Unit -1

Defects
 Objectives

 Learn the various defects in the crystal and properties

affected by the defects
 Crystal Defects
 Ideal Crystal

Crystal == Lattice + Basis

Bringing all the atoms together to try to form a perfect crystal, we lower the total
potential energy of the atoms as much as possible for that particular structure.
 Crystal Defects

 Real Crystal

Deviations from the ideal case - No crystal is perfect.

Impurities , Imperfections

Effect: defects are very important in determining material properties

Properties of the crystal
 Defects
Classifications of Defects :

1. Zero dimensional (or) Point defects

Vacancy, Substitutional impurity, Intersitial impurity,
Colour centers ...
2. One dimensional (or) Line defects
Dislocations - Edge and Screw
3. Two dimensional (or) Surface/ Planar defects
Grain Boundary, Twin Boundary, Stacking fault..
4. Three dimensional (or) Volume defects
Pores, Cracks, Precipitate and other phases..
Volume defect will not be part of this lecture
 Point Defects
Vacancy :

There will be small amont of vanccancies should be present in

crystals (at equilibrium). Above the absolute zero temperature,
all crystals have atomic vacancies or atoms missing from lattice sites
in the crystal structure.

Why ?
 Point defects -Vacancy
Vacancy :

There will be small amont of vanccancies should be present in crystals (at

equilibrium). Why ?

 Cystals with vacancies have lower Gibb's free energy than perfect crystals.

So, the vacancies exist as a requirement of thermal equilibrium and are called
thermodynamic defects.
 Point defects -Vacancy
• Atoms vibrate in the equilibrium position with a distribution of energy closely to
Boltzmann distribution

• Atoms with greater energy – breaks the bond- creates vacancy

• Vacancy then propagates

 Point defects -Vacancy

Generation of a vacancy by the diffusion of atom to the surface and the subsequent
diffusion of the vacancy into the bulk.
 Point defects - impurities
The crystal structure may contain impurities, either
naturally or as a consequence of intentional addition (doping)

• If the impurity atom substitutes directly for the host atom, the result is called
a substitutional impurity
Examples: Si doped with arsenic, Cu in Ni (Increases the strength of the Nickel)

• The impurity atom can also place itself in an interstitial site, that is, in a void between the
host atoms the impurity is called an interstitial impurity
Example: carbon in BCC iron crystal the Fe becomes steel

 A dopant, also called a doping agent, is a trace impurity element that is artifically
inserted into a substance in order to alter the electrical properties or the optical
properties of the substance.
 Point defects -Vacancy
Equilibrium concentration of vacancies :

  Ev 
nv  N exp 
 kT 

nv - vacancy concentration
N - number of atoms per unit volume in the crystal
Ev - energy required to create a vacancy/ enthalpy of vacany formation
k - Boltzmann's constant = 1.38 × 10-23 J/ K = 8.62 × 10-5 eV/ K
T - Temperature in kelvin
 Point defects - impurities
• Distortion of lattice takes place around the impurities
 Point defects in Ionic Crystals

 Missing of cation-anion pair especially

in ionic crystals such as NaCl (which
may have migrated to the surface), so
the neutrality is maintained . This type
of defect is called Schottky defect

 These Schottky defects are responsible

for the major optical and electrical
properties of alkali halide crystals.

 when a host ion is displaced into an interstitial position, leaving a vacancy at its
original site. The interstitial ion and the vacancy pair constitute the Frenkel defect
 Point defects in Ionic Crystals
 Ionic crystals can also have substitutional and
interstitial impurities that become ionized in the
lattice.

 Overall, the ionic crystal must be neutral

 Suppose Mg2+ ion substitutes for an Na+ ion in

the NaCl crystal, either one Na+ ion is missing
Two possible imperfections caused by somewhere in the crystal, or an additional Cl−
ionized substitutional impurity atoms ion exists in the crystal.
in an ionic crystal
 when a doubly charged negative ion, such as O2−,
substitutes for Cl−, there must either be an
additional cation (usually in an interstitial site)
or a missing Cl−
 Dislocations

 Dislocation is a linear or one dimensional defect around which some of the

atoms are misaligned
 Dislocations are responsible for the slip phenomenon, by which most metals
deform plastically
 Dislocations are also intimately connected with nearly all other mechanical
properties such as strain hardening, yield point, creep etc

Dislocation is of two types:

• Edge dislocation
• Screw dislocation
Perfect Crystal
Edge Dislocation
 Edge Dislocation

Extra
Half
Plane

Missing
Half
Plane a 2a
Edge Dislocation
Edge Dislocation
Edge Dislocation
Edge Dislocation
Edge Dislocation
 Edge Dislocation

Edge only the bottom

Dislocation edge of the extra
line half plane is defect
not the
entire half plane
Edge Dislocation
Eventhough the
defect appears to be
cylindrical ,
comparing the
dimensions...
the diameter is
negligible
to the length of the
cylinder

So, it will look as line

defect
 Edge Dislocation

Around the dislocation there is a strain field as the atomic bonds have been compressed
above and stretched below the dislocation line
Screw Dislocation

Why it is screw ???

