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Defects in crystals
It is not possible to make crystals that are prefect
in every respect
some are more perfect than others
It takes energy to create defects in crystals
The presence of defects increases the entropy of
the crystal
above absolute zero always expect some intrinsic
defects
Stoichiometry
Non-stoichiometric compounds
Types of defect
Defects may occur in isolation due to the increase
in entropy of the crystal
intrinsic point defects
May occur in isolation to balance the presence of
an impurity
extrinsic point defect
Defect may occur throughout the crystal
extended defect
Intrinsic point defects
Two common types of intrinsic point defect
Schottky and Frenkel
A Schottky defect consists of charge balancing
cation and anion vacancies
Found in NaCl
A Frenkel defect is a charge balancing interstitial
and vacancy
can have cation or anion Frenkel defects
Values of ns/N
T/K HS = 5 x 10-19 J HS = 1 x 10-19 J
300 6.12 x 10-27 5.72 x 10-6
1000 1.37 x 10-8 2.67 x 10-2
Defects in AgCl
Ag+ + Vi Agi+ + VAg
K = [Agi+][VAg] / [Ag+][Vi]
Let N be the number of lattice sites and Ni the
number of interstitial sites
Ni = [VAg] = [Agi+]
[Ag+] = N - Ni
[Vi] = N
number of interstitials is simply related to number of
lattice sites for most materials
Color centers
Electrons trapped in vacant sites give rise to
colored materials
color centers
color arises due to transitions between electron in a box
levels
Trapped electrons can be produced by
irradiation of the sample
treatment with an electron donor like sodium or
potassium vapor
F, H and V centers
Irradiation can lead to defects where an electron has bee lost or added
Treatment with alkali metal vapor can lead to excess electrons in material
Imaging plates
Color centers are useful in medical X-rays
using BaFBr:Eu2+ phosphors
BaFBr:Eu2+ phosphors
Nonstoichiometric 3d oxides
FeO
Aliovalent substitution
Interstitial anions
Not common due to limited size of interstitial sites but
occurs for fluorite structure
Ca1-xYxF2+x
U4+1-xU6+xO2+x
Anion vacancies
Important in ionic conductors
Zr1-xCaxO2-x 0.1 < x < 0.2
Interstitial cations
Lix(Si1-xAlx)O2 stuffed quartz structure (0 < x < 0.5)
Characterizing solid solutions
Can determine if solid solution forms by
measuring lattice constants of material using
x-ray diffraction
Lattice constants typically vary linearly with solid
solution composition
Vegards law
Can work our mechanism of solid solution
formation with the aid of density
determination
Magneli phases
Homologous series
Each member of the homologous series has a
different repeat distance between shear planes
Consider W11O32
Block structures
Crystallographic
shear planes running
in two directions can
lead to double shear
or block structures
W4N26O77 consists
of 4 x 4 and 3 x4
blocks
Tungsten bronzes
MxWO3
M is an alkali metal or alkaline earth or H
They can be prepared by
electrocrystallization of melts
treatment of WO3 with alkali metal sources
hydrogen spillover
There are a variety of possible crystal structures
Are used as bronze pigments
The structures of tungsten bronzes
Stacking faults