Perfect Crystals

All unit cells consist of the ideal arrangement

of atoms or molecules as defined by the crystal
system

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
distortion
 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

crystals

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
defects
 Crystal Defects
Distortion or violation of regularity in the atomic
arrangement
Imperfections in the regular geometrical
arrangement of the atoms
- depend upon temperature and presence of
impurities
Result from
- Deformation of the solid
- Rapid cooling from high temperature
- High-energy radiation (X-rays or neutrons)
striking the solid
- Heating

 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
colourless
Iron and titanium impurities impart to -
alumina a blue colour, and the resulting gem-
quality 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
- Impurities (P and As) deliberately added to
silicon in the manufacture of integrated
circuits
- 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
Density
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
temperature.

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
million.

For many purposes, this fraction would be intolerably large,

although this number may be reduced by slowly cooling the
sample.
 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 (zero dimension)
Linear defects (0ne dimension)
Area/planar defects (Two dimensions
Volume defects (three dimensions)
Note: 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
forming
- 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
charges
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

Complexes
- Can form between different kinds of point
defects
-- If a vacancy encounters an impurity, the
two may bind together if the impurity is too
large for the lattice
Interstitials
- Can form 'split interstitials' or 'dumb-bell'
structures
-- 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 Dumb-bell-shaped

near an interstitial in a configuration of an
primitive cubic lattice 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
circuits

- 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
centres
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
Example

- 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
interstitial

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
Types
- Intrinsic point defects
-- Vacancies: Substitutional & interstitial,
Single-, di- or tri- vacancies
- Interstitials
-- Atoms of same species in interstitial
position
-- Single interstitial, di-interstitials, and tri-
interstitials
- 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
(heating)
- Formation energy of interstitial
-- 2-4 times higher than that of vacancy
formation

- 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%) Interchanged
e.g. Zn replaces some Atoms
of Cu atoms in brass
 1
3

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.
 Centers
Point defects (vacancy) especially in ionic crystals

Types
- 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 non-

stoichiometric 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
levels
- 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
volume
Exposure of the crystals to high energy
radiations like X-rays or -rays or by bombarding
them with energetic electrons or neutrons
 F-Centres
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
absorbed
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
X-ray
F-center
 V-Centres
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 F-
and 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
V-center
 Colour Centers
Examples
- 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
site
- Types of substitutional defects
-- Isovalent substitution and aliovalent
substitution
-- 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
cubes
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
impurity

Interchanged
Atoms
 Phonons
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
same

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
positions
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
dislocations
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
components
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
 Dislocations
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
 Dislocations
Play a major role in controlling end properties of
materials
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
dislocations
 Dislocations
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
 Dislocations
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 Dislocations in a single crystal GaN thin film

corrosion on the surface of LiF
 Planar/Area/Surface defects
Interfaces between homogeneous regions of
materials

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

plane
 Planar/Area/Surface defects

Boundaries between two homogeneous regions

Grain boundaries
Antiphase boundaries
Stacking faults
Twins
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
 Interfaces/Boundaries
between two homogeneous regions of materials

Domain structure in Sub-grain boundary

a single crystal
 Antiphase Boundaries
Occur in ordered alloys wherein the
crystallographic direction remains the same, but
each side of the boundary has an opposite
phase

- 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
material
Types
- 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
or 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

Diagram of optical micrograph

of a low angle grain boundary
Dislocations in a similar
in Ge
orientation and position
introduce an angular
misorientation between the
two halves of the crystal
 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.
ABABABCABABA. ----- HCP
ABCABCAB_ABCABC.. ----- FCC
More common in materials with layered
structures
 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
atoms)
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
 Twinning

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
one

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 Void

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
matrix