Crystal Defects (Imperfections)

Submitted by: Muhammad Shareef (bsf2201078)

Ghulam Hussain (bsf2201082)
Faisal Shahzad (bsf2201101)
Submitted to: Dr. M. Adnan Asghar
Semester: 6th (Morning)
Session: 2022 - 2026
Department of Chemistry
Division of Science and Technology
Univeristy of Education, Lahore

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 Table of Contents

1. Point Defects .................................................................................................................................. 3

1.1. Vacancies ....................................................................................................................................... 3
1.1.1. Schottky Defect .......................................................................................................................... 5
1.2. Interstitials .................................................................................................................................... 5
1.2.1. Self-Interstitial ........................................................................................................................... 5
1.2.2. Foreign Interstitial ..................................................................................................................... 5
1.2.3. Frenkel Defect ............................................................................................................................ 6
1.3. Impurities ...................................................................................................................................... 6
1.3.1. Substitutional Impurity............................................................................................................... 6
1.3.2. Interstitial Impurity .................................................................................................................... 7
2. Line Defects (Dislocations) .............................................................................................................. 8
2.1. Edge Dislocations ........................................................................................................................... 9
2.1.1. Positive Edge Dislocation ...........................................................................................................11
2.1.2. Negative Edge Dislocation..........................................................................................................11
2.2. Screw Dislocations ........................................................................................................................12
3. Plane (Surface) Defects ...................................................................................................................13
3.1. External Surfaces ........................................................................................................................ 13
3.2. Grain Boundaries ........................................................................................................................ 14
3.3. Twin Boundaries ......................................................................................................................... 16
3.4. Stacking Fault ............................................................................................................................. 17
4. Volume (Bulk) (Void) Defects ....................................................................................................17

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 Crystal Defects (Imperfections)
Real crystals are never perfect, there are always defects! Actually, all crystals are imperfect. Controlling
defects is one of the main goals of materials science and engineering. Crystal defects are imperfections
in crystals caused by deviations from the individual lattice structure. Crystals are like people, it is
their defects that make them more interesting. Imperfections give properties of crystalline solids, i.e., they
dominate the material properties. They always contain a considerable density of defects and imperfections
that affect their physical, chemical, and mechanical properties. The existence of defects also plays an
important role in various technological processes and phenomena such as annealing, precipitation,
diffusion, sintering, oxidation, and others. It should be noted that defects do not necessarily have adverse
effects on the properties of materials. A crystalline defect refers to a lattice irregularity having one or
more of its dimensions about an atomic diameter. Classification of crystalline imperfections is frequently
made according to the geometry or dimensionality of the defect.
Classification of Crystal Defects (Imperfections)
1. Zero Dimensional: Point Defects
2. One Dimensional: Line Defects (Dislocations)
3. Two Dimensional: Plane (Surface) Defects
4. Three Dimensional: Volume (Bulk) (Void) Defects
1. Point Defects
A point defect is a much-localized disruption in the regularity of a lattice. It is a defect of dimensions just
like a point (zero dimensions). The size of the defect could be one atom, or two atomic diameters, which
is just like a point. A point defect extends its influence only a few atomic diameters beyond its lattice
position.
Types of Point Defects
1.1. Vacancies
1.2. Interstitials
1.3. Impurities
1.1. Vacancies
When an atom is missing from its lattice site in a crystal structure, it is called a vacancy (or vacant lattice
site). The atoms surrounding a vacancy experience a slight displacement into the empty lattice site, and
thus, a vacancy is a center of approximately spherical distortion in the lattice. There could be di-vacancies
(an association of two vacancies) or even tri-vacancies.

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The necessity of the existence of vacancies is explained using principles of thermodynamics; in essence,
the presence of vacancies increases the entropy (i.e., the randomness) of the crystal. The equilibrium
number of vacancies Nv for a given quantity of material (usually per meter cubed) depends on and
increases with temperature according to

In this expression, N is the total number of atomic sites (most commonly per cubic meter), Q v is the
energy required for the formation of a vacancy (J/mole or eV/atom), T is the absolute temperature in
kelvins, and k is the gas or Boltzmann’s constant. The value of k is 1.38× 10-23 J/atom-K, or 8.62×10-5
eV/atom-K, depending on the units of Qv. Thus, the number of vacancies increases exponentially with
temperature.

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1.1.1. Schottky Defect
It refers to the missing of pair of positive and negative ions in an ionic crystal. A neutral defect that
involves paired vacancies on the cation and anion sub lattices is called a Schottky defect.

