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Perfect Crystals

All unit cells consist of the ideal arrangement

of atoms or molecules as defined by the crystal
Atomic arrangements are in a specific order all
through maintaining a periodicity in
their structure
The positions of atoms or
molecules keep on
repeating after fixed
distances determined by
the unit cell parameters

All cells line up in a three

dimensional space with no

perfect crystal

Important !!!

No crystal is perfect in true sense since

Perfect crystals could be produced at absolute

zero only (hypothetical case)

Very difficult and expensive to produce perfect


Even the best crystals have 1ppb defects

No matter how carefully produced in practice,

bound to have some defects

Defective Crystals
Deviation from idealism

Possess superior mechanical properties with

increasing defects (within limits) but always
inferior to that of a perfect crystal

Two-dimensional model of
polycrystalline solids with

Crystal Defects

Distortion or violation of regularity in the atomic


Imperfections in the regular geometrical

arrangement of the atoms
- depend upon temperature and presence of

Result from

Deformation of the solid

Rapid cooling from high temperature

High-energy radiation (X-rays or neutrons)

striking the solid


Crystal Defects

Located at single points, along lines, or on

whole surfaces in the solid

Influence mechanical, electrical, and optical

behaviour due to
- Creation of distortion/deformation around it

Forming local inhomogeneity in the crystal

Causing displacement of atoms from their

equilibrium positions

A relatively small number of defects have a

profound impact on the macroscopic properties
of material

Typical Modes of Deviations from Perfect

Crystal Ordering

Absence of atoms/ions

Entrapment of extra atoms/ions

Presence of grain boundaries

Interrupted rows of atomic layers compared

to that of an ideal or imaginary crystal lattice

Incorporation of impurities

Misalignment of cells

Practical Relevance of Crystal Defects

Number and type of defects in a diamond crystal
that define the cost of a given crystal size

Production of advanced semiconductor devices

requires perfect Si crystal with specific defects in
small areas of the sample
- A defect free (ideal) silicon crystal would be of
little use in modern electronics
Presence of defects which affect the colour can
make these crystals valuable as gems

- ruby (chromium replacing a small fraction of

the aluminium in aluminium oxide: Al203)

Practical Relevance of Crystal Defects

Plastic deformation in a material occurs due to

the movement of defects (dislocations)
leading to strengthening /shaping of material

Colour of an insulating crystal or the

conductivity of a semiconductor crystal may
be much more sensitive to the presence of
small number of defects

Impurities often make crystals more useful

In the absence of impurities, -alumina is


Iron and titanium impurities impart to alumina a blue colour, and the resulting gemquality mineral is known as sapphire

Practical Relevance of Crystal Defects

Pure semiconductors rarely conduct

electricity well at room temperature

Ability to conduct electricity caused by

- Impurities (P and As) deliberately added to
silicon in the manufacture of integrated
- In fluorescent lamps, the visible light is
emitted by impurities in the phosphors
(luminescent materials)

Much of materials science involves the study

and engineering of defects so that solids will
have desired properties

Structure Insensitive Properties

Elastic Constants
Melting point
Specific heat
Coefficient of thermal expansion

Structure Sensitive Properties

Electrical conductivity
Mechanical properties
- Yield stress
- Strength
- Hardness

Defect Concentration

Number of defects at equilibrium concentration at a

certain temperature:
n = N exp [-Ed / kT]

Where n - number of imperfections, N - number of

atomic sites per mole, k - Boltzmann constant, Ed - free
energy required to form the defect and T - absolute
E = 1 eV, k = 8.62 X 10-5 eV /K, T = 1000 K
n/N = exp[-1/(8.62 x 10-5 x 1000)] 10-5, or 10 parts per
For many purposes, this fraction would be intolerably large,
although this number may be reduced by slowly cooling the

