Defects, non-stoichiometry, solid solutions and ionic conductivity in the solid state

Not based on Atkins and Shriver, although the solid state section does cover some of this material

Defects in crystals
It is not possible to make crystals that are perfect 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 VO x MnxO NixO LixV 2 O 5 TiO TiO 2 VO MnO NiO 0.65 < x < 1.25 1.998 < x < 2.000 0.79 < x < 1.29 0.848 < x< 1.000 0.999 < x < 1.000 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

Hf for defects

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 300 1000 HS = 5 x 10-19 J HS = 1 x 10-19 J 6.12 x 10-27 1.37 x 10-8 5.72 x 10-6 2.67 x 10-2

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 ClV 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:Eu phosphors

2+

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 - cation vacancies Ca2+ or Cd2+ in NaCl

Real crystals contain both intrinsic and extrinsic defects

the dominant defect type depends upon temperature and doping/nonstoichiometry level

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

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 Extensive 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 have 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

Ionic conductors
Ionic solids contain defects that allow the migration of ions in an electric field Some solid materials have very high ionic conductivities at reasonable temperatures
useful in solid state devices

mobile vacancy

mobile interstitial

Applications of solid ionic conductors

Membranes in separation processes Electrolytes in sensors Electrolytes in fuel cells and batteries
should be a poor electronic conductor

Electrode materials in solid state batteries

should be a good electronic and ionic conductor

Factors effecting the conductivity

=nZe Conductivity is influenced by 1)the carrier concentration n, 2) the carrier mobility Usually, defects act as the charge carriers
not many defects in most ionic solids mobility is usually low at room temperature Material Ionic conductors Ionic crystals Solid Electrolytes Liquid electrolytes Electronic conductors Metals Semiconductors Insulators Conductivity (S m-1) < 10-16 10-2 10-1-103 10-1-103 103-107 10-3-104 < 10-10

Ionic conductivity in NaCl

NaCl is a poor ionic conductor Conduction involves migration of cation vacancies Cation vacancies are present due to
doping - extrinsic defects Schottky defects - intrinsic defects

Conduction is an activated process

= 0 exp (-Ea/kT) - Arrhenius equation

Temperature dependence of conductivity

= (0/T) exp(-Ea/kT)
Contribution from mobility and defect formation

Idealized conductivity for NaCl

At low T, conductivity is dominated by mobility of extrinsic defects At High T, conductivity is due to thermally formed (intrinsic) defects

Intrinsic versus extrinsic conductivity

Extrinsic conductivity
= (0/T) exp(-Ea/kT) carrier concentration is fixed by doping

Intrinsic conductivity
carrier concentration varies with temperature = (0/T) exp(-Ea/kT) exp(-HS/2kT) slope of plot gives Ea + HS/2

Experimental conductivity of NaCl

Broadly as expected
Get deviation at low T due to vacancy pairing Get deviation at high T due to screening of mobile defects by defects of opposite charge
Debye-Huckle type model

Energetics of ionic conduction in NaCl

Process Migrationof Na+, Em Migration of ClFormation of Schottky pair Dissociation of vacancy pair Dissociation of vacancy Mn2+ pair Activation energy (eV) 0.65-0.85 0.90-1.10 2.18-2.38 ~1.3 0.27-0.50

AgCl
The predominant defect in AgCl is cation Frenkel Cation interstitials are more mobile than cation vacancies Cation interstitials can migrate by one of two mechanisms
direct movement indirect movement

Migration mechanism in AgCl

Two possible pathways for interstitial migration: 1) move directly from interstitial to interstitial 2) interstitial displaces regular cation onto interstitial position Migration actually occurs by second pathway

Evidence for the indirect mechanism

Both charge and mass transport through a crystal can be measured
conductivity gives charge mobility diffusion measurements using radiolabelled Ag+ gives mobility of Ag+

Charge is transported twice as fast as Ag+ ions suggesting the indirect mechanism is correct

Solid electrolytes
There is a technological need for solids that have very high ionic conductivities Such materials are referred to as FAST ION CONDUCTORS They include:
AgI Na alumina NASICON, Na1+xZr2[(PO4)3-x(SiO4)x] Stabilized zirconias

Ionic conductivity of some good solid electrolytes

 - alumina
Na1+xAl11O17+x/2 () and Na1+xMgxAl11-xO17 () are good sodium ion conductors at moderate temperatures Na ions have high mobility and can be ion exchanged with a wide variety of other cations M2O.x Al2O3 x = 5 - 11
M = Alkali+, Cu+, Ag+, Ga+, In+, Tl+, NH4+ x = 5-7 usually produces material x = 8 - 11 gives material material usually stabilized by addition of Li+ or Mg2+

The structures of and alumina

The sodium sulfur cell

Sodium sulfur cells have a high energy density
useful for electric vehicles

There are safety concerns

molten sodium

2Na(l) 2Na+ + 2e2Na+ + 5S(l) + 2eNa2S5(l)

Silver iodide
At low temperatures AgI adopts either a Wurtzite or zinc blende structure
Ag+ fills half of the tetrahedral holes in a close packed Iarray

Above 146o C it transforms to a BCC structure with the Ag+ filling a small fraction of the available tetrahedral sites
the cation sublattice melts ~ 130 Sm-1

The structure of - AgI

Cation sites in - AgI

Ionic conduction in - AgI

There are many possible sites for Ag+
12 tetrahedral 24 trigonal 6 octahedral

There are only 2 Ag+ ions per unit cell!

these ions are found disordered on the tetrahedral sites

Motion between sites is facile

~0.05 eV activation barrier

RbAg4I5
AgI is polymorphic. The high temperature phase has a high ionic conductivity associated with a melted Ag+ sublattice
At low T ionic conductivity drops RbAg4I5 discovered while trying to find materials that still had AgI structure at low T

RbAg4I5
Highest room temperature ionic conductivity of any crystalline solid, 0.25 S cm-1
Not stable < ~25 C

Stabilized zirconias
Y2O3 and CaO can be dissolved in ZrO2
creates a lot of oxygen vacancies

At high temperatures the defects are mobile

oxide ion conductor

Applications of stabilized zirconia

Oxide conductors are of use for
oxygen sensors
based on concentration cell, can be used to measure O2 in exhaust gases, molten metals

fuel cell membranes

ZrO2 is only usable at high temperatures

An oxygen sensor
An O2 concentration cell can be built E = [2.303RT/4F] log(p/pref)

Fuel cells
Fuel cells are devices for the direct conversion of fuels such as CH3OH, H2, CO to electrical energy

Solid oxide fuel cells

Fuel cells offer an efficient and clean way of using fossil fuels, but
high cost thermal cycling problems

Electrochromic devices
Color changes such as those needed in smart windows can be achieved by moving ions into a suitable solid

Lithium batteries
Batteries based on lithium are attractive as they can be light a have a very high voltage output
Considerable current research on cathodes and electrolytes for these devices