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Defects and nonstoichiometry

 Simple intrinsic point defects


 The thermodynamics of defect formation
 Extrinsic defects
 Defects in nonstoichiometric materials
 Defect clustering
 Solid solutions
 Extended defects
CS planes and shear structures

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

 Many solid materials are non-stoichiometric


all that really matters is charge balance
 Non-stoichiometry is common amongst
transition metal compounds
FexO where 0.957 >x > 0.833
YBa2Cu3O7-x, 1 > x > 0
 Non-stoichiometry can control properties

Non-stoichiometric compounds

TiO x TiO 0.65 < x < 1.25


TiO 2 1.998 < x < 2.000
VO x VO 0.79 < x < 1.29

Mn xO MnO 0.848 < x< 1.000

NixO NiO 0.999 < x < 1.000

LixV2 O 5 0.2 < x < 0.33


The thermodynamics of defect formation
 All macroscopic samples of materials contain some
defects as defect formation is entropically favored
when defect formation is enthalpically very unfavorable there
may be very small numbers of defects

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

Schottky and Frenkel defects

Shottky defect in NaCl


- both cation and anion are missing from
their regular lattice sites
-at room temp on 1 in 1015 sites are vacant in NaCl
-200 kJmol-1 creation energy

Cation Frenkel defect in AgCl


-cation is displaced from regular lattice
site onto interstitial site
- 130 kJ mol-1 creation energy
Frenkel defects
 Frenkel defects may occur on either the anion or
cation sublattice
 Cation Frenkel defects are more common than
anion defects
cations are smaller than anions and hence easier to
accommodate in interstitial positions
 Fluorite structures (CaF2, SrF2, ZrO2, UO2) are
good at accommodating anion Frenkel defects

Kroger-Vink notation for defects


 Defect is denoted by symbol of atom involved or by V if it is a vacancy
 Superscript indicates a net charge of +1, superscript indicates a net
charge of 1. Superscript x indicates no net charge
 Subscript indicates nature of site in crystal lattice, s for surface, I for
interstitial, element symbol for normal lattice site
 Examples:
VNa sodium ion vacancy net charge 1
VCl chloride ion vacancy net charge +1
Na Na, ClxCl Na and Cl on their normal lattice sites
x

CdNa cadmium on Na site net charge +1


Agi silver on interstitial site net charge +1
Fi fluoride on interstitial site net charge -1
Estimation of defect concentration

 It is possible to calculate the equilibrium


concentration of defects in a solid using statistical
mechanics
 ns ~ N exp(-HS / 2RT)
 nF ~ (NNi)1/2 exp(-HF/2RT)
 Defect concentration depends upon the energy
needed to form a defect and the temperature

Typical values of the defect concentration


 Most simple ionic solids have low defect
concentrations
 However, small changes in the energetics for defect
formation can lead to high defect concentrations

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

Defects in AgCl continued


 K ~ Ni2 / N2
Substitute into equilibrium constant
 G = -RT lnK, so
 [VAg] = Ni = N 1/2 exp(-G/2RT)
Hf for defects

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

F Center electron trapped in anion vacancy


Example of color center as trapped electron leads to
absorption in visible

H Center interstitial Cl atom


bonds to lattice Cl-
V Center electron removed
from lattice anion site, resulting
Cl atom pairs with neighboring Cl-

Imaging plates
 Color centers are useful in medical X-rays
using BaFBr:Eu2+ phosphors
BaFBr:Eu2+ phosphors

Extrinsic point defects


 If cationic impurities are introduced into a solid and the
dopant does not have the same valence as the cation it is
replacing extrinsic defects will be introduced
Fe1-xO has cation vacancies
Ca2+ in ZrO2 - anion vacancies
Y3+ in ZrO2 - anion vacancies
Ca2+ or Cd2+ in NaCl - cation vacancies
 Real crystals contain both intrinsic and extrinsic defects
the dominant defect type depends upon temperature and
doping/nonstoichiometry level
Defect clusters and aggregates
 Point defects interact and effect the structure around
them
This may lead to clustering
 Even in something as simple as NaCl, cation and
anion vacancies tend to pair up as they are
electrostatically attracted to one another

Nonstoichiometric 3d oxides
FeO

 Wustite is a very well studied example of a


nonstoichiometric compound
 The compound FeO is not stable
 The stoichiometry is always Fe1-xO

The iron oxygen phase diagram


The nature of the defects in FeO
 Density measurements confirm that the
nonstoichiometry is incorporated by having vacant
iron sites
 There is Fe(III) present to charge compensate the
system

The defect structure of FeO


 The defect structure is more complicated than
random iron vacancies and Fe(III)
Koch clusters in Fe1-xO

The Fluorite structure


Defect clusters in UO2+x
 Excess oxygen is
incorporated in interstitial
sites
This leads to displacement
of oxygens from normal
sites
Arrangement of defects is
similar to structure of U4O9
Can view defects as forming
clusters of U4O9 in UO2
matrix