Types of Crystal Defects

A) Based on the source of defects

Stoichiometric (intrinsic) defects

- Frenkel defects
- Schottky defects
- Complexes
- Interstitials

Non-stoichiometric (extrinsic) defects

B) Based on the Scale of occupation

Point defects
Linear defects
Area/planar defects
Volume defects

(zero dimension)
(0ne dimension)
(Two dimensions
(three dimensions)

Linear and area/planar defects are called lattice

defects since they extend over the microscopic
region of the crystal

Types of Crystal Defects

C) Other types

Metal excess defects

Metal deficiency defects

Defect Clusters

Types of Crystal Defects

Stoichiometric (intrinsic) defects


Caused by a deviation in the ratio of ions

in stoichiometric ionic solids due to
thermal activation

Stoichiometric solids are those in which

numbers of positive and negative ions are
exactly in the ratio indicated by their
chemical formulae

Non-stoichiometric (extrinsic) defects

- Generated by doping pure crystals with
impurity atoms from external sources

Stoichiometric (Intrinsic) Defects

Frenkel defect

Occurs when an atom/ion vacates its position in the lattice

and transfers to an interstitial position in the crystal
- A vacancy and interstitial

Usually referred to as Frenkel pair of defects

Frenkel defect (vacancy-interstitial pair)

Stoichiometric (Intrinsic) Defects

Schottky defects

Consists of a pair of vacant sites

- an anion vacancy and a cation vacancy

Formed when
- A pair of holes or vacancies exists in the
crystal lattice due to one cation and one
anion missing from the normal lattice sites

Pair of point defects stays near each other due to

strong coulombic attraction of their opposite

Occurs in highly ionic compounds with a high

coordination number and where the ions (both
cations and anions) are of similar size

Alkali metal halides such as NaCl, KCl, KBr and

CsCl show this defect

Stoichiometric (Intrinsic) Defects

Schottky defects

A pair of cation and anion vacancies in an

ionic crystals

Stoichiometric (Intrinsic) Defects

- Can form between different kinds of point
-- If a vacancy encounters an impurity, the
two may bind together if the impurity is too
large for the lattice

- Can form 'split interstitials' or 'dumb-bell'
-- where two atoms effectively share an
atomic site resulting in neither atom
actually occupying the site

Split interstitial in a
BCC metal
Split interstitial in an FCC metal
Solid/blackcircle: interstitial atoms
Open circle: normal lattice site
Rectangle: octahedral site

Atomic displacement
near an interstitial in a
primitive cubic lattice

configuration of an
interstitial atom

Non-stoichiometric (Extrinsic) Defects

Generated by doping pure crystals with

impurity atoms from external sources

Impurities (P and As) deliberately added to

silicon in the manufacture of integrated

Ruby (chromium replacing a small fraction of

the aluminium in aluminium oxide: Al203)

Metal Excess Defects

Form due to
A) Anionic vacancies created by the absence
of a negative ion from its lattice site, leaving
a hole occupied by an electron that was
associated with the negative ion and
remains trapped in the vacancy thereby
maintaining the electrical neutrality
-- The electrons trapped in anion vacancies
are referred to as F centres (F = Farben
in German means colour) or colour
B) Extra cations (positive ions) occupying an
interstitial position in the lattice.
-- The free electron is trapped in another
interstitial site close to the vicinity of the
interstitial cation. This electron helps to
maintain the electrical neutrality.

Metal Excess Defects

- When NaCl is treated with sodium vapour, a
yellow coloured non-stoichiometric form of
NaCl is obtained in which there is an excess
of sodium ions. Sodium atom removes
chlorine atom from the anionic lattice site
leaving its electron trapped in the vacancy
and makes the lattice excess of solid ions.

Metal Deficiency Defects

Occur in metals with variable oxidation states,

i.e., the transition metals

A cation may be missing from its lattice site

but the electrical neutrality is maintained when
the adjacent metal ion acquires higher
oxidation state

Examples: FeO, FeS and NiO.

