IMPERFECTION/DEFECTS IN CRYSTALLINE SOLIDS

Imperfections or defects: Any deviation from the perfect atomic arrangement

in a crystal is said to contain imperfections or defects. Some defects are
intentionally introduced to manipulate the properties of a material. Adding
alloying elements to a metal is one way of introducing a crystal defect. Crystal
imperfections have strong influence upon many properties of crystals, such as
strength, electrical conductivity and hysteresis loss of ferromagnets. Thus, some
important properties of crystals are controlled by as much as by imperfections
and by the nature of the host crystals.

 The conductivity of some semiconductors is due entirely to trace amount

of chemical impurities.
 Color, luminescence of many crystals arises from impurities and imperfections
 Atomic diffusion may be accelerated enormously by impurities or imperfections

 Mechanical and plastic properties are usually controlled by imperfections

Imperfections in crystalline solids are normally classified according to their

dimension as follows

 Point defects (Zero dimensional defects: Vacancies, Interstitials, Impurities),

 Line defects (One-dimensional defects: Edge and Screw Dislocations),
 Planar defects/Surface (Two-dimensional defects: Grain, Tilt & Twin boundaries,
Microcracks),
 Volume defects (three dimensional defects Voids).
 Crystal defect

Point defects Line defects Surface defects Volume defects

Vacancy Edge dislocation Grain boundaries Inclusions
Schottkey Screw Dislocation Titl boundaries Voids
Self interstitial Twin boundaries
Frenkel Stacking faults
Substitutional
Colour centres
Polarons
Excitons

What are Defects in Solids?

Any irregularity in the pattern of crystal arrangement in solids is called
imperfection in solids. The occurrence of defects takes place when the process
of formation of crystals happens. It may occur at a very fast or at an
intermediate rate. It happens because particles do not get enough time to
arrange themselves in a regular pattern.
Crystalline Defects
The ideal crystal has an infinite 3D repetition of identical units, which may be atoms
or molecules. Real crystals are limited in size, and they have some disorder in
stacking which are called defects.
No crystals are absolutely perfect. Only at the unattainable absolute 0 K
temperature will a crystal be perfect. A departure from the complex order and
deviation from the periodic arrangement of the particles in a crystal lattice is
called a crystal defect.

Causes of Crystal Defect

Defects occur in crystals due to the following factors:
1. Vacancies in the lattice
2. Dislocation of a particle in the lattice
3. Nonstoichiometric proportions of the ions
4. Impurities in the lattice

Types of Defects in Solids

Point defect- The imperfection in the crystal lattice due to the dislocation of a
particle from one position to another position in the lattice.

Or
Point defects are where an atom is missing or is in an irregular place in the
lattice structure. Point defects include self interstitial atoms, interstitial impurity
atoms, substitutional atoms and vacancies.

Types of Point Defects

Stoichiometric Defects
This type of defect is also called intrinsic defect or thermodynamic defect. In
stoichiometric defects, the proportion of the elements in the solid is not
disturbed. This defect arises when there is some vacancy in the crystal lattice
or when some constituent particles move from their original sites and occupy
interstitial sites. Stoichiometric defects have been observed in both the non-
ionic and ionic solids.

Stoichiometric Defect in Non-ionic Solids

There are two types of defects in non-ionic solids-
I. Vacancy defect
Vacancies are empty spaces where an atom should be, but is missing. They are common, especially at high
temperatures when atoms are frequently and randomly change their positions leaving behind empty lattice
sites. In most cases diffusion (mass transport by atomic motion) can only occur because of vacancies

1. It arises when some sites in the crystal lattice are vacant; that is, there is
no particle of the solid at some sites.
2. This type of defect is observed in metals and non-ionic solid substances.
3. This defect is caused when the crystal is heated abruptly.
4. This defect causes a decrease in the density of the crystal.

II. Interstitial Defect

1. This defect arises when some additional constituent particles of the crystal
occupy the interstitial site. However, there is no vacant site in the lattice.
2. This type of defect is observed in metals and non-ionic solid substances.
3. This defect causes an increase in the density of the crystal.