The defect structure of TiO

 TiO spans the composition range TiO0.65 -


TiO1.25
 The stoichiometric phase TiO has many vacancies
At high temperatures the vacancies are disordered
At low temperatures the Ti and O vacancies exist in an
ordered array
Defects in TiO
 Based on NaCl
structure
1 in every six atoms
is missing
vacancies order at low
temp

The structure of TiO1.25


 Based on NaCl with all anions present, but has
ordered Ti vacancies
Order disorder

 Many materials show temperature dependent


ordering phenomena
 Spinels frequently show temperature dependent
ordering
Mgtet[Al2]octO4 (normal) and Mgtet[MgTi]octO4
(inverted) but other compositions may be partially
inverted and the degree of inversion may depend on
synthesis temperature

Substitutional solid solutions


 In many compounds it is possible to replace a metal
atom or ion with another element that has similar size
and bonding requirements
In metal alloy can replace metal atom with another element
that is within 15% size
Can get complete solid solution formation between Al2O3
and Cr2O3 Al2-xCrxO3
Exstensive solid solution formation is favored by high
temperatures due to the disorder associated with the solid
solution
Criteria for solid solution formation
 Typically, for an ionic solid the ion size difference
should be less than 15-20% to get complete solid
solution formation
> 30% size difference usually precludes solid solution
formation
 End member of solid solution should hve same
structure if complete solid solutions is to form
Zn2SiO4 and Mg2SiO4 have different metal coordination
So Zn2-xMgxSiO4 and Mg2-xZnxSiO4 have different structures

Interstitial solid solutions


 Some solid solutions involve inserting
atoms into interstitial sites in a parent
structure
PdHx 0 < x < 0.7 - hydrogen occupies
interstitial sites in fcc Pd
Carbon in interstitial sites of fcc Fe
Aliovalent substitution
 If you replace an ion by one with a different
oxidation state (aliovalent substitution) there has
to be a charge compensation mechanism
 Cation vacancies
Dope calcium into NaCl Na1-2xCaxVxCl
Replacement of Mg2+ by Al3+ in spinel
[Mg1-3xVxAl2x]tet[Al2]octO4
Oxidation of NiO
Ni2+1-3xVxNi3+2xO

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

 The oxides of metals such as W, Mo and Ti


display a wide range of compositions
WO3-x, MO3-x, TiO2-x

 Magneli realized that these compounds were best


represented as homologous series of phases rather
than solid solutions
TinO2n-1, MonO3n-1 etc
Crystallographic shear structures
 The homologous series can be formed by
incorporating crystallographic shear planes into the
structures
these are extended defects
 The shear planes change the stoichiometry of the
material
at the CS plane may have face sharing rather than edge
sharing or edge sharing rather than corner sharing
 Can get shear planes in 2 or 3-D leading to
slab structures and block structures

Molybdenum and tungsten oxides

 A wide variety of tungsten and molybdenum


oxides are known
 Many of them belong to homologous series
MnO3n-1 or MnO3n-2
for example, Mo4O11, Mo5O14 and Mo6O17
Defects in molybdenum and
tungsten oxides
 Why are there so many different oxides?
 The parent oxide WO3 has a ReO3 structure at high
temperature
 All of these different stoichiometry oxides can be
derived from WO3 by incorporating an ordered array
of planar defects
crystallographic shear planes

The ReO3 structure


The incorporation of a shear plane

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

 NaxWO3 - often ReO3 based


 KxWO3 - 0.19 < x < 0.33 from reaction of K with
WO3 is hexagonal
potassium is bigger than sodium and needs a larger site
 KxWO3 - x < 0.19 regular intergrowth structure
 Tetragonal bronzes are known for Na and K

Tungsten bronze structure types

Tetragonal tungsten bronze

Hexagonal tungsten bronze


Intergrowths
 It is possible to combine slabs of simple
structures together to build up a solid
 If the slabs grow together in an order array
you have an ordered intergrowth
new structure type if order is long range
 If slabs are randomly stacked together you
have a random intergrowth

Intergrowth tungsten bronzes

Double rows hexagonal


structure intergrown
with ReO3 structure

Single rows hexagonal


structure intergrown
with ReO3 structure

 Hexagonal KxWO3 stable for 0.19 < x 0.33, lower


values of x can be accommodated by intergrowing
with ReO3 type WO3
Intergrowth bronze BaxWO3
 Single rows of hexagons can be seen. Some
of sites are not filled by Ba2+

Stacking faults

 Many structures can be thought of as


consisting of an ordered stack of layers
 Sometimes this ordering of the layers
breaks down
ABCABCABC..... normal
ABCBCABCABC...... with stacking fault
Antiphase domain boundaries
 Atan antiphase boundary the ordering pattern within a
crystal structure abruptly changes
This could be a change in metal atom or cation ordering, for
example in CuAu where there is ordering of Cu and Au

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