Metal deficient compounds conduct electricity

through positive hole conduction mechanism
and are therefore p-type semi-conductors

Defect Clusters

Involves two atoms, both of which are on

distorted interstitial sites giving rise to split

For ionic crystals, the smallest cluster is either

an anion vacancy/cation vacancy pair or an
impurity/cation vacancy pair

Split interstitial in an FCC metal

Split interstitial in a BCC metal

Solid/ black circle: interstitial atoms; Open circle: normal lattice site
Rectangle: octahedral site

Types of Crystal Defects

Point Defects:
- Created due to a missing or irregularly placed
atom in the lattice structure
- Localized to the vicinity of only a few atoms
- Intrinsic point defects
-- Vacancies: Substitutional & interstitial,
Single-, di- or tri- vacancies

-- Atoms of same species in interstitial

Single interstitial, di-interstitials, and triinterstitials

Colour Centres

Types of point defects

- Intrinsic
-- Vacancy
-- (self) interstitial

Vacancies and interstitials could be produced

in materials by plastic deformation or high
energy particle irradiation (nuclear reactor
installations) or through thermal activation

Formation energy of interstitial

-- 2-4 times higher than that of vacancy

- Extrinsic
-- Impurity (external) atoms
--- Interstitial and substitutionals type

Impurity (foreign) atoms

Interstitial atoms

Foreign atoms that replace some of the

atoms making up the solid or that squeeze into
the interstices e.g. C in Fe (steel)

Too many impurities of the insoluble variety

coalesce to form precipitates and constitute
large defect
Substitutional impurities
form when the
impurity atoms replace
the original atoms (size
difference less than 15%)
e.g. Zn replaces some
of Cu atoms in brass



Schematic representation of different point defects in a crystal.

(1) vacancy; (2) self interstitial; (3) interstitial impurity; (4) small
substitutional impurity and (5) big substitutional impurity. The
arrows show the local stresses introduced by the point defects.


Point defects (vacancy) especially in ionic crystals


Luminescence centres/Colour centres

-- F-centres
-- V-centres

Loss of oxygen (electron trap)

Gain of oxygen (donor of electron)

Luminescence Center/ Colour Center

Formed in ionic crystals due to their nonstoichiometric properties i.e., when crystals
have an excess of one of their constituents

Point defects producing optical absorption

bands in an otherwise transparent crystal by
absorption of light

Electrons/holes in the defect region only absorb

light at certain range of wavelength

The colors seen are due to lights not absorbed

The color depends on the host crystal but not

on the source of the electron/hole

Ways to Colour Crystals

Addition of suitable chemical impurities like

transition element ions with excited energy
- Alkali halide crystals can be coloured by ions
whose salts are normally coloured
Introduction of stoichiometric excess of the
cation by heating the crystal in the alkali metal
vapour and then cooling it quickly
The colours produced depend upon the nature
of the crystals
Crystals so coloured contain an excess of alkali
metal atoms, typically 1016 to 1019 per unit
Exposure of the crystals to high energy
radiations like X-rays or -rays or by bombarding
them with energetic electrons or neutrons


The term F derived from a German word

Farbe meaning colour

Formed due to an excess of metal (+ve) ion

in alkali halides leading to an electron trapped
on the accompanying anion vacancy to maintain
neutrality (regions called F-centres)

When such a crystal is exposed to white light, a

proper component of energy excites the trapped
electron to a higher energy level and gets

The unabsorbed part of the light helps the crystal

to emit a specific colour

Can be prepared by heating an alkali halide in

vapor of an alkali metal or by irradiation with



Formed due to an excess of halogen in alkali

halides introduced by heating the halide crystal
in the vapour of the halogen

The excess halogen atom enters the normal

lattice positions as anion (negative ions)

Positive holes are thus formed which are

situated near a positive ion vacancy where they
can be trapped

A hole trapped at a positive ion (cation)

vacancy forms a V-centre

The optical absorption associated with a

trapped hole may be due to the transition of
an electron from the filled band into the hole