1.2. Interstitials
When extra atoms occupy interstitial spaces with in the crystal structure without removing parent atoms,
they are known as interstitials. The defect is called interstitial defect.

Types of Interstitials
1.2.1. Self-Interstitial
1.2.2. Foreign Interstitial
1.2.1. Self-Interstitial
A self-interstitial is an atom from the crystal that is crowded into an interstitial site—a small void space
that under ordinary circumstances is not occupied. In metals, a self-interstitial introduces relatively large
distortions in the surrounding lattice because the atom is substantially larger than the interstitial position
in which it is situated. Consequently, the formation of this defect is not highly probable, and it exists in
very small concentrations that are significantly lower than for vacancies.

1.2.2. Foreign Interstitial

If impurity atom (foreign atom) occupies the interstitial position without replacing the parent atom, it is
called foreign interstitial. These can exist only ionic and covalent crystals. Here the impurity atom has
very small size as that of the host atoms.

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1.2.3. Frenkel Defect
A vacancy associated with interstitial impurity is called Frenkel defect. Here a missing atoms occupies
interstitial position .This defect always occurs in ionic crystal, If a positive ion moves into an interstitial
site in an ionic crystal, a cation vacancy is created in normal site, this vacancy- interstitial pair is known
as Frenkel defect.

1.3. Impurities
When the foreign atoms (impurities) are added to crystal lattices, they are known as impurities. The defect
is called impurity defect.
Types of Impurities
1.3.1. Substitutional Impurity
1.3.2. Interstitial Impurity
1.3.1. Substitutional Impurity
An impurity (foreign) atom if present on the lattice by substituting the lattice site atom. Substitutional
atoms may either be larger than the normal atom in the lattice (in which case, the surrounding atoms are
compressed, or smaller (causing the surrounding atoms to be in tension). The number of defects is
relatively independent of temperature.

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1.3.2. Interstitial Impurity
An impurity (foreign) small-sized atom if present in the interstitial site. Therefore, the surrounding lattice
is compressed and distorted. The number of interstitial atoms in the structure remains constant, even when
the temperature is changed. Normally, the concentration of these atoms in very pure materials is lower
than the concentration of vacancies. Foreign atoms also play a role in changing the electrical conductivity
of the semiconductors.

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It is often necessary to express the composition (or concentration) of an alloy in terms of its constituent
elements. The two most common ways to specify composition are weight (or mass) percent and atom
percent. The basis for weight percent (wt%) is the weight of a particular element relative to the total alloy
weight. For an alloy that contains two hypothetical atoms denoted by 1 and 2, the concentration of 1 in
wt%, C1, is defined as:

Where m1 and m2 represent the weight (or mass) of elements 1 and 2, respectively. The concentration of 2
is computed in an analogous manner. When an alloy contains more than two (n) elements, Equation takes
the form:

The basis for atom percent (at%) calculations is the number of moles of an element in relation to the total
moles of the elements in the alloy. The number of moles in some specified mass of a hypothetical element
1, nm1, may be computed as follows:

Here, m1 and A1 denote the mass (in grams) and atomic weight, respectively, for element 1. Concentration
in terms of atom percent of element 1 in an alloy containing element 1 and element 2 atoms, C 1 is defined
by:

In like manner, the atom percent of element 2 is determined. Atom percent computations also can be
carried out based on the number of atoms instead of moles, because one mole of all substances contains
the same number of atoms.
2. Line Defects (Dislocations)
Line defects, or dislocations, are lines along which whole rows of atoms in a solid are arranged
anomalously. The resulting irregularity in spacing is most severe along a line called the line of
dislocation. Line defects can weaken or strengthen solids. Dislocations are generated and move when
stress is applied. The motion of dislocations allows slip–plastic deformation to occur. Dislocation is the
region of localized lattice distortion that separates the slipped and unslipped portion of the crystal. The
upper region of the crystal over the slip plane has slipped relative to the bottom portion. The line (AD)
between the slipped and unslipped portions is the dislocation. The magnitude and direction of slip
produced by dislocation (pink shaded) is the burger vector of the dislocation. The burgers vector is a
quantitative characteristic describing the distortions of the crystal lattice around a dislocation.

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Burger Vector
A burger vector expresses the dislocation lines. It indicates the amount and direction of shift in lattice on
slip plane. The figure shows a perfect crystal and crystal with a positive edge dislocation. Consider a
point starting from p in figure (b) which moves in particular direction as shown and it complete atomic
distance in the form of a circuit called burger circuit or burger loop. If the same circuit is drawn starting
from pin figure. Then the circuit would not complete, this is because of the presence of a dislocation. If
we wish to arrive at starting point p from Q, then we must move an extra distance bas shown in figure.
The vector b+PQ connects end point with starting point. This is burger vector of the dislocation.

