking ions or free electrons, molecular crystals are
poor electrical conductors. Eg: Ice, solid CO2
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• In ice each water molecule is hydrogen bonded to 4 other
neighboring water molecules to form ice crystal.

• In liquid water, each molecules is H−bonded to

approximately 3.4 other water molecules.

• These H−bonds are constantly being formed and breaking up

because of rapid thermal motions of molecules but in ice
hydrogen bonds are stable.

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Close Packing in Crystals
• It is a space efficient arrangement of constituent particles in a
crystal lattice.

• To minimize the complexities let us assume all particles (atoms,

molecules and ions) are of the same spherical solid shape.

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One Dimensional Close Packing

• In this arrangement, the atoms are arranged in a row.

• All the atoms are closely packed and are in contact with each other.

• So one atom is in contact with the atom on both the sides.

• So there are two atoms near any one particular atom. This makes the
coordination number of the one-dimensional structure 2.

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 Two Dimensional Close Packing

• This stacking of the rows can be done in 2 ways.

• AAA type and ABA type

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• AAA Type: In this type of packing, two rows are stacked right above each other.

• One row is packed directly above or below the other one.

• Each sphere is directly touching the 2 spheres above and below, and 2 spheres to the
right and left. So the coordination number of this will be 4.

• ABA Type: In this type the spheres of the second row to be seated on the first row in a
staggered manner, that is, in the depressions of the first layer.

• The stacking is not uniform as in the AAA type. Here the spheres are in contact with six
other spheres, so the coordination number is 6. Also when you join these contact points
it will form a hexagonal shape.

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 Three Dimensional Close Packing
• This is the real structure of the space lattice. It is a 3D arrangement of
atoms. Now, this structure forms by the continuous and repetitive
stacking of the two-dimensional structures above each other. It can
also happen in two ways. AAA type and ABA type

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 Close packed system exhibited by different materials can be classified into 4
categories

(i) Simple cubic ; (ii) BCC ; (iii) FCC & (iv) HCP

• Cubic Close Packing: Here the layers are placed exactly above each
other in symmetry. This shape takes the form of a cube and hence the
name. The coordination of such a structure is 6, 8 & 12.

• Hexagonal Close Packing: Here the alternating layers cover each

others gap. Spheres in one layer align to fit in the gaps of the previous
layer.
• The first and the third rows have the same alignment.
• So we call this ABA type.
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Atomic packing fraction = packing efficiency of a unit
cell
• APF is the fraction of volume actually occupied by the atoms in a
unit cell.

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simple cubic unit cell

• CN = 6

• No. of atoms per unit cell = (1/8 x 8) = 1

• Eg: Polonium

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simple cubic unit cell

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BCC unit cell

• CN = 8

• No. of atoms per unit cell = (1/8 x 8) + 1 = 2

• Eg: Li, Na, K, Fe, . . .

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In triangle ADF body centered cubic unit cell

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FCC unit cell

• CN = 12

• No. of atoms per unit cell = (1/8 x 8) + (1/2 x 6) = 4

C
• Eg: Cu, Al, Pb, Ag

A
B
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 In triangle ACD,

APF in FCC

A
B
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HCP unit cell

• CN = 12

• No. of atoms per unit cell =

(1/6 x 6) + (1/6 x 6) + (1/2 x 2) + 3 = 6

• Zn, Mg, Cd

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HCP close packing : ABA type

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 APF in HCP
Area of
equilateral
triangle is

101
102
103
104
Symmetry: repetition of something in space and/or in time
A MAN, A PLAN, A CANAL, PANAMA

AMANAPLANACANALPANAMA

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• The elements of symmetry in a crystal are

Plane of symmetry

Axis of symmetry and

Centre of symmetry.

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Plane of symmetry is the imaginary plane which passes
through the centre of the unit cell and divides it into 2 equal parts
(just mirror images of each other).
(i) Rectangular & (ii) Diagonal POS

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Rectangular planes of symmetry = 3

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109
Axis / line of symmetry is an imaginary straight line.
• Rotating a crystal along this axis for 360o gives similar appearance
more than one time.
It is 2 fold, 3 fold, 4 fold and 6 fold rotation respectively
along 2 fold, 3 fold, 4 fold and 6 fold axis of symmetry.

2 fold rotation
180o
3 fold rotation 4 fold rotation
110
120o 90 o
 2 fold axis of symmetry
Line joining the center of
opposite parallel edges.

12 edges in a cube.

Six number of 2 fold axis

of symmetry are
possible

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 3 fold axis of symmetry
Line joining the corner points of 2
opposite edges (corners).

8 edges in a cube.

4 diagonals in a cube.

Four number of 3 fold axis of

symmetry are possible.

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4 fold axis of symmetry
Line joining the center of
opposite parallel faces.

6 faces in a cube.

3 axis in a cube.

Three number of 4 fold axis

of symmetry are possible.
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Axis of symmetry in cube
2 fold symmetry = 6

3 fold symmetry = 4

4 fold symmetry = 3

Total number of axis of symmetry in a cube = 13

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6 fold axis of symmetry in hexagonal crystal

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 Centre of symmetry or Inversion point
• is an imaginary point in the unit cell, when a line is drawn through
it, will intersect the surface of the unit cell at equal distance on
either sides.
A crystal can have only 1 centre of symmetry.
If body diagonals are drawn through the cube in opposite direction
we get a center of symmetry.

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117
 Crystal defects / Imperfection in Crystals
• Any deviation in the ordered arrangement of particles in the crystal.
• There is no perfect crystal.