Comparison of Mechanism of Forming Fand V-Centres

The accompanying cation vacancies trap

holes in the case of V-centres just as the anion
vacancies trap electrons in F-centres

The new (V) centres have holes in cation

vacancies in place of electrons in anion
vacancies (F-centres)

A whole new series of colour centres

produced in the case V-centre as by excess
alkali metal atoms in case of F-centres


Colour Centers


Replacement of Al3+ for Si4+ in quartz gives

rise to the color of smoky quartz

Heating of ZnS to 773 K causes a loss of

sulfur, and this material fluoresces strongly
in ultraviolet light
Diamond with C vacancies (missing carbon
atoms) absorbs light, and these centers
give green color

NaCl heated in sodium vapour gives rise

to a an excess of sodium ions emitting
yellow colour

LiF heated in Li vapour colours it pink

Excess of K in KCl colours it blue

Excess of Na in NaCl makes the crystal yellow

Centres due to Loss or Gain of Oxygen

NiO gains oxygen on heating in air resulting

in having Ni3+ sites acting as electron trap
- p-type semiconductor

ZnO loses oxygen on heating and the excess

Zn metal atoms in the sample are ready to
give electrons
- n-type semiconductor

Off-center ions
- Where the radius of the substitutional atom
(ion) is substantially smaller than that of the
atom (ion) it is replacing, its equilibrium
position can be shifted away from the lattice
- Types of substitutional defects

Isovalent substitution and aliovalent

-- Isovalent substitution
--- Ion that is substituting the original ion is
of the same oxidation state as the ion it
is replacing
-- Aliovalent substitution
--- The ion that is substituting the original
ion is of a different oxidation state as
the ion it is replacing

Antisite defects

Occur in an ordered alloy or compound when

atoms of different types exchange positions

If type A atoms sit on the corners of a cubic

lattice, and type B atoms sit in the center of the

If one cube has an A atom at its center, the

atom is on a site usually occupied by a B atom

Neither a vacancy nor an

interstitial, nor an



Defects created as a result of thermal

vibration due to temperature rise

Lead to a deviation in the symmetry and shape

of atoms

Greatly affect magnetic and electric properties

of materials

Topological Defects

Regions in a crystal where the normal chemical

bonding environment is topologically different
from the surroundings

For instance, in a perfect sheet of graphite

(graphene) all atoms are in rings containing six
atoms. If the sheet contains regions where the
number of atoms in a ring is different from six,
while the total number of atoms remains the

Example is the Stone Wales defect in nanotubes,

which consists of two adjacent 5-membered and
two 7-membered atom rings

Linear Defects

Created due to groups of atoms in irregular


Propagate as lines or as a two dimensional net

in the crystal

Dislocations are
- Important linear defects found in materials
- Regions of localized lattice disturbance
separating the slipped and unslipped regions
in a crystal
- edge, screw and mixed types

Dislocations in well annealed crystals exist as

an ill-defined network called frank net

Linear Defects: Dislocations

Edge Dislocations
- Burgers vector perpendicular to the
dislocation line
- Move in the direction of (parallel to) the
dislocation line

Positive edge dislocation

Negative edge dislocation

Edge Dislocations
Direction of Dislocation motion

Extra half plane

Extra half plane

Dislocation core
Dislocation line

Burgers vector

Extra half plane

Dislocation line

-ve edge dislocation

+ve edge dislocation

Direction of dislocation motion

Screw Dislocations

Introduced by Burger in 1939

Also called Burger's dislocation

More difficult to visualize than edge


Basically comprises a structure in which a

helical path is traced around the linear defect
(dislocation line) by the atomic planes of
atoms in the crystal lattice

