A perfect crystal is an idealization; there is no such thing in nature.

Atom
arrangements in real materials do not follow perfect crystalline patterns.
Nonetheless, most of the materials that are useful in engineering are
crystalline to a very good approximation. There is fundamental physical
reason for this. The preferred structures of solids at low temperature are those
that minimize the energy. The low-energy atomic configurations are almost
invariably crystalline since the regular pattern of the crystal lattice repeats
whatever local configuration is most favorable for bonding. There is also a
fundamental physical reason why the crystal is imperfect. While a perfect
crystalline structure may be preferred energetically, at least in the limit of low
temperature, atoms are relatively immobile in solids and it is, therefore,
difficult to eliminate whatever imperfections are introduced into the crystal
during its growth, processing or use.
• The properties of some materials are profoundly influenced by
the presence of imperfections. Consequently, it is important to
have a knowledge about the types of imperfections that exist
and the roles they play in affecting the behavior of materials.
For example, the mechanical properties of pure metals
experience significant alterations when alloyed. 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.
Intrinsic point defects :
The presence of intrinsic point defects is related to the nature of the
atom. Atoms in a solid are subject to thermal vibrations at any
temperature. The average amplitude of the atomic displacements
increases with increasing temperature. Therefore, it is easy to imagine
a localized area within the crystal where the vibrations are intense
enough to cause a single atom to jump to a different location, either to
the surface of the crystal or to an intermediate or interstitial position
within the crystal. If the atom moves to the surface of the crystal, a
Schottky defect is said to have formed, leaving a vacancy as the
defect. However if the atom jumps to an interstitial position within the
crystal lattice, it is said to have formed a Frenkel defect, creating both
a vacancy and a self-interstitial.
This leads to the conclusion that the imperfect crystal has a lower free
energy than a perfect crystal. From thermodynamics, we know that the
change in the free energy of a system, ΔG, is related to the changes in
enthalpy, ΔH, and entropy, ΔS, as shown in Eq, where T is absolute
temperature:
ΔG=ΔH-TΔS
The energy to form a defect, ED , is a positive contribution to the enthalpy
term, thus increasing the free energy of the system. However, the creation of
the defect increases the disorder of the crystal, thus increasing the entropy of
the system and causing a decrease in the free energy of the system. The
balance of these two factors leads to an equilibrium number of defects
naturally occurring within the crystalline lattice. Through calculating the
minimum free energy condition as a function of temperature, Boltzmann
determined that the equilibrium number of defects, ne, can be written
according to Eq.

, where N is the number of atoms

in the crystal, A is a constant often taken as unity, T is the absolute
temperature, and kb is Boltzmann’s constant. By dividing ne by N , the
equilibrium concentration of defects, ne , may be found.
Vacancies
A vacancy is produced when an atom or an ion is missing from its
normal site in the crystal structure, as in Figure. When atoms or ions
are missing (i.e., when vacancies are present), the overall randomness
or entropy of the material increases, which increases the
thermodynamic stability of a crystalline material.
• All crystalline materials have vacancy defects. Vacancies are
introduced into metals and alloys during solidification, at high
temperatures, or as a consequence of radiation damage. Vacancies
play an important role in determining the rate at which atoms or
ions can move around, or diffuse in a solid material, especially in
pure metals.

• In some other applications, we make use of the vacancies created in

a ceramic material to tune its electrical properties. At room
temperature (~300 K), the concentration of vacancies is small, but
the concentration of vacancies increases exponentially as we
increase the temperature, as shown by the following Arrhenius type
behavior
nv is the number of vacancies per cm3;
n is the number of atoms per cm3;
Qv is the energy required to produce one mole of vacancies, in cal/mol or
Joules/mol ;
R is the gas constant, (1.987 cal / mol – K) or (8.31 Joules / mol – K) ;and
T is the temperature in degrees Kelvin.
The probability that a given site is vacant is proportional to the
Boltzmann factor for thermal equilibrium:
P = exp (- EV /kBT),
Where EV is the energy required to take an atom from a lattice
site inside the crystal to a lattice site on the surface. If there are
N atoms, the equilibrium number n of vacancies is given by the
Boltzmann factor :
• Due to the large thermal energy atoms have near the melting
temperature of a material, there may be as many as one vacancy per
1000 atoms. Note that this equation provides for equilibrium
concentration of vacancies at a given temperature.
• It is also possible to retain a non-equilibrium concentration of
vacancies produced at a high temperature by quenching the material
rapidly. Thus, in many situations the concentration of vacancies
observed at room temperature is not the equilibrium concentration
predicted by Equation.
• Vacancies trapped in the structure may be one thousand times
greater than the equilibrium number of vacancies at room
temperature. Thus, vacancy concentrations encountered in relatively
pure materials are often dictated by both the thermodynamic and
kinetic factors.
Interstitial Defects
An interstitial defect is formed when an extra atom or ion is inserted
into the crystal structure at a normally unoccupied position, as in
Figure.
• Interstitial atoms or ions, although much smaller than the atoms or
ions located at the lattice points, are still larger than the interstitial
sites that they occupy. Consequently, the surrounding crystal region
is compressed and distorted.
• interstitial defect can be of two types:

Self-Interstitial Defect: occurs when atom of the same crystalline solid

occupies the interstitial position leaving its original lattice site.
Interstitial Defect: occurs when a foreign atom occupies the interstitial
position.
Effects of interstitial defects:
• Although an extra atom occupies the empty interstitial space, the
atom's size is typically more than that of the space. As a result, the
atoms in the vicinity are squeezed and deformed.
• The presence of a large number of interstitial atoms can alter the
solid's mechanical and thermal properties. However, this might be
advantageous at times, and so interstitial flaws can be used in a
regulated manner to improve certain aspects of the solid.
• A sufficient number of interstitial atoms can help in changing an
electrically non-conductive material into a conductive one.
 Calculate the equilibrium number of vacancies per cubic meter for copper at
1000˚C. The energy for vacancy formation is 0.9 eV/atom; the atomic weight
and density (at 1000˚C) for copper are 63.5 g/mol and 8.4 g/cm3, respectively.
Schottky defect it is one type of Point Defect that occurs in ionic crystals.
Schottky defect occurs when oppositely charged atoms (cation and anion)
leave their corresponding lattice sites and create a pair of Vacancy Defects.
Since both cation and anion leave the lattice sites at the same time, so overall
electrical neutrality of the crystal is maintained; however, density reduces
because of the vacancies.
Frenkel Defect is one type of Point Defect; in fact, it is a combination of
both Vacancy and Interstitial type of point defects. Usually, this type of defect
is observed in ionic solids, where size of anion is substantially larger than the
size of cation. Basically, a Frenkel Defect is one type of point defect where an
atom (better to say ion, especially cation) leaves its original lattice site and
occupies an interstitial position on the same crystal. When an atom leaves the
original lattice site then Vacancy Defect is created. Alternatively, when an
atom (of same crystal or foreign crystal) occupies the interstitial site then
Interstitial Defect is created. Since, in Frenkel Defect, one atom leaves the
original lattice site and occupies an interstitial site in the same crystal, so
Frenkel Defect is a pair of Vacancy & Self-interstitial Defects. The following
image depicts a typical crystal with Frenkel Defect.
characteristics of the Frenkel Defect
• The lattices formed in a Frenkel Defect are relatively open.
• The Frenkel Defect occurs when the size of cations is smaller in comparison to
the anions.
• The coordination number of a solid-state in the Frenkel Defect is low.
• The Frenkel Defect does not change the chemical properties of a substance.
• Frenkel Defect has no impact on the density of the structure, therefore it
preserves the mass and volume of the solid.
• Substances maintain their electrical neutrality in the undertaking of the
Frenkel Defect.
The formula for calculating the Frenkel defect is given by:
𝛥𝐻
n= 𝑁𝑁′𝑒 2𝑅𝑇
Where,
N= Normally occupied positions , N'= Number of available positions
ΔH= One Frenkel Defect's enthalpy formation
R = Gas constant , T = Temperature

n of Frenkel defects is much smaller than the number of lattice sites N and the
number of interstitial sites N‘, the result is:
n = (NN ‘ )1/ 2 exp(-EI /2kBT)
where EI is the energy necessary to remove an atom from a lattice site to an
interstitial position. Lattice vacancies
What are the Characteristics of Schottky Defect?
•There is a small difference between the size of the anion and cation.
•Usually, two vacancies are formed.
•Anion and Cation both leave the solid crystal at the same time.
•Atoms also move out of the crystal permanently.
•The density of the solid reduces considerably.
Schottky Defect Formula :
Schottky defects are formed by applying heat to the solid crystal. At a given
temperature, following formula can be used for calculating Schottky Defect:

ns ≈ N exp ( −ΔH
2RT
s
)

Where,
ns= number of Schottky defects per unit volume at temperature T (in Kelvins)
ΔHs = Enthalpy for creating one defect.
R = Gas constant
T = Absolute temperature (in K)
N can be computed by using the following formula:

Densityoftheioniccrystalcompound × NA
𝐍=
MolarmassoftheIonicCrystalCompound
In ionic crystals it is usually energetically favorable to form
roughly equal numbers of positive and negative ion vacancies.
The formation of pairs of vacancies keeps the crystal
electrostatically neutral on a local [Link] a statistical
calculation we obtain:

for the number of pairs, where Ep is the energy of formation of a

pair.
The number of Vacancies with a positive charge (nc) is equal to the number of
Vacancies with a negative charge (na), meaning that:
nc=na=n
The ωc probabbility of the different ways in which a positive ion can be removed and
expelled out of the crystal to be replaced by a positive vacacies is given by the
mathematical relationship:

In the same way, the probability ωa of extracting a negative ion and expelling it
outside the crystal to replace it with a negative vacancy is given by the following
relationship:
The total probability that a pair of positive and negative vacancies can be formed is:
ω = ωc ωa
From the above equations, we find that:

The occurrence of voids inside the crystal leads to a change in the free energy (H) of
Helmholtz, which in turn depends on the change of both the enthalpy E and the
entropy S, as mentioned in the equation:
ΔH=ΔE-TΔS
Where: E is the internal energy of the crystal
T is the absolute temperature
S entropy in relation:
Where: KB is the Boltzmann constant
ω is the probability
Increasing the number of vacancy formed leads to an increase in entropy, and
therefore entropy can be calculated from the relationship:

What is meant by internal energy here is the formation energy of pair

vacancies it is symbolized by EP, and therefore the formation energy is
defined as the energy required to form a pair of positive and negative
vacancies. Since the occurrence of n pairs of vacancies, the internal
energy can be written instead of the formation energy:

Substituting the above equations into each other:

Using stirling's formula:
Ln x! = x lnx – x
so
2[NlnN-(N-n) ln (N-n)-n ln n]

By Substituting we get

If the temperature of the crystal rises from T1 to T2, the number of vacancies will
gradually increase to a point where the increase stops, i.e. the vacancies reach the
saturation limit, and this means that the number of vacancies becomes a constant
quantity in the case of thermal equilibrium, and the first derivative of the free energy
in relation to the number of vacancies is equal to zero.
And since the number of vacancies in the crystal is usually much smaller than the number
of ions in the crystal, that is, n<<N on it, (n) can be neglected from the numerator so that
the equation becomes as follows:

The equation is called the Schottky equation

Suppose that the crystal consists of (N) number of atoms. When an atom is displaced
from its position to an interstitial site, it will work to create a vacancy, so the number
of vacancies (nv) will be equal to the number of interstitial atoms (ni), meaning that:
nv = ni = n
We suppose that the interstitial atom can occupy one site out of the total number (Ni)
of the interstitial sites, the probability (ωv) of the different methods of displacing an
atom from its original position to replace it with a vacancy is:

The probability (ωi) of the different ways that the interstitial atom can occupy in (Ni)
sites is:

The total probability (ω ) with which vacancy-interstitial atom pairs can be formed is:
ω = ωv ωi
Substituting the equations together, we get:

The occurrence of vacancy- interstitial atom pairs inside the crystal leads to a change
in the free energy (H) of Helmholtz, which in turn depends on the change of both the
internal energy E and the entropy S, which was mentioned in an equation previously.
The change in entropy can be calculated from the following equation:

The internal energy E in Frenkel defects is represented by the Frenkel formation

energy Ei , which is defined as the energy required to move an atom from its original
position to an interstitial site. Since the occurrence of (n) vacancy-interstitial atom
pairs is, the internal energy can be written in terms of the formation energy, that is:
E = n Ei
Substituting the two equations above, we get:

Using stirling's formula we get :

In the case of thermal equilibrium, the first derivative of the free energy with respect
to the number (n) is zero:

And when (n) is much smaller than (N) and also much smaller than (Ni), then (n) can
be neglected from the numerator to become the equation
Substituting the two equations above, we get:

The equation is called the Frenkel equation

 Schottky defect Frenkel defect
It occurs when the atoms are just displaced from their
It occurs when the atoms are totally missing from the
position to some voids or interstitial sites of the crystal
crystal lattice.
lattice.
It generally occurs in crystal lattice where the size ratio of It occurs generally in the lattice where the size ratio of
cation and anion is nearly 1 cation and anion is large
In this, both the cation and the anion leave the lattice, thus In this, only the smaller ion is displaced. Cation is smaller
ensuring that the overall crystal is neutral. and so it gets displaced in interstitial sites.