• The mechanical, electrical, electronic and optical properties are controlled

by these defects.

• Eg: few ppm of Al will change the character of Si.

• Dislocations of planes will increase the resistivity of metals, cause significant leakage
of current in a p-n junction and can cause unwanted noise/heat in various
semiconductor devices.

• Dislocations of planes will decrease the mechanical strength of crystals.

• The occurrence of defects can be controlled or eliminated by carefully

growing the crystals.
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• Crystal defects can arise during the crystal growth process, as a
result of external influences, or due to intrinsic material
characteristics.

• By studying crystal defects, we can gain insights into material

deformation, failure mechanisms, and the overall performance of
crystalline materials in various applications.

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Crystal Defects
1. Point defects

2. Line defects

3. Planar defects

4. Volume defects

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Point Defects / Thermodynamic defects
• As a requirement of thermal equilibrium.
• These defects destroy the perfect periodicity in the crystal.

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Point defects:
(a) Stoichiometric defects & (b) Non-stoichiometric defects

(a) Stoichiometric Defects

• These are the point defects that do not disturb the stoichiometry
of the solid.

• They are also called intrinsic or thermodynamic defects.

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Point defects
Stoichiometric Defects
• (i) Vacancy defect

• (ii) Substitutional defect

• (iii) Interstitial defect

• (iv) Frenkel defect

• (v) Schottky defect

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• (i) Vacancy defect: When an atom is missing from its lattice site, then that lattice
site remain vacant and it creates a vacancy defect.

• The planes around the vacancy will be distorted from its perfect arrangement.

• This vacancy volume will be smaller than the volume of missing atom.

• Due to this, the density of a substance decreases.

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• (ii) Substitutional defect: An impurity atom will replace the host atom (big/
small/ equal in size)

• When Silicon is doped with Arscenic.

• C in iron.

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• (iii) Interstitial defect: It is a defect in which an atom or molecule
occupies the intermolecular spaces in crystals.
• In this defect, the density of the substance increases.

• A non-ionic compound mainly shows vacancy and interstitial defects.

• An ionic compound shows the same in Frenkel and Schottky defect.

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• (iv) Frenkel Defect: Among ionic solids, the smaller ion (cation) moves out of its
lattice position and occupies an intermolecular space.

• In this case, a vacancy defect is created on its original position and the interstitial
defect is experienced at its new position.

• It is also known as dislocation defect.

• The density of a substance remains unchanged.

• It happens when there is a huge difference in the size of

anions and cations.

• Example: ZnS and AgCl.

• Atomic radius: Zn-180pm, S-100pm, Ag-144pm, Cl-79pm 127

• (v) Schottky Defect: This kind of vacancy defects is found in Ionic
Solids.

• Equal number of anions and cations will be missing from the

compound.

• It reduces the density of the substance.

• In this, the size of cations and anions are of almost the same.

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(b) Non-Stoichiometric Defects

• Some inorganic solids can have constituent elements in

non-stoichiometric ratio due to defects in their crystal structures.

• These defects are of two types:

(i) Metal deficiency defects & (ii) Metal excess defects

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 Metal excess defects
• In this, the solids have more number of metals relative to
the desired stoichiometric proportion.

• This type of defect occurs in alkali halides such as NaCl and

KCl.

• When NaCl crystals are heated in an environment of

sodium vapour, sodium atoms are deposited on the crystal
surface.

• Cl– ions diffuse to the crystal’s surface and react with Na

atoms to form NaCl. Na will loose 1 electron to become
Na+ ion.

• This free electron sit in the original place of Cl- ion.

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Metal deficiency defect
• In this, the solids have less number of metals relative to the desired
stoichiometric proportion.
• There are many solids which are difficult to prepare in the stoichiometric
composition. They contain less number of metal as compared to the
stoichiometric proportion.
• A typical example of this type is FeO (ferrous oxide) which is mostly found
with a composition of Fe0.95O. It may actually range from Fe0.93O to Fe0.96O.
• M. deficiency defect is seen when variable valencies are shown by a
metal
• Some cations leave the lattice site. Some of the remaining cations in
the lattice will increase their valency to maintain electrical neutrality
of the compound.
• In crystals of FeO some Fe2+ cations are missing and the loss of positive
charge is made up by the increase of oxidation state form Fe2+ to Fe3+ ions.
• Electrical neutrality is maintained, but the number of metal atoms will be
lesser. 131
132
Metal deficiency defect: Uses
• Superconductivity- Numerous superconductors are non-
stoichiometric solids.

• For example, yttrium barium copper oxide [YBa2Cu3O7] is a non-

stoichiometric solid.

• It is a well-known high-temperature superconductor.

• The superconductor’s critical temperature is dependent on the

precise composition.
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Intrinsic defects
• Intrinsic defect is the imperfections within a material that occur
naturally during the crystal growth.
• There will not be any impurities or foreign atoms.
• It could be vacancies (unoccupied lattice sites), self-interstitials (an
extra atom squeezed in between other atoms), or Frenkel and
Schottky defects.
• Eg: vacancy in a silicon crystal

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Extrinsic defects
• Extrinsic defect is the imperfection in a material caused by the
inclusion of atoms of a different element.
• These defects may cause the material to exhibit foreign or altered
properties.
• Extrinsic defects can be induced purposely (doping) to enhance a
material's properties, for instance, in semiconductors to control their
electrical properties.
• Or in the form of impurity.
• Eg: n / p type Si

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