[Link].H.

Hadi Notes Engineering Materials 2016

Lecture 6:

Defects in solids: Point defects and line defects

Imperfections or defects: Any deviation from the perfect atomic arrangement in a crystal is said to
contain imperfections or defects. In fact, using the term “defect” is sort of a misnomer since these
features are commonly intentionally used to manipulate the mechanical 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 arise from impurities and imperfections
 Atomic diffusion may be accelerated enormously by iumpurities or imperfections
 Mechnical and plastic properties are usually controlled by imperfections

Imperfections in crystalline solids are normally classified according to their dimension as follows
1. Point imperfections (Zero dimensional defects)
2. Line imperfections (one dimensional defects)
3. Plane or surface imperfections (Two dimensional defects)
4. Volume imperfections (three dimensional defects)

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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

Point Defects: 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.
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.

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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. 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. Schottkey imperfection is a type of vacancy in which an atom being
free from regular site, migrates through successive steps and eventually settles at the crystal surface.
In a ionic crystal, however a vacancy on either a cation or anion site must be electrically balanced by
some means. This may be achieved if there are an equal number of cation and anion vacancies, or if
for every ionic crystal vacancy a similar charged interstitial appears.

The combination of anion cation vacancies (in pairs) is called Schottkey imperfections. The
combination of a vacancy and interstitial is called a Frankel imperfection.
Line Imperfections:
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.
To extreme types of dislocations are distinguish as
1. Edge dislocations and
2. Screw dislocations.

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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.

Screw Dislocations: 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

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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.

Planar defects, which are interfaces between homogeneous regions of the material. Planar defects
include grain boundaries, stacking faults and external surfaces.
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 from a previous discussion 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.

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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

Another type of planer defect is the grain boundary. Up to this point, the discussion has focused on
defects of single crystals. However, 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 know 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.

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

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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.

Effect of point defect:

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Lecture 11: Introduction to Band Theory-Metals, Semiconductors and Insulators

There are many energy levels (~1023) in a given band. A given atom in a solid has a fixed number of
nearest neighbors, but many distant neighbors as shown in Fig. 1.
If we consider just a single plane and an arbitrary atom, there may be four nearest neighbors as in Fig.
1(a). Isolated from others, this system should give rise to four split energy levels. With the widest
energy separations; the interaction occurs between neighbors.

E E E

(a) (b) (c) Figure 1: Splitting of valence band

As we move away from an atom, there are more and more neighbors. For example, an atom may have
eight 4th neighbors in one plane as shown in Fig. 1(b). In isolation from the rest, the energy would
have split into nine narrowly separated levels, since the atoms are further isolated. In a crystal, there
are hundreds and thousands of distant neighbors, so the number of narrowly-split
energy level will correspondingly be very large. The outermost energy band that is completely or
partially filled is called the valence band in solids. The band that is above the valence band and is
empty at 0 K, is called the conduction band.
According to the nature of band occupation by electrons, all solids can be classified broadly into two
groups.
Firstly, the group in which there is partially filled band immediately above the uppermost filled
valence band. This is possible in two ways. One - the balance band is only partially filled. Second- A
completely filled valence band overlaps the partially filled conduction band as shown in Fig. 2.

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Conduction Band (CB)

CB

Valence Band (VB) VB

(a) (b)
Fig. 2: Metals have partially filled or overlapping bands.
Secondly, the groups which include empty bands lying above completely filled band levels. The
solids of this group conveniently subdivided into insulators (dielectrics) and semiconductors
depending on the width of the forbidden band.

Conduction Band (CB) Conduction Band (CB)

1.1 eV
Eg= 5.4 eV

Valence Band (VB) Valence Band (VB)

(a) (b)
Fig. 3: The difference between a semiconductor and an insulator in terms of energy gap.
Insulators include solids with relatively wide forbidden bands. For typical insulators the band gap,
Eg > 3 eV. (Diamond: 5.4 eV, BN: 4.6 eV, Al2O3: 7 eV).
On the other hand, semiconductors include solids with relatively narrow forbidden bands. For
typical semiconductors, Eg  1 eV. ( Ge: 0.7 eV, Si: 1.12 eV, InSb: 0.17 eV, GaAs: 1.43 eV)
According to Pauli’s exclusion principle, each energy level must be occupied by no more than two
electrons. Thus, Monovalent metals such as Cu, Ag, and Au have one electron in the outermost
shell and hence the corresponding energy band is only half filled. On the other hand, the divalent
metals such as Be, Mg, Ca, etc. have overlapping valence and conduction bands. The trivalent
metals Al, Ga, etc. have similar band structure as monovalent metals.
The tetravalent nonmetals such as C, Si, etc. have even number of electrons in the outermost (4
electrons in each case) shell like divalent atoms. The corresponding valence band is full but unlike
the divalent metals there is no overlapping of the VB with the CB in this case.

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