Imperfections in Solids - II

Point Defects

Vacancy
Non-ionic Interstitial
Impurity
crystals Alloying element/Dopant Substitutional
0D
(Point defects)
Frenkel defect
Ionic
Other ~
crystals
Schottky defect

 0D (point) defects are imperfect point-like regions in the crystal about the size of 1-2
atomic diameters.
 The extent of the distortion field may however extend to a larger distance.
 Point defects can be created by ‘removal’, ‘addition’ or displacement of an atomic
species (atom, ion).
 Defect structures in ionic crystals can be more complex

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 Typical enthalpies for defects
Typical enthalpies of formation of Schottky and Frenkel defects

Schottky Defects Frenkel Defects

∆Qs (J) ∆Qfr (J)
Compound ∆Qs (eV) Compound ∆Qfr (eV)
× 10–3 × 10–3
LiI 2.08 1.30 β-AgI 1.12 0.70
LiBr 2.88 1.80 AgBr 1.92 1.20
NaCl 3.69 2.30 AgCl 2.56 1.60
CaO 9.77 6.10 CaF2 4.49 2.80
MgO 10.57 6.60 ZrO2 6.57 4.10

 Even in solids like LiI with low ∆Qs (enthalpy of formation of Schottky defects) (1.30 eV)
the fraction of defects at RT (300K) is small (1.2×10–11). At 1000K the fraction is 5.3×10–4.
 This implies there are very few Schottky defects at room temperature.
 Depending on the values of ∆Qs & ∆Qfr both these defects may be present in a crystal
(though one of them dominates in most systems).

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 Ionic defects

Calculate the number of Schottky defects per cubic meter in potassium chloride at 500 0C.
The energy required to form each Schottky defect is 2.6 eV, whereas the density for KCl (at
500 0C) is 1.955 g/cm3.

first compute the value of N (the number of lattice

sites per cubic meter)

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 How to create point defects

• Growth and synthesis Impurities may be added to the material

during synthesis

• Thermal & thermochemical treatments and other stimuli

o Heating to high temperature and quench
o Heating in reactive atmosphere
o Heating in vacuum e.g. in oxides it may lead to loss of
oxygen

• Plastic Deformation

• Ion implantation and irradiation

o Electron irradiation (typically >1MeV) → Direct momentum
transfer or during relaxation of electronic excitations)
o Neutron irradiation

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 Specifying Composition of a Solid Solution

• Weight
percent:

• Atom
Percent:

Conversion of weight percent to atom percent

Derivation of Composition-Conversion Equation

Conversion of atom percent to weight percent

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 Specifying Composition of a Solid Solution
Determine the composition, in atom percent, of an alloy that consists of 97 wt%
aluminum and 3 wt% copper.
CAl = 97 CCu = 3 ACu = 63.55 g/mol AAl = 26.98 g/mol

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 Specifying Composition of a Solid Solution
convert concentration from weight percent to determine the density and atomic
to mass of one component per unit volume weight of an alloy given weight percent
of material or atom percent composition.

Concentrations in
kg/m3
Density and Atomic weight
of the alloy

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 Line Defects – Edge Dislocation
an extra portion of a plane of atoms, or half-plane, the Points to note:
edge of which terminates within the crystal.
• Burger’s vector

• Dislocation line

• Dislocation motion

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 Line Defects – Screw Dislocation

Screw dislocation, may be thought of as being formed by a shear stress that

is applied to produce the distortion

The atomic distortion associated with a screw

dislocation is also linear and along a dislocation line

The screw dislocation derives its name from the spiral or helical path or
ramp that is traced around the dislocation line by the atomic planes of
atoms.

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 Line Defects – Screw Dislocation

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 Line Defects – Mixed Dislocation
Most dislocations found in crystalline materials are probably neither pure edge
nor pure screw, but exhibit components of both types; these are termed mixed
dislocations.

Dislocations can be observed in

crystalline materials using electron- Transmission Electron Microscopic
microscopic techniques. Image of a Ti alloy

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 Dislocation

Permanent deformation of most crystalline materials is by the motion of dislocations.

Burgers vector is an element of the theory that has been developed to explain this
type of deformation.

Dislocations are involved in the plastic deformation of

• crystalline materials, both metals and ceramics
• Polymers

Virtually all crystalline materials contain some dislocations that were

introduced
• during solidification,
• during plastic deformation, and
• rapid cooling.

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 Interfacial Defects

• Interfacial defects are boundaries that have two dimensions and normally separate
regions of the materials that have different crystal structures and/or crystallographic
orientations.
o external surfaces
o grain boundaries
o phase boundaries
o twin boundaries
o stacking faults.

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 Interfacial Defects – External Surfaces
• Every object terminates at some point and hence, has boundaries or surfaces.

• External surfaces are themselves interfacial defects as they are deprived of some
nearest neighbouring atoms, unlike in the case of interior ones.

• As a result, surfaces have some surface energy (J/m2) associated with them. The
surfaces tend to lower this energy by minimizing the surface area. Liquid droplets
are spherical due to this reason. Solids, being rigid, cannot.

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 Interfacial Defects – Grain Boundaries
boundary separating two small grains or crystals having different crystallographic
orientations in polycrystalline materials.

Grain boundaries are 2D defects in the

crystal structure
o Decrease the electrical
o Decrease the thermal conductivity
of the material.

SEM Image of grain

boundaries

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 Interfacial Defects – Grain Boundaries

When this orientation mismatch is slight,

on the order of a few degrees, then the
term small- (or low-) angle grain
boundary

High-angle grain boundary

• The atoms along the grain boundaries are

less regularly arranged.

• Grain boundaries also are at a higher energy

state. The magnitude of this energy is
function of the degree of the misorientation.

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 Interfacial Defects – Grain Boundaries

• The adjacent figure shows a type of interfacial

defect called tilt boundary.

• A similar type of defect is twist boundary which

can be described using screw type of
dislocations.

Tilt boundary due to

alignment of edge
Twist Boundary
dislocations

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 Interfacial Defects – Phase Boundaries

• Phase boundaries exist in multiphase materials, wherein a different phase

exists on each side of the boundary; furthermore, each of the constituent
phases has its own distinctive physical and/or chemical characteristics.
• The best examples for phase boundaries coming with precipitates are the
iron carbide (Fe3C) particles invariably found inside steel. Whenever they
grow or shrink, the phase boundary separating their surface from the
crystal must move.
• Phase boundaries move as soon as atoms can move around

• Pretty much all of semiconductor technology and in particular

optoelectronics relies on phase boundary engineering

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 Interfacial Defects – Twin Boundaries

A special type of grain boundary across which there is a

specific mirror lattice symmetry

• Mechanical Twins – application of shear

force
• Annealing Twins – due to annealing (heat
treatment)

Annealing twins – found in FCC crystal

structure metals

Mechanical twins – in BCC and HCP metals.

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 Interfacial Defects – Miscellaneous
• A stacking fault – say, in FCC, a break in the sequence of stacking of {111}
planes ABCABCABC…

• Phase boundaries in multiphase materials.

• Ferromagnetic domain walls

domain wall defect

re-orientation of the magnetic moments between two 180-
degree domain

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 Bulk or Volume Defects

• Voids, pores, cracks, foreign inclusions and other phases (precipitates).

• Most common are second phases (eg. Salt in water)

• Cracks represent macroscopic volumetric defect

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