Crystal defects

Solid State Chemistry – An Introduction Smart & Moore

Fundametal concepts of Inorganic Chemistry A. K. Das
Essentials of Materials Science and Engineering D. R. Askelard & P. P. Fulay
 Point defects Line defects Surface defects
Vacancy Edge dislocation Grain boundary
Interstitial defect Screw dislocation Stacking faults
Substitutional defect Twin boundary

A vacancy is produced when an atom or an ion is missing from its normal site in the
crystal structure.
An interstitial defect is formed when an extra atom or ion is inserted into the crystal
structure at a normally unoccupied position.
A substitutional defect is introduced when one atom or ion is replaced by a different type
of atom or ion.

Stoichiometric defects
Non-stoichiometric defects

In ionic crystals, only point imperfection is important.

 Point defects
A point defect typically involves one atom or ion, or a pair of atoms or ions,
their presence is ‘‘felt’’ over much larger distances in a crystalline material.

Point defects (a) vacancy, (b) interstitial atom, (c) small substitutional atom,
(d) large substitutional atom, (e) Frenkel defect , (f) Schottky defect. All of these defects
disrupts perfect arrangement of the surrounding atoms and create a strain in the crystal
structure
Vacancy defect:
V T (Equilibrium concentration of V at given T)
nv= n exp-(Q/RT)
nv= no. of vacancies/cc
n=no. of atoms/cc
Q=Energy required to create 1 mole of vacancies
(Cal/mol or J/mol)
R=1.987 cal mol-1K-1
Interstitial defect : T independent
PdHx (impurity)
Fe+C=Carbon steal (dopant)

Substitutional defect: T independent

MgO to NiO
Cu in Ni
 Stoichiometric point defects

Schottky defect Frenkel defct

Missing of cations and anion produces a Some of the constituent ions
pair of holes leading to Schottky defects. occupy the interstitial positions
rather that their lattice cites.
Highly ionic crystals of high coordination Crystals having low coordination
numbers eg. NaCl, CsCl, KCl, KBr numbers AgBr, AgI, ZnS.
 NaCl-type AgCl

Ag+

Type of point
defect?

Cl-
Td coordination of an interstitial Ag + ion in AgCl
 Anion Frenkel

CaF2
CaF2
Redrawn primitive cubic array of anion

octant
 Kröger Vink Notation
Defect Chemistry Equation
 Number of defects
The number of Schottky/Frenkel defects in a crystal of composition MX is given by:

where Ns is the number of Schottky defects per unit volume, at T K, in a crystal with N
cation and N anion sites per unit volume; ∆Hs is the enthalpy required to form one defect.

where NF is the number of Frenkel defects per unit volume, N is the number of lattice sites
and Ni the number of interstitial sites available. ∆HF is the enthalpy of formation one
Frenkel defects.
 Value of Ns/N

T/K H=5x 10-19 J H=1x 10-19 J

300 6.12 x10-27 5.72 x10-6

1000 1.37 x10-8 2.67 x10-2
 Nonstoichionmetric (Berthollide) defect
Solid chemical compounds where the elemental composition cannot be represented
by a ratio of small whole numbers.
 a)Metal excess (A1+B)
Crystal heating with the alkali metal vapor or
small amount of alkali metal is doped
with alkali metal halide crystals, this type of
defect origintes.
Appers in the crystals that are prone to Schottky
defects.

NaCl-yellow
KCl-Violet
KBr-blue green

Farben centre (‘Farbe’-color)

n-type semiconductor
 Colour Centres

F-centre NaCl in Cl2 vapor

H-centre (Halogen Centre)

Mineral Fluorite (CaF2) Blue John-Blue purple

 Mineral Fluorite (CaF2) Blue John-Blue purple
When fluorite is bombarded by high-energy radiation (cosmic rays from outer space or
gamma rays from a radioactive source), a fluorine ion can be ejected from the crystal,
creating a vacancy. Momentarily, the crystal is no longer electrically neutral: it is missing a
negative charge. To regain stability, it grabs an available electron close to the crystal and
sticks it in the vacancy.

transparent fluorite

Purple colored fluorite

 Quartz varieties SiO2

Rock crystal Clear No colour centres

Smoky quartz Brownish Si4+ ↔ Al3+ + H+

Radiation creates h+ AlO45- + H+ → AlO44- + H
(hole centre)

Amethyst Purple Si4+ ↔ Fe3+ + H+

Radiation creates h+ FeO45- + H+ → FeO44- + H

One Al atom for every 10000 Si atoms change in color, hole center absorbs the light to
Product the gray to brown to black color of smoky quartz.
 The addition of Al to the SiO2 structure results in a change in color in the crystal. If
Al3+ replaces the Si4+ ion in the SiO2 to maintain electrical neutrality of the crystal, a
proton (H+) could be present. If irradiation ejects an electron from an oxygen atom
near the Al ion, the electron can be trapped by the proton. The whole (AlO4)5- entity
creates a "hole" color centre, being converted to (AlO4)[Link] hydrogen atom does not
absorb light. (AlO4)4-) absorbs light to produce the gray-to-brown-to-black color of
smoky quartz.

Irradiation, either man-made or naturally

occurring while the quartz is in the ground
over many thousands of years, converts
(about 1 Al atom for every 10000 Si atoms)
colorless quartz to smoky quartz.
The aluminum is in the form Al3+. A
hydrogen or sodium ion (H+ or a Na+) will
always be found nearby to neutralize its
charge.
 a)Metal excess (A1+B)
ZnO heated in Zn vapour
The excess cation occupy interstitial voids
The electrons released stay associated to the interstitial cation

This type of defects generally occur in the crystal

where the Frenkel defects predominate.

The trapped electron gives the color and electrical conductivity.

n-type semiconductor
 a)Metal deficiency (A1-B)
Cation Vacancies:

p-type semiconductor

Wustite
 Interstitial position in fcc unit cell

1-4 Oct interstitial sites

5-12 Td interstitial sites
Many crystals can be viewed as being generated by close packing of large anions. Cations are viewed
as smaller ions fit into the interstitial sites of the close packed ions
 Extra anions occupying interstitial sites: In the case, the extra anions may be
occupying interstitial positions. The extra negative charge is balanced by the
extra charges on the adjacent metal ions. Such type of defect is not common
because the negative ions usually very large and they cannot easily fit into the
interstitial sites.

UO2+x (0x 0.25)

O’’

O’
Sometimes, the cations are missing and electrical neutrality is maintained by some
foreign cations.
m
Line defect or Dislocation
Solidification
Material processing
Strengthening of materials

The line along with shearing occurs is a

Screw dislocation
b II dislocation

The bottom edge of the

extra plane is an edge
b prep to dislocation Dislocation.
Screw Dislocation
 Screw Dislocation

Schematic diagram (lattice planes) showing

an edge dislocation. Burgers vector in black,
Crystal lattice showing atoms and
dislocation line in blue.
lattice planes
Mixed Dislocation
 Grain Boundary

Considerable resistance to the flow of current from one grain to other

Strengthen the metallic materials
Stacking Fault ( extra plain or missing plane)
Intrinsic Fault: a plane is missing…ABCACABC
Extrinsic Fault:Extra plain interpose…ABCABACABCABCA
 Twin boundary
Twin boundary separtes two grains that are related by mirror symmery