INTRODUCTION TO MATERIAL SCIENCE

PHY- 613
B.S 7TH SEMESTER
 Lecture 7
Defects in Solids
 Lecture Outlines

Defects and their

Types
A crystalline defect refers to a
irregularity lattice having one or more
dimensions onoftheitsorder of an atomic diameter.

www.mse.berkeley.edu/groups/morris/MSE205/Extras/defects.pd
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 Crystalline Defects
There is no such thing as a perfect crystal!
o Thermodynamically “impossible”
o “defects” lower the energy of a crystal & make it more stable
o always have vacancies and impurities, to some extent

Defect does not necessarily imply a bad thing

o addition of C to Fe to make steel
o addition of Cu to Ni to make thermocouple wires
o addition of Ge to Si to make thermoelectric materials
o addition of Cr to Fe for corrosion resistance
o introduction of grain boundaries to strengthen materials
o …… and so on

“Defect” (in this context) can be either desirable or

undesirable
o In general, a defect simply refers to a disruption in the
crystalline order of an otherwise periodic material.
 Types of Defects

Crystal imperfections are broadly classified into four

major classes :

1. Point defects (Zero Dimensional):

o Vacancy atoms, Interstitial atoms, Substitutional atoms

2. Line defects (One Dimensional):

o Dislocations: They are lines along which the crystal pattern is
broken

3. Planar or surface defects (Two Dimensional):

o Grain Boundaries and external surface along which distinct
crystallites are joined together

4. Volume defects (Three Dimensional):

o Precipitates which are small volumes of different crystal structure
o Voids – a small 3D regions where there are no atoms
Point defects - 0D imperfections
 Point defects - 0D imperfections
Point Defects
• Atoms in solid possess vibrational energy, some atoms have
sufficient energy to break the bonds which hold them in equilibrium
position. Hence once the atoms are free they give rise to Point
Defects.
• A point defect disturbs the crystal pattern at an isolated site

Classes of point defects:

• It is useful to distinguish intrinsic defects, which can appear in a
pure material, from extrinsic defects, which are caused by solute
or impurity atoms.

❑ Intrinsic defects. ❑ Extrinsic defects

1. Vacancy 1. Substitutional
2. Self-Interstitial 2. Interstitial
 Intrinsic Point defects
Vacancies
• An intrinsic defect, vacancy, is formed when an atom is missing from a
position that ought to be filled in the crystal. Thus a ‘vacancy’ is a lattice
position that is vacant because the atom is missing.
• There are naturally occurring vacancies in all crystals
• The concentrations of vacancies increase with:
o increasing temperature
Vacanc
o decreasing activation energy y

distortion
of planes

Scanning probe micrograph that shows a vacancy

on a (111)-type surface plane for silicon.
 Intrinsic Point defects

Self-Interstitial
• When an atom occupies an interstitial site where no atom would
ordinarily appear, causing an interstitialcy

• If the matrix atom occupies its own interstitial site, the defect is called
Self Interstitial.

• Self-interstitials in metals introduce large distortions in the surrounding

lattice.

self-
interstitial
distortion
of planes
 Intrinsic Point defects

Vacancy and Interstitial defects

• Because the interstitial sites in most crystalline solids are small

(or have an unfavorable bonding configuration, as, for
example, in the diamond lattice) interstitialcies are high-energy
defects that are relatively uncommon.

• Vacancies, on the other hand, are present in a significant

concentration in all crystalline materials. Their most
pronounced effect is to govern the migration of atoms on the
crystal lattice (solid state diffusion). In order for an atom to
move easily from one crystal lattice site to another the target
site must be vacant.

• Vacancy and intestinal are inverse phenomena.

 Intrinsic Point defects

Frenkel and Schottky defects

• Ordered compounds can have more complex intrinsic defects. In most
compounds the different species are charged to at least some degree.

• An intrinsic defect destroys the local charge balance, which must be

restored in some way. The compound defects that preserve charge
are easiest to visualize in binary ionic solids like NaCl.

• An isolated vacancy in an ionic solid creates an excess charge.

The excess charge can be compensated by a paired vacancy on the
sub- lattice of the other specie; for example, the excess charge
associated with a Na-vacancy is balanced if there is a Cl-vacancy
nearby.

• Alternatively , The charge imbalance caused by the vacancy can be

corrected by adding an interstitial of the same specie; a Na-vacancy is
compensated by a Na-interstitial
 Intrinsic Point defects

Frenkel and Schottky defects

 Intrinsic Point defects

Frenkel and Schottky defects

• Schottky defect; In ionic crystals, a neutral defect that forms when oppositely
charged ions leave their lattice sites, creating a paired vacancies on the cation
and anion sub-lattices.

• The charge imbalance caused by the vacancy can be corrected by adding an

interstitial of the same specie; a Na-vacancy is compensated by a Na-interstitial

• A Frenkel defect is a type of defect in crystalline solids wherein an atom or ion

is displaced from its lattice position to an interstitial site, creating a vacancy at
the original site and an interstitial defect at the new location within the same
element without any changes in chemical properties

• In compounds whose atoms are less strongly ionized it is energetically possible

for species to exchange sites, so that an A-atom appears on the B-sublattice or
vice versa. This type of point defect is called an anti-site defect, and is fairly
common in semiconducting compounds such as GaAs.
 Intrinsic Point defects

Frenkel and Schottky defects

For Ionic Solids, Frenkel and Schottky defects are likely to form

Schottky Defects

When cation vacancy is associated with anion vacancy, the

defect is called Schottky Defect.

Frenkel Defects

When an atom leaves its regular site and occupy nearby interstitial
site it gives rise to two defects i.e. one vacancy and other self
interstitial these two defects are called as Frenkel Defects.
 Intrinsic Point defects

Frenkel and Schottky defects

 Extrinsic Point defects
Interstitial and Substitution
The extrinsic point defects are formed by the introduction of foreign atoms,

o If these foreign atoms are which are added intentionally to the

material, they are called solutes . If they are not introduced intentionally
, they are called impurities

o The foreign atom may occupy a lattice sites (proper regular atomic site),
in which case it is called a substitutional solute (or impurity) or it may
fill an interstitial site ( not s proper regular atomic site), in which case it is
called an interstitial solute (or impurity).
- Substitutional impurity atoms (usually large)
- Interstitial impurity atoms (usually small)

o Since the interstitial sites are relatively small, the type of the solute is
largely determined by its size.

o Small atoms, such as hydrogen, carbon and nitrogen are often found in
interstitial sites. Larger atoms are usually substitutional.
 Extrinsic Point defects
Interstitial and Substitution
• A small sized foreign atom occupies the space between the atoms of the
crystal without dislodging the parent atoms.
• This interstitial atom is much smaller in size than the atoms among which it is
present.
• Such defects can cause an increase in the density of the substance
Point defects - 0D imperfections
Point defects - 0D imperfections

Self-interstitial dimers in graphene at 80 kV

AC-HRTEM.
 REFERENCES

Callister, W. D., and D. G. Rethwisch. 2014. Fundamentals of

Materials Science and Engineering: An Integrated Approach. Wiley,
9th Edition.
Shackelford. J. F. 2014. Introduction to Materials Science for
Engineers. Prentice Hall, 8th Edition
http://www.doitpoms.ac.uk
All ebooks are available on Zlibrary websit
https://z-lib.org/Or https://b-ok.cc/