Two atoms are removed from the lattice for 1 single defect Number of atoms remain same before and after the defect.

Thus,there is decrease in the density of the crystal Thus,the density of the crystal is unaffected

Two vacancies are created when 1 pair of ions are removed One vacancy is created and one interstitial site is occupied

Eg NaCl, KCl, KBr Eg ZnS, AgCl, AgBr

Extrinsic point defects :
Extrinsic point defects, are caused by an outside source, such as
growth conditions or processing factors. They are created when a
foreign atom embeds itself within the crystal. If the atom is located on
a lattice site, i.e. replacing the native atom, then it is called a
substitutional impurity. The foreign atom may also be located at an
interstitial site, and is thus termed an interstitial impurity.
Substitutional Defects A substitutional defect is introduced when one
atom or ion is replaced by a different type of atom or ion as in Figures.
The substitutional atoms or ions occupy the normal lattice sites.
Substitutional atoms or ions may either be larger than the normal
atoms or ions in the crystal structure, in which case the surrounding
interatomic spacings are reduced, or smaller causing the surrounding
atoms to have larger interatomic spacings. In either case, the
substitutional defects alter the interatomic distances in the surrounding
crystal. Again, the substitutional defect can be introduced either as an
impurity or as a deliberate alloying addition, and, once introduced, the
number of defects is relatively independent of temperature.
Where Substitutional defects can be found?
• Substitutional defects can be found in brass, where zinc atoms
replace copper atoms.
• In semiconductor materials also.

Causes of Substitutional defect in solids:

• Presence of foreign atoms as natural impurities within the solid.

• Deliberate addition, such as during iron to steel conversion, heat

treatment, sputtering, etc.
• Diffusion, caused by close contact between two different materials.
Effects of Substitutional defects in solids:
• If the foreign atom is smaller in size as compared to the original
atom of the solid, the neighboring atoms will remain in tensile
stress.
• If the foreign atom is larger in size as compared to the original atom
of the solid, the neighboring atoms will remain in compressive
stress.
• So, presence of foreign atom may distort the original lattice
structure
• Presence of substantial number of foreign atoms can change the
mechanical and thermal properties of the solid. However, this is
sometime beneficial, and thus substitutional defects can be applied
in a controlled way to enhance various properties of the solid.
• 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.
• Dislocations are line imperfections in an otherwise perfect crystal. They
are introduced typically into the crystal during solidification of the material
or when the material is deformed permanently. Although dislocations are
present in all materials, including ceramics and polymers, they are
particularly useful in explaining deformation and strengthening in metallic
materials. to extreme types of dislocations are distinguish as :
1. Edge dislocations
2. Screw dislocations
3. mixed dislocation
Screw Dislocations the screw dislocation can be illustrated by cutting
partway through a perfect crystal, then skewing the crystal one atom spacing.
If we follow a crystallographic plane one revolution around the axis on which
the crystal was skewed, starting at point x and traveling equal atom spacing's
in each direction, we finish one atom spacing below our starting point (point
y). The vector required to complete the loop and return us to our starting point
is the Burgers vector b. If we continued our rotation, we would trace out a
spiral path. The axis, or line around which we trace out this path, is the screw
dislocation.
The magnitude and direction of the lattice distortion associated with a
dislocationis expressed in terms of a Burgers vector

Edge Dislocations An edge dislocation can be illustrated by slicing partway

through a perfect crystal, spreading the crystal apart, and partly filling the cut
with an extra plane of atoms.
The bottom edge of this inserted plane represents the edge dislocation.
If we describe a clockwise loop around the edge dislocation, starting at
point x and going an equal number of atoms spacings in each
direction, we finish, at point y, one atom spacing from the starting
point. The vector required to complete the loop is, again, the Burgers
vector. In this case, the Burgers vector is perpendicular to the
dislocation. By introducing the dislocation, the atoms above the
dislocation line are squeezed too closely together, while the atoms
below the dislocation are stretched too far apart. The surrounding
region of the crystal has been disturbed by the presence of the
dislocation. Unlike an edge dislocation, a screw dislocation cannot be
visualized as an extra half plane of atoms.
Mixed Dislocations mixed dislocations have both edge and screw
components, with a transition region between them. The Burgers
vector, however, remains the same for all portions of the mixed
dislocation.
(a) Schematic (a) A
representation of a screw dislocation
dislocation that has within a crystal.
edge, screw, and (b) The screw
mixed character. dislocation in (a) as
(b) Top view, where viewed from above.
open circles denote The dislocation line
atom positions extends along line
above the slip plane. AB. Atom positions
Solid circles, atom above the slip plane
positions below. are designated by
At point A, the open circles, those
dislocation is pure below by solid
screw, while at point circles.
B, it is pure edge.
For regions in
between where there
is curvature in the
dislocation line, the
character is mixed
edge and screw.
Slip The process by which a dislocation moves and causes a metallic material
to deform is called slip. The direction in which the dislocation moves, the slip
direction, is the direction of the Burgers vector for edge dislocations. During
slip, the edge dislocation sweeps out the plane formed by the Burgers vector
and the dislocation. This plane is called the slip plane. The combination of
slip direction and slip plane is the slip system. A screw dislocation produces
the same result; the dislocation moves in a direction perpendicular to the
Burgers vector, although the crystal deforms in a direction parallel to the
Burgers vector. The Peierls-Nabarro stress is required to move the dislocation
from one equilibrium location to another,