Burgers vector parallel to the dislocation line

Move in a direction perpendicular to the that

of the dislocation line

Left hand screw dislocation

Right hand screw dislocation

Screw Dislocations
Direction of Dislocation motion

Direction of Dislocation motion

Direction of dislocation motion

Dislocation line

Burgers vector

Mixed Dislocations

Dislocations occur generally as mixed

dislocations containing edge and screw

Existence of Dislocations: Some Observations

Metals are generally much softer than expected
Malleable and ductile properties of metals
Process of work-hardening of metals
Spirals on the surface of well-formed crystals
Plastic deformation caused at much less shear
stress (0.5-10 MPa) than theoretical (~ G/2 =
3000-25000 MPa) in metals (G = 20000 150000 MPa)
Until the 1930s, one of the enduring challenges
of materials science was to explain plasticity in
microscopic terms


First discovered by Taylor, Orowan and Polyani

in 1934

A crystallographic defect, or irregularity within

a crystal structure
Regular atomic arrangement is broken/
disturbed near dislocations

Some of the atoms of the crystal lattice are

misaligned around dislocations
Produces lattice strain (distortion)

Direction and magnitude of such distortion is

expressed in terms of a Burgers vector b
Dislocations are characterized by Burgers
vector, b

Play a major role in controlling end properties of
Movement of dislocations leads to slip
Dislocations can move if the atoms from one of
the surrounding planes break their bonds and
rebond with the atoms at the terminating edge

Plastic deformability characteristics of a metal

could be explained in terms of dislocation
generation, movement, interaction and pile up

Explain why metals undergo plastic

deformation at forces much smaller than the
theoretical strength
TEM allowed to show that the strength and
ductility of metals are controlled by


Presence of dislocations and their ability to

readily move (and interact) under external loads
leads to the characteristic malleability of
metallic materials

Dislocations can be observed using transmission

electron microscopy, field ion microscopy
and atom probe techniques (resolution ~ nm)

Millions of dislocations result from plastic

forming operations such as rolling and extruding

Any defect (including dislocations) in the

regular lattice structure disrupts/impedes
further motion of dislocations (pinning) making
slip or plastic difficult material strengthening

Move along the densest planes of atoms in a
material because the stress needed to move the
dislocation increases with the spacing between
the planes

FCC and BCC metals have many dense planes, so

dislocations move relatively easily and these
materials have high ductility
. As a material plastically deforms, more
dislocations are produced and they will get into
each others way and impede movement
- This is why strain or work hardening occurs

Dislocation Density

Expressed as volume density and surface (area) density

Volume density = Total length of dislocation lines per unit
volume of the crystal
Area density = Number of dislocations lines intersecting
per unit area of the crystal

If all dislocations are parallel,

Area density = volume density of dislocations
For fully randomly oriented dislocations

Volume density = twice the surface (area) density

Ranges from 102103 in the best germanium and silicon
crystals to 10111012 dislocations/cm2 in heavily
deformed metals

Observations of dislocations in Crystalline solids/ metals

Example of pits formed by

corrosion on the surface of LiF

Dislocations in a single crystal GaN thin film

Planar/Area/Surface defects
Interfaces between homogeneous regions of
May arise at the boundary between two grains,
or small crystals, within a larger crystal
Rows of atoms in two different grains may run
in slightly different directions, leading to a
mismatch across the grain boundary
Arise from the clustering of line defects on to a

Planar/Area/Surface defects
Boundaries between two homogeneous regions
Grain boundaries

Antiphase boundaries
Stacking faults

External surfaces
- Actual external surface of a crystal is also
a surface defect because the atoms on the
surface adjust their positions to accommodate
for the absence of neighbouring atoms outside
the surface


between two homogeneous regions of materials

Domain structure in
a single crystal

Sub-grain boundary

Antiphase Boundaries

Occur in ordered alloys wherein the

crystallographic direction remains the same, but
each side of the boundary has an opposite
- For example, if the ordering is usually
ABABABAB, an antiphase boundary takes the
form of ABABBABA