Types of Line Defects

2.1. Edge Dislocations
2.2. Screw Dislocations
2.1. Edge Dislocations
Edge dislocations occur when an extra half-plane is inserted. The slip plane is at the end of the plane. This
line runs along the top of the extra half-plane. The inter-atomic bonds are significantly distorted only in
the immediate around of the dislocation line. In edge dislocations the burger vector is perpendicular to
the dislocation line and the distortion produces an extra half-plane above the slip plane.

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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 the 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 is
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 edge dislocation moves parallel to the direction of
stress.
Types of Edge Dislocations
2.1.1. Positive Edge Dislocation
2.1.2. Negative Edge Dislocation
2.1.1. Positive Edge Dislocation
If the extra plane of atoms in above the slip plane of the crystal than the edge dislocation is called positive
as shown in figure. It is denoted by the symbol ┴.
2.1.2. Negative Edge Dislocation
If the extra plane of atoms is below the slip plane than the edge dislocation is called negative. It is
denoted by the symbol ┬.

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2.2. Screw Dislocations
Screw dislocations result when displacing planes relative to each other through shear. The Burgers vector
is parallel to the dislocation line.

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. 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 explain a screw dislocation, imagine a
block of metal with a shear stress applied across one end so that the metal begins to rip. It can be seen that
only a portion of the bonds are broke at any given time. The movement in this manner requires a much
smaller force than breaking all the bonds across the middle plane simultaneously. If the shear force is

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increased, the atoms will continue to slip to the right. A row of the green atoms will find their 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. The net plastic deformation of both edge and screw dislocations are the same.
The 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 easy and these materials have high ductility. Metals are
strengthened by making it more difficult for dislocations to move. This may involve the introduction of
obstacles: interstitial atoms or grain boundaries. In ionically bonded materials, the ion must move past an
area with a repulsive charge in order to get to the next location of the same charge. Therefore, slip is
difficult and the materials are brittle. Likewise, the low-density packing of covalent materials makes them
generally more brittle than metals.
3. Plane (Surface) Defects
Come form: between different phases, or between different crystals. It may arise at the boundary between
two grains, or small crystals, within a larger crystal. The rows of atoms in two different grains may run in
slightly different directions, leading to a mismatch across the grain boundary. The 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 neighboring atoms outside the surface.
Types of Plane Defects
3.1. External Surfaces
3.2. Grain Boundaries
3.3. Twin Boundaries
3.4. Stacking Fault
3.1. 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.

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3.2. Grain Boundaries
Polycrystalline material comprised of many small crystals or grains. The grains have different
crystallographic orientation. There exist atomic mismatch within the regions where grains meet. These
regions are called grain boundaries. Surfaces and interfaces are reactive and impurities tend to segregate

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there. Since energy is associated with interfaces, grains tend to grow in size at the expense of smaller
grains to minimize energy. This is accelerated at high temperatures. The density of atoms in the region
including the grain boundary is smaller than the bulk value, since void space occurs in the interface.

It is convenient to separate grain boundaries by the extent of the mis-orientation between the two grains.
Low angle grain boundaries: are those with a misorientation of less than about 11 degrees.
High angle grain boundaries: whose misorientation is greater than about 11 degrees.

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3.3. Twin Boundaries
A twin boundary has different crystal orientations on its two sides. However, unlike a grain boundary, the
orientations are not random, but related in a specific, mirror image way. 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 belonging
to the crystal structures of both twins.
The twinned crystals come from:

 Crystallization or the result of mechanical or thermal work.

 Grown twins because of change in the lattice during growth due to a larger substituting ion.
 Annealing results a change in crystal system during cooling.
 Gliding twins are the result of stress on the crystal.

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3.4. Stacking Fault
Is any defect that alters the periodic sequence of layers. These defects may be a wrong layer inserted into
the sequence, a change of the layer sequence or a different translation between two subsequent layers. The
common example of stacking faults is in close-packed crystal structures. Face-centered cubic (FCC)
structures differ from hexagonal close packed (HCP) structures only in stacking order: The stacking
sequence ABABABA... produces a hexagonal crystal (HCP; hexagonal close packed). The stacking
sequence ABCABCA... produces a cubic face-centered FCC crystal.

4. Volume (Bulk) (Void) Defects

Are two-dimensional 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.
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