Interstitial atom could be self or substitutional

A self-interstitial atom is an extra atom that has crowded its way into an
interstitial void in the crystal structure. Self interstitial atoms occur only in low
concentrations in metals because they distort and highly stress the tightly packed
lattice structure.
A substitutional impurity atom is an atom of a
different type than the bulk atoms, which has
replaced one of the bulk atoms in the lattice.
Substitutional impurity atoms are usually close in
size (within approximately 15%) to the bulk atom.
An example of substitutional impurity atoms is the
zinc atoms in brass. In brass, zinc atoms with a
radius of 0.133 nm have replaced some of the
copper atoms, which have a radius of 0.128 nm.
Interstitial impurity atoms are much smaller than
the atoms in the bulk matrix. Interstitial impurity
atoms fit into the open space between the bulk
atoms of the lattice structure. An example of
interstitial impurity atoms is the carbon atoms that
are added to iron to make steel. Carbon atoms, with
a radius of 0.071 nm, fit nicely in the open spaces
between the larger (0.124 nm) iron atoms.

Stoichiometric Defect in Ionic Solids

4
There are two types of such defects in ionic solids-
I. Schottky Defect
The idea of this defect was given by German scientist Schottky in 1930.

This type of defect is also called point defect. It is observed when an equal
number of cations and anions are missing from the lattice. The presence of the
Schottky defect does not change the stoichiometry of the crystal. However, the
presence of this defect lowers the density of the solid.
The presence of the Schottky defect provides a facile mechanism by which
atoms can move within the lattice. An example of this defect can be seen
in NaCl, KCl and other such ionic compounds.

II. Frenkel Defect

The idea of this defect was given by Russian scientist Frenkel in 1926.

In a crystal, when an ion leaves its regular site and occupies an interstitial site,
the defect is termed as Frenkel defect. This defect is most likely to occur in
crystals in which the cation and anion differ in size. This defect does not alter
the density of the crystal.
Frenkel defects provide a facile mechanism by which the ions can move within
the crystal lattice.
An example of this defect can be seen in AgCl.AgCl and AgBr.AgBr.

Non Stoichiometric Defect

Nonstoichiometric defects arise because of the following two reasons-
1. The solid substance contains more proportion of cations than anions in the
lattice. This defect is also called metal excess defect.
2. The solid substance contains a lesser proportion of cations than anions in the
lattice. This defect is also called a metal deficiency defect.
Metal Excess Defect
It arises when the crystal lattice contains more proportions of metal cations as
compared to anions. There are two types of defects-
i. Anionic Vacancy
This type of defect arises when an anion is missing from its position, and an
electron occupies that space to maintain the electrical neutrality of the solid.
The electron trapped in an anion vacancy of a crystal lattice is referred to as
the F-centre. The cavities containing electrons in the crystal lattice are colour
centres.
The given figure below describes this defect-
Alkali metal halides show this type of defect like NaCl, KCl, LiCl. Normally alkali
metal halides are colourless solids. However, they exhibit characteristic colours
because of the presence of the F-centre.
Alkali halide Colour of the crystal
Sodium Chloride Yellow
Potassium Chloride Violet
Lithium Chloride Pink

ii. Extra Cations

The defect arises when an extra cation occupies an interstitial site in the crystal
lattice. The extra positive charge is balanced by an appropriate number of
electrons occupying other interstitial sites of the crystal lattice.
The figure given below describes this defect-

An example of this defect can be seen when zinc oxide is heated and loses
electrons.

Impurity Defects in Ionic solids

In ionic solids, the impurities can be introduced by adding a chemical impurity
that contains ions in different oxidation states.
For example, when a small quantity of SrCl2 is added as an impurity to NaCl a
solid solution is obtained in which Sr2+ ions occupy some of the lattice points
of Na+ ion. Introduction of every Sr2+ ion leads to the removal of Na+ ion, thus
maintaining electrical neutrality. The defect produces a cation vacancy in the
lattice.
The below-given figure shows this defect-
 Consequences of Defects in Solids

Defects may be advantageous or disadvantageous as they affect material

properties.
i. The interstitial defect increases the density of the substance.
ii. The closeness of the charge brought about by the Frenkel defect tends to
increase the dielectric constant of the crystal. Compounds with such defects
conduct electricity across the crystal.
iii. The presence of a large number of Schottky defects lowers the density of the
crystal.

