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Frenkel
Defect
1
Schottky and Frenkel defects
Schottky defects in NaCl
Both cation and anion are
missing from their regular
lattice sites
At room temperature, 1 in
1015 sites are vacant
200 kJ/mole (2.7 eV) creation
energy
Cation Frenkel defects in
AgCl
Cation displaced from
regular lattice site onto
interstitial site
150 kJ/mole (1.6 eV)
creation energy 3
Impurities
• Impurities must also satisfy charge balance = Electroneutrality
• Ex: NaCl Na + Cl -
cation
• Substitutional cation impurity vacancy
Ca 2+
Na +
Na +
Ca 2+
initial geometry Ca 2+ impurity resulting geometry
Cl - Cl -
initial geometry 2-
O impurity resulting geometry
4
2
Crystalline 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
– Ca2+, Y3+ in ZrO2 have anion vacancies
– Ca2+ or Cd2+ in NaCl creates cation vacancies
• Real crystals contain both intrinsic and extrinsic
defects
• The dominate defect type depends on temperature
and doping level
– Typically
• High temperatures
– intrinsic
• Low temperatures
– extrinsic defects
5
Kröger-Vink notation
• Standard notation for defects in ionic crystals
• Composed of 3 parts
• Main body identifies the defect
– V = vacancy
– M = metal
– X = non-metal
• Subscript denotes site the defect occupies
– i = interstitial
– x = non-metal
– M= cation site
• Superscript identifies the effective charge
– • = positive charge
– ' = negative charge
3
Examples
Consider MgO
''
VMg A vacancy on the Mg site
It has a double negative charge since Mg is 2+
•
AlMg An Al on a Mg site
It has a positive charge since Al is 3+ and Mg is 2+
'
LiMg An L on a Mg site
It has a negative charge since Li is 1+ and Mg is 2+
7
4
Defect reactions
Reactions occur for defects, just like other chemical
species in the lattice
Defect reactions
# !"gs &
KS = equilibrium constant = [VM' ][VX• ] = exp % (
$ kT '
When these are the only defects present, then
# !"gs &
[VM' ] = [VX• ] = exp % (
$ 2kT '
Frenkel defects
Electronic defects
! = np
K e = [e '][h]
e '+ h! ! null
10
5
Rules for defect reactions
• These rules must be satisfied:
– Mass conservation
• Not creating or destroying matter!
– Electroneutrality
• The + and - charges must be balanced on each side of
reaction equation
– Site ratio conservation
• Different crystal structures are not created
ai Ai ! bi Bi
" [B ]bi % #$G (
k= i i
= exp '
" [Ai ]ai & kT *)
i 11
M (g) e CB
VO•
VO••
VM''
VM'
12
e VB
6
Oxidation and reduction
1
O2 (g) +VO•• ! OO + 2h!
2
p2 # !"gO &
KO = •• 1/2 = KOo exp % (
[VO ]pO2 $ kT '
1
OO ! VO•• + 2e '+ O2 (g)
2
# !"gR &
K R = [VO•• ]n 2 pO2
1/2
= K Ro exp % (
$ kT '
13
Examples
1. Sodium tungstate bronze
'
NaxWO3 x: 0.32-0.93 perovskite with VNa
n-type for x < 0.25
Metallic conductivity for x > 0.25
2. Ce3S4
Ce2.67S4 ρ ~ 10-3 Ω-cm
Ce3S4 ρ ~ 109 Ω-cm
7
Impurity induced, ion compensated
Frenkel defects
M X M X M AgBr, CaF2
X M X M X
M
M X M X M
X M X M X
" !Q %
nF = (NN * )1/2 exp $ F ' = number of Frenkel painr
# 2kT &
16
8
Assumptions
• Only have one type of predominate defect
– Schottky or Frenkel
• Assume a dilute solution
– Neglect interactions between defects
• Constant volume
• Energy for defect formation independent
of T
17
9
At high temperatures, there are additional vacancies from
Schottky defects that swamp the effect of the impurity
-1/
k(ΔHNa
* + 1/2Δhs)
ln D (cm2/sec)
-1/
k(ΔHNa
*)
high T
intrinsic
low T
extrinsic
1/T 19
1
O (g) = OO +VCo K1 = [VCo ]aO!1/2
2 2 2
'
[V ]p x = [VCo ] + [VCo
'
] + [VCo
''
]
VCo = VCo
'
+ h! K2 = Co
[VCo ]
''
[VCo ]p electrical conductivity is p-
'
VCo = VCo
''
+ h! K3 = '
type
[V ]
Co
20
10
Diffusion in highly doped oxide - cubic
stabilized ZrO2
'' ZrO Usually 8-15% added
CaO !!!