Screw Dislocation

Screw Dislocation - shearing of one

portion of the crystal with respect to
another, by one atomic distance.

The displacement occurs on either side

of the screw dislocation line.
Screw Dislocation

Dislocation line

Parallel planes perpendicular

to the dislocation line join to
form a spiral ramp with
dislocation line as its axis
 Dislocations

 Both edge and screw dislocations are generally created by stresses resulting from
thermal and mechanical processing.

 A line defect is not necessarily either a pure edge or a pure screw dislocation; it
can be a mixture

A mixed dislocation
 Dislocations
How dislocations are examined or seen ? ....

 interface dislocations are called misfit dislocations -- mismatch of lattice parameters

in the heterostructure
 threading dislocation is one that extends from the surface of a strained layer system,
goes through the layer
 Dislocations
Affect the properties of materials ....

 The presence and motion of these dislocation leads to Permanent deformation of

metals and hence effect the mechanical properties.

 In electrical circuits, these dislocations increases the resistivity of the material, which
leads to leakage current in pn junction and produces noise in the devices

 In a metal interconnection line on a chip, there may be an average of 10 4-105

dislocation lines per mm2 of crystal, whereas a silicon crystal wafer that is
carefully grown may typically have only 1 dislocation line per mm 2 of crystal.
 Dislocations
What you have seen in the previous slide is because of this ....
 Planar defect: Grain boundaries
o A grain boundary separates regions of different crystalline orientation (i.e. grains)
within a poly crystalline solid.

o The atoms in the grain boundary will not be perfect crystalline arrangement.

o Grain boundaries are usually the result of uneven growth when the solid is
crystallising.

o Grain sizes vary form 1micro to 1mm. Grain boundaries tend to decrease the
electrical and thermal conductivity of the matieral
 Planar defect: Grain boundaries
How grain boundaries are formed ? ...

Solidification of a polycrystalline solid from the melt (liquid).

Nucleation ( a goup of solidified atom)  Growth ( nuclei combines together ) 
forms solidified polycrystalline solid. (For simplicity cubes represent atoms)

 Grows from initial nucleation sites with random orientation.

 These grow into individual grains
Planar defect: Grain boundaries

 The grain boundaries have

broken bonds, voids, vacancies,
strained bonds and “interstitial”
type atoms

 The structure of the grain

boundary is disordered and the
atoms in the grain boundaries
have higher energies than those
within the grains
 Planar defect: Grain boundaries

Grain boundaries are very messy, allowing diffusion, movement and annealing (grain
growth driven by surface energy)

Even more complicated if a current is flowing. The electron moves things around,
particularly along boundaries --- Electrons are scattered in the grain boundaries increase
resistance
 Volume Defects

• Form when a cluster of point

F. Gao,J. Qu, Materials Letters Volume 73, 15 Apr.2012, 92–94
defects join
• Vacancies join: they form
– voids
– Pores
• Cracks
• Cluster of impurity atoms join
 precipitate

Journal of Non-Equilibrium Thermodynamics,

33(1):25-45, 2008
 Volume Defects

Dislocations bend and terminate to form voids

GaN film grown conventionally on a sapphire substrate, and (b) GaN film regrown
with embedded voids
[Link]
 Problems
The energy of formation of a vacancy in the aluminum crystal is about 0.70 eV. Calculate
the fractional concentration of vacancies in Al at room temperature, 300 K, and very close
to its melting temperature 660 ͦ C . What is the vacancy concentration at 660 ͦͦ C given that
the atomic concentration in Al is about 6.0 x 1022 cm-3?

Solution :
Problems
 Problems
The energy of vacancy formation in the Ge crystal is about 2.2 eV. Calculate the fractional
concentration of vacancies in Ge at 938 ͦͦ C, just below its melting temperature. What is the
vacancy concentration given that the atomic mass Mat and density ρ of Ge are 72.64 g mol-1
and 5.32 g cm-3, respectively?

Solution :
the fractional concentration of vacancies at 938 °C or 1211 K is
Problems