Vacancies increase Entropy (randomness) of the crystal

Equilibrium Number of vacancies in a material is given by

Where N = total number of atom sites

Qv = energy required for formation of vacancy
T = absolute temperature , K = Boltzmann’s constant
 Nv increases with T

Line Imperfections/dislocation

Line defect- The imperfection extending over a microscopic region along a row
of the crystal lattice is known as a line defect.
In linear defects groups of atoms are in irregular positions. Linear defects are
commonly called dislocations. Any deviation from perfectly periodic arrangement
of atoms along a line is called the line imperfection. In this case, the distortion
is centered only along a line and therefore the imperfection can be considered
as the boundary between two regions of a surface which are perfect themselves
but are out of register with each other. The line imperfection acting as boundary
between the slipped and un-slipped region, lies in the slip plane and is called a
dislocation. Dislocations are generated and move when a stress is applied. The
strength and ductility of metals are controlled by dislocations.
Two extreme types of dislocations are distinguished as
1. Edge dislocations and
2. Screw dislocations.
Edge Dislocations:

The inter-atomic bonds are significantly distorted only

in the immediate vicinity of the dislocation line. As
shown in the set of images above, the dislocation
moves similarly moves a small amount at a time. The
dislocation in the top half of the crystal is slipping one
plane at a time as it moves to the right from its position
in image (a) to its position in image (b) and finally
image (c). In the process of slipping one plane at a time
the dislocation propagates across the crystal. The
movement of the dislocation across the plane
eventually causes the top half of the crystal to move
with respect to the bottom half. However, only a small fraction of the bonds are
broken at any given time. Movement in this manner requires a much smaller force
than breaking all the bonds across the middle plane simultaneously.

The Berger’s vector b is perpendicular () to dislocation line

A dislocation has associated with it two vectors:
t  A unit tangent vector along dislocation line
b  The Burgers vector
b describes size and direction of a dislocation.
Screw Dislocations: (Symbol ) The
screw dislocation is slightly more difficult to
visualize. The motion of a screw
dislocation is also a result of shear stress,
but the defect line movement is
perpendicular to direction of the stress
and the atom displacement, rather than
parallel.
To visualize a screw dislocation, imagine a block of metal with a shear stress
applied across one end so that the metal begins to rip. This is shown in the upper
right image. The lower right image shows the plane of atoms just above the rip.
The atoms represented by the blue circles have not yet moved from their original
position. The atoms represented by the red circles have moved to their new
position in the lattice and have reestablished metallic bonds. The atoms
represented by the green circles are in the process of moving. It can be seen that
only a portion of the bonds are broke at any given time. As was the case with the
edge dislocation, movement in this manner requires a much smaller force than
breaking all the bonds across the middle plane simultaneously.
If the shear force is increased, the atoms will continue to slip to the right. A row
of the green atoms will find there way back into a proper spot in the lattice (and
become red) and a row of the blue atoms will slip out of position (and become
green). In this way, the screw dislocation will move upward in the image, which is
perpendicular to direction of the stress.
Burger vector b is  (parallel) to dislocation line

In the average crystal structure, there are ~1012 m of dislocation lines per m3 of
crystal. Combinations of edge and screw dislocations are often formed as edge
dislocations can be formed by branching off a screw dislocation.
Planar/Surface defects are interfaces between homogeneous regions of the
material. Planar defects include grain boundaries, stacking faults and external
surfaces. A Planar Defect is a discontinuity of the perfect crystal structure across a
plane.

Grain Boundaries
A Grain Boundary is a general planar
defect that separates regions of different
crystalline orientation (i.e. grains) within a
polycrystalline solid. The atoms in the
grain boundary will not be in perfect
crystalline arrangement. Grain boundaries
are usually the result of uneven growth
when the solid is crystallizing. Grain sizes
vary from 1 µm to 1 mm.

Grain boundaries limit the lengths and motions of dislocations. Therefore, having
smaller grains (more grain boundary surface area) strengthens a material. The size
of the grains can be controlled by the cooling rate when the material cast or heat
treated. Generally, rapid cooling produces smaller grains whereas slow cooling
result in larger grains.
Tilt Boundaries
A Tilt Boundary, between two slightly mis-
aligned grains appears as an array of edge
dislocations.

Twin Boundaries
A Twin Boundary happens when the
crystals on either side of a plane are mirror
images of each other.
The boundary between the twinned
crystals will be a single plane of atoms.
There is no region of disorder and the
boundary atoms can be viewed as
belonging to the crystal structures of both
twins.
Twins are either grown-in during
crystallization, or the result of mechanical
or thermal work.