2
" CaZr +VO•• + OO
Brouwer approximation:
''
[CaZr ] = [VO•• ]
defect
clustering
Large concentration
of oxygen vacancies
compared with most
single cubic oxides
phase
ΔG* = 1 eV (small)
tetragonal
cubic +
21
Electrical conductivity
• Conductivity values range over 25 orders of magnitude
– Most insulating LiF (band gap > 12 eV)
– Superconductors (no band gap)
• Electrical conductivity arises from
– Movement of charged ions
• Ionic conductivity
– Sensors, electrochemical pumps, solid electrolytes in fuel cells, high T battery systems
– Movement of electrons
• Measured electrical conductivity
– From both ions and electrons
– σtotal = σelec + σion
– ti = transference number = σi/σtotal
• If telec > tion electronic conductor
• If tion > telec ionic conductor
• Oxides that are easily reduced are n-type semiconductors
– e.g. TiO2, SnO2, ZnO, BaTiO3
• Oxides that are easily oxidized are p-type semiconductors
– e.g. transition metal monoxides (NiO, FeO, CoO)
22
11
(Ω-cm)-1
IONIC CONDUCTORS ELECTRON CONDUCTORS
!
YBa2Cu3O7-x
106 RuO2 (thick films)
TiO
metallic
LaNiO3 (fuel cell electrode)
SnO2•In2 O 3 (transparent elect.)
SrTiO3 (photoelectrode)
100
Na/S battery Na β-Al2 O 3 V2O 3 •P2O3 (glass)
Mobility
velocity
Mobility =
driving force chemical, electric field, mechanical
24
12
Mobility and diffusivity
1 # "µ! i &
Ji = civi = ciBiFi Ji = ! % ( Bc
NA $ "x ' i i
µ! i = µo + RT ln ai = µo + RT ln ! i c i " µo + RT ln c i
d µ! i # 1 & dc
= RT % ( i
dx $ c i ' dx
1 # RT dc i & RT dc i dc
Ji = ) Bc = ) B = )Di i
NA %$ c i dx (' i i NA i dx dx
d!
Fi (electrical) = zi e = zi eE
dx
"D % z ec D E
Ji = c i Bi Fi = c i $ i ' (zi eE) = i i i
# kT & kT
zi ec i Di E
Ji = c i v i =
kT
zi eDi
vi = E
kT
v z eD z FB
µi = i = i i = zi eBi = i i = zi FBi' F = Faraday's constant =96,500
E kT NA C/mole = eNA
13
Ionic conductivity
zi eDi
! i = zi e µi c i µi =
kT
D Difference is ~ 2 x 1011
tracer cm2/sec
conductivity
1/T 28
14
The electrochemical potential
• Gradients in chemical potential (concentration)
and electric field mobilize defects
• Even in the absence of an external field,
internal electric fields are present
– Non uniform distribution of space charge
• Driving force for mass transport is the
electrochemical potential (η) instead of just the
chemical potential
F = Faraday's constant = eNA
!i = µi + zi "F = 96,500 C/mole
29
1 # d "i &
Fi = !
NA %$ dx ('
!c i Bi # d"i & !c i Bi # d µ! i d) &
Ji = % ( = % + zi F (
NA $ dx ' NA $ dx dx '
30
15
Ambipolar diffusion
• Coupled transport of different charged species
• Ionic crystals must maintain charge neutrality
– Long range charge separation must be avoided
– Charge species are coupled
• Effect of slowing down faster diffusing species and
speeding up slower diffusing species
• Both diffuse with a common diffusivity
– Chemical or ambipolar diffusion coefficient D!
31
'' ''
VMg +VO•• ! null KS = [VMg ][VO•• ]
Consider MgO
e '+ h• ! null K i = np
1
OO ! VO•• + 2e '+ O2 (g) KO = VO•• n 2 pO1/2
2 2
µe > µh
2JVO = Je
Using the ambipolar diffusion coefficient:
" dc % " dn %
JV •• = !D! $ and Je ' = !D! $ '
VO
'
O $# dx '& # dx &
32
16
~
How does D depend on DVO and De?
O
O
De + 2DV
O
33
~
If De >> DVO, the D = 3DVO
34
17