where τ is the shear stress required to move the dislocation, d is the

interplanar spacing between adjacent slip planes, b is the magnitude of the
Burgers vector, and both c and k are constants for the material.
It is assumed that there is a periodic shearing force required to move
the top row of atoms across the bottom row which is given by the

where τ is the applied shear stress, G is the shear modulus, b the

spacing between atoms in the direction of the shear stress, a the spacing
of the rows of atoms and x is the shear translation of the two rows away
from the low-energy position of stable equilibrium (x=0)
are the boundaries, or planes, that separate a material into regions,
each region having the same crystal structure but different
orientations. Or two-dimensional defects, refer to irregularities in the
crystalline lattice that occur across a planar surface of the crystal.
These may be due to an internal error in the crystal structure, or
interfaces between two different materials, including interfaces with
different phases of matter. Include:
1-Internal planar defects
- Twin boundaries,
- Grain boundaries,
- Stacking fault
2-external planar defects
Grain Boundaries
Another type of planer defect is the grain boundary. 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.
By reducing the grain size, we increase the number of grains and,
hence, increase the amount of grain boundary area.
Any dislocation moves only a short distance before encountering a
grain boundary and being stopped, and the strength of the metallic
material is increased. The Hall-Petch equation relates the grain size to
the yield strength (σy )

where d is the average diameter of the grains, and s0 and K are constants for
the metal. Recall that yield strength (σy ) of a metallic material is the
minimum level of stress that is needed to initiate plastic (permanent)
deformation.
A twin boundary is a plane across which there is a special mirror
image misorientation of the crystal structure. Twins can be produced
when a shear force, acting along the twin boundary, causes the atoms
to shift out of position. Twinning occurs during deformation or heat
treatment of certain metals or alloys. The twin boundaries interfere
with the slip process and increase the strength of the metal. Movement
of twin boundaries can also cause a metal to deform.
Volume defects, also known as bulk defects, are clusters of point
defects. Clusters of defects are produced when the crystal become
supersaturated. Each point defect introduced into a crystal has a
certain level of solubility, which defines the maximum concentration
of the impurity in the host crystal. In general, solubility is temperature
dependent and decreases as the crystal is cooled down. When the
concentrations of defects exceed their solubility limit or the crystal is
cooled down after it gets saturated, it becomes supersaturated with that
defect. The crystal under a supersaturated condition tries to achieve an
equilibrium condition by condensing the excess defects into clusters
with different phase regions.
• Volume defects are two-dimensional defects
• Volume defects such as cracks may arise in crystals during the
process of crystal growth.
• While growing, any possible small electrostatic dissimilarity
between the stacking layers may result in crack.
• A large vacancy may arise due to missing of clusters of atoms which
is a volume defect.
• Inclusion of foreign particles or non-crystalline regions of
dimensions of at least 10-30Å also belong to the category of volume
defects.
• Using optical microscopes, presence of volume defects can be
detected.
• Interferometric techniques can also be applied to study the volume
defects.
• Introduction to Dislocations by D. Hull and D.J. Bacon Pergamon
Press, Oxford (1984).
• Theory of Dislocations by J. P. Hirth and J. Lothe McGraw-Hill,
New York (1968).
• Essentials of Materials Science and Engineering Second Edition
by Donald R. Askeland & Pradeep P. Fulay.
• Introduction to Dislocations Fifth Edition D. Hull and D. J. Bacon.
• Fundamentals of Solid State Engineering 3rd Edition by Manijeh
Razeghi.
• Introduction to Solid State Physics eighth edition by Charles Kittel