Microcracks
A Microcrack occurs where internal broken
bonds create new surfaces. They are
about 10 µm in size and there is a
tendency to form on the surface of a solid
rather than in the bulk. They also form at
grain boundaries and other regions of
disorder.
The region across which the bonds are broken is known as the separation plane.
Microcracks are formed when there is abrasion (or impacts) with dust particles.
They are important in determining how, and where, a solid may fracture. When a
crystal has more than one type of atom, there will be Chemical as well
as Physical disorder in the grain-boundaries.

Stacking Faults and Twin Boundaries

A disruption of the long-range stacking sequence can produce two other common
types of crystal defects: 1) a stacking fault and 2) a twin region. A change in the
stacking sequence over a few atomic spacings produces a stacking fault whereas
a change over many atomic spacings produces a twin region. A stacking fault is
a one or two layer interruption in the stacking sequence of atom planes. Stacking
faults occur in a number of crystal structures, but it is easiest to see how they
occur in close packed structures. For example, it is know that face centered cubic
(fcc) structures differ from hexagonal close packed (hcp) structures only in their
stacking order. For hcp and fcc structures, the first two layers arrange
themselves identically, and are said to have an AB arrangement. If the third
layer is placed so that its atoms are directly above those of the first (A) layer,
the stacking will be ABA. This is the hcp structure, and it continues ABABABAB.
However it is possible for the third layer atoms to arrange themselves so that
they are in line with the first layer to produce an ABC arrangement which is that
of the fcc structure. So, if the hcp structure is going along as ABABAB and
suddenly switches to ABABABCABAB, there is a stacking fault present.
Alternately, in the fcc arrangement the pattern is ABCABCABC. A stacking fault
in an fcc structure would appear as one of the C planes missing. In other words
the pattern would become ABCABCAB_ABCABC. 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. For
example 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. The red region in the stacking sequence that goes
ABCABCACBACBABCABC is the twin plane and the twin boundaries are the A
planes on each end of the highlighted region.

Grain Boundaries in Polycrystals

Solids generally consist of a number of crystallites or grains. Grains can range
in size from nanometers to millimeters across and their orientations are usually
rotated with respect to neighboring grains. Where one grain stops and another
begins is known as a grain boundary. Grain boundaries limit the lengths and
motions of dislocations. Therefore, having smaller grains (more grain boundary
surface area) strengthens a material. The size of the grains can be controlled by
the cooling rate when the material cast or heat treated. Generally, rapid cooling
produces smaller grains whereas slow cooling result in larger grains. For more
information, refer to the discussion on solidification.

1) (External Surfaces) : The environment of an atom at a surface differs from that of an atom in the
bulk, in that the number of neighbors (coordination) decreases. This introduces unbalanced forces
which result in relaxation (the lattice spacing is decreased) or reconstruction (the crystal structure
changes). Surface atoms have unsatisfied atomic bonds, and higher energies than the bulk atoms ⇒
Surface energy, γ (J/m2)
• Surface areas tend to minimize (e.g. liquid drop)
• Solid surfaces can “reconstruct” to satisfy atomic bonds at surfaces.
Volume or Bulk Defects
Bulk defects occur on a much bigger scale
than the rest of the crystal defects
discussed in this section. However, for the
sake of completeness and since they do
affect the movement of dislocations, a few
of the more common bulk defects will be
mentioned. Voids are regions where
there are a large number of atoms
missing from the lattice. The image to the
right is a void in a piece of metal. The
image was acquired using a Scanning
Electron Microscope (SEM). Voids can
occur for a number of reasons.
When voids occur due to air bubbles becoming trapped when a material solidifies,
it is commonly called porosity. When a void occurs due to the shrinkage of a
material as it solidifies, it is called cavitation.
Another type of bulk defect occurs when impurity atoms cluster together to form
small regions of a different phase. The term ‘phase’ refers to that region of space
occupied by a physically homogeneous material. These regions are often called
precipitates or inclusions.
Microcracks are formed when there is abrasion (or impacts) with dust particles.
They are important in determining how, and where, a solid may fracture. When a
crystal has more than one type of atom, there will be Chemical as well
as Physical disorder in the grain-boundaries.