Point Defects

Presented By:
Anuradha Verma
Ph. D Scholar

Layout of Presentation
Imperfections and their types

Point Defects

Thermodynamics of Point Defects

Vacancy Concentration temperature
dependence

Color Center

Why would we want

to study defects?

Affect properties of material

Electrical
(all defects, especially point
defects)

Mechanical e.g., strength,

toughness, hardness, etc) (all
defects, especially
dislocations)

Optical

(all defects,
especially point
defects)

Kinetic e.g., diffusion

Magnetic
(all defects)

(all defects,
especially point
defects)

Imperfections in Solids

Ideal structure
of a solid

Deviations from
ideal structure

Every lattice point

has exactly the same
environment

Defects

0DPoint
Defects

Vacancies
Interstitials

1D-Line
Defects

Types
of
Imperfections

Dislocations

2DPlanar or
Area
Defects
3D-

Volume
Defects

Inclusion
Voids

Grain
boundary
Stacking fault

Vacancy
Non-ionic
crystals
0D
(Point
defects)

Ionic
crystals

Interstitial
Impurity

Substitutional

Frenkel defect
Other ~
Schottky defect

Vacancies: vacant atomic sites in a structure

Vacancy
distortion
of planes

Self-Interstitials: "extra" atoms positioned between atomic

sites

selfinterstitial
distortion
of planes

Schottky defect and Frenkel defect

Schottky Defect:
Forms
when
oppositely
charged ions leave their lattice
sites, creating vacancies.
These
vacancies
are
formed
in stoichiometric units, to maintain
an overall neutral charge in the ionic
solid.
Density of the solid crystal is less
than normal
Occurs only when there is small
difference in size between cations
and anions.

Missing Anion

Missing Cation

Frenkel Defect:
Smaller ion (usually the cation) is
displaced from its lattice position to
an interstitial site.
Creates a vacancy defect at its
original site and an interstitial
defect at its new location.
Does not change the density of the
solid.
Shown in ionic solids with large size
difference between the anion and
cation.

Antisite Defects
Occur in an ordered alloy or compound when atoms of
different type exchange positions.
AssumeType A atoms- at corners of cubic lattice
Type B atoms- center of cube.
If one cube has an A atom at its center, the atom
is on a site usually occupied by a B atom, and is thus
an antisite defect.

This is neither a vacancy nor an interstitial, nor an

impurity.

Thermodynamics of intrinsic defects

Formation of a vacancy- missing bonds and distortion of the lattice
Potential energy (Enthalpy) of the system increases
Work required for the formation of a point defect
Enthalpy of formation (Hf) [kJ/mol or eV/defect]

n defects are distributed over N lattice sites

W possible arrangements
Now

and

Therefore,
For minimum

G
0
n

H f

N n
ln

kT
n

For n << N

H f
n
exp
N
kT

Vacancy Concentration Dependence on

Temperature
The equilibrium number of vacancies for a given quantity of material
depends on and increases with temperature as follows:
Energy required to form vacancy

Equilibrium no. of vacancies

Nv
= exp
N

k T

T = absolute temperature
in Kelvin

Total no. of atomic sites

k = gas or Boltzmanns constant

Nv
N
exponential
dependence!

defect concentration

Color Centers
Imperfections in crystals
Causes color (by absorption of light)

Examples:
Diamond with C vacancies- Green color.
Replacement of Al3+ for Si4+ in quartzsmoky quartz color.
Ruby (Al2O3) with < 1% - Pink or red
color.
F center: Excess alkali atoms are added to
an alkali halide crystal, a corresponding
number of negative vacancies are
created.
M center: An M center consists of two
adjacent F centers.
R center: An R center consists of three
adjacent F centers