Grain Boundaries

Regions where one grain stops and another

begins is known

Interface between two grains in a

polycrystalline material

Occur where the crystallographic direction of

the lattice abruptly changes

Usually formed when two crystals begin

growing separately and then meet

Defects in the crystal structure

Disrupt the motion of dislocations through a


- Low angle boundaries
- High angle boundaries

Grain Boundaries

Grain size can be controlled by the cooling rate

during casting/ heat treatment
- Rapid cooling produces smaller grains

Grains can range in size from nm to mm

across and their orientations are usually
rotated with respect to neighboring grains

Reducing crystallite/grain size (more grain

boundary surface area) improve strength

- Hall-Petch relationship: d-1/2

-- : strength, d: grain diameter

Grain boundary barrier to dislocation motion:

slip plane discontinues or change orientation

Low angle boundaries

An array of dislocations

Boundaries of two crystallites or crystal grains at

a low angle inclination (<5o) with each other can
be considered to be a regular array of dislocations

The boundary plane contains a crystal axis

common to the two crystals
- Such a boundary called a pure tilt boundary.

Crystal orientations on both sides of the

boundary plane are symmetric with each other
such a boundary has a vertical arrangement of
more than two edge dislocations of same sign

Low angle boundaries

The interval D between the dislocations so formed is
given by
tan /2 = b/2D

D = b/

= < 5o for low angle boundaries

= 5-15o for high angle boundaries
Where b is the Burgers vector of
the dislocations and is small

Low angle grain boundary: (a) two crystals joined together

(b) Grain boundary formed with 2 rows of dislocations; the
crystals have been rotated by /2 left and right of these axes

Low Angle Grain Boundaries

Dislocations in a similar
orientation and position
introduce an angular
misorientation between the
two halves of the crystal

Diagram of optical micrograph

of a low angle grain boundary
in Ge

Stacking Fault

A planar defect

A local region in the crystal with interrupted

sequence of atomic planes

Results from a one or two layer interruption in

the stacking sequence of atom planes

- A missing layer or an added layer, either of

the same type or of a different type with
respect to the bulk layers
Normal stacking sequence is interrupted by the
presence of wrong layers e.g.

----- HCP

More common in materials with layered


Stacking Fault

Displacement (slip) of an entire plane of atoms

perpendicular to the fault plane

Described by two vectors

- The stacking vector (perpendicular to the
fault plane) and the slip vector (describing
the displacement direction of the plane of
Defect in the stacking of atomic layers
A change/fault in the stacking sequence of
layers over a few atomic spacings

Extrinsic and intrinsic stacking faults

Extrinsic stacking faults

- Created by introducing an extra layer

Intrinsic stacking faults

- Created by removing an existing layer


A special type of grain boundary defect, in which

a crystal is joined to its mirror image

Twin boundaries may be produced by

deformation of materials

Gives rise to shape memory effect in metals,

which can recover their original shape if heated
to a high temperature

Shape-memory alloys are twinned and when

deformed they untwin

At high temperature the alloy returns back to

the original twin configuration and restore the
original shape

Twin Region

A change over many atomic spacings produces a

twin region

If a stacking fault does not corrects itself

immediately but continues over some number of
atomic spacings, it will produce a second
stacking fault that is the twin of the first

If the stacking pattern is ABABABAB but

switches to ABCABCABC for a period of time
before switching back to ABABABAB, a pair of
twin stacking faults is produced

Twin Region
Twin Direction

Volume Defects

Occur on a much bigger scale than the

rest of the crystal defects
- Due to a large number of atoms
missing from the lattice


Air bubbles becoming trapped when

a material solidifies, it is commonly
called porosity/void

Impurity atoms clustering together to form

small regions of a different phase (precipitate)
- phase is a region occupied by a physically
homogeneous material
- Precipitate is a region of clusters/compounds
of selected elements different from that of the