Diffusion

• Diffusion occurs from a concentration gradient

• The difference between diffusion in metals and
in ceramics is that the diffusing species in
ceramics is often charged (vacancies,
interstitials)
• The movement of a charged ion results in a
current
• Thus diffusion and ionic conductivity are
linked
1

Defects in ceramic structures

• Frenkel Defect
--a cation is out of place.
• Shottky Defect
--a paired set of cation and anion vacancies.
Shottky
Defect:

Frenkel
Defect

• Equilibrium concentration of defects ~ e !QD / kT

2

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

• Substitutional anion impurity anion vacancy

O2-

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+

VO•• A vacancy on the O site

It has a double positive charge since O is 2-
An Al interstitial
Ali•••
It has a triple positive charge since it is 3+

•
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

Defection associations and

concentrations

Concentrations given in brackets:

•
[AlMg ] [e '] = n = concentration of electrons
'' ! = p = concentration of holes
[h]
[VMg ]

4
Defect reactions
Reactions occur for defects, just like other chemical
species in the lattice

Consider Shottky defects in MX (M=cation, X=anion)

There is a random distribution of cation and anion vacancies

VM' +VX• ! null

KS = equilibrium constant = [VM' ][VX• ]

From the definition of the equilibrium constant:
1
# !"gs & # !"hs + T "ss & # "s & # !"hs & # !"hs &
K s = exp % ( = exp % ( = exp % s ( exp % ( ) exp % (
$ kT ' $ kT ' $ k ' $ kT ' $ kT '
9

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

MM ! VM' + M i• K F = [VM' ][M i• ]

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

Oxidization and reduction

1/
M O M O M O 2O 2 (g)
2e
O M O M O M
M O M O M O
2h Oxidation - generate holes
O M O M O M Reduction - generate electrons

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

3. BaTiO3 heated and quenched in H2

BaTiO3-x good semiconductor
Ti4+→Ti3+ + h•
4. ZnO sintering rate increases as pO2 decreases
formation of Zni
14

7
Impurity induced, ion compensated

There is no such thing as a 'pure' material

Can get 99.9999% pure (4 9's, Alfa Aesar, e.g.)

Concentration of impurities is 100 ppm or 10-4

Consider adding CdCl2 to NaCl
Assume Cd sits on Na site (not interstitial, too large)

Cd is 2+, for charge balance must form Na vacancies or

Cl interstitials (unlikely)
CdCl2 !!!
2NaCl
" Cd Na
•
+VNa
'
+ 2ClCl Na1-2xCdxCl
ZrO2
CaO !!!
" Ca +V + OO''
Zr
••
O
Zr1-xCaxO2(1-x)
15

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

N = number of normal sites

N* = number of interstitial sites

" !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

Diffusion in lightly doped NaCl

Consider adding CdCl2 to NaCl
CdCl2 !!!
2NaCl
" Cd Na
•
+VNa
'
+ 2ClCl

The Na diffusion coefficient is

% #$GV * (
DNa = [V ]!" exp '
' 2 Na
*
Na
'& kT *)

ΔGVNa* is the energy for migration of free vacancies

At low temperatures, extrinsic behavior observed

$ #S * ' $ *#HNa * '
DNa = [CdCl2 ]!" 2 exp & Na ) exp & )
% k ( % kT (
18

9
 At high temperatures, there are additional vacancies from
Schottky defects that swamp the effect of the impurity

% #$GNa * ( % #$sS ( % #$SNa * ( % #$HS ( % #$HNa * (

DNa = [VNa
'
]!" 2 exp ' * = !" 2
exp ' 2k * exp ' * exp ' 2kT * exp ' *
& kT ) & ) & k ) & ) & kT )

-1/
k(ΔHNa
* + 1/2Δhs)
ln D (cm2/sec)

-1/
k(ΔHNa
*)

high T
intrinsic
low T
extrinsic

1/T 19

Diffusion in cation-deficient oxides

The transition metal oxides are typically cation deficient

Ni1-xO, Co1-xO, Mn1-xO, Fe1-xO

x↑
3 x 10-4 10-2 at 1300˚C
Can get up to x = 0.15, then
form F2O3
Consider Co1-xO

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 +

Ca1-xZrxO2(1-x) fast ion

conductor

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)

Oxygen sensor ZrO2-Y2O3 (1000˚C) fast ion

Li2 O-LiCl-B2O3 conductor semiconducting
(glass, 300˚C)
Primary battery KxPb1-xF1.75 TiO2-x (oxygen sensor)
10-6
solid
fluorine ion LaF3, EuF2
electrolyte
specific electrode
NaCl
TiO2
10-12 ZnO (varistor)
insulator insulating

passivation on Al2O3 (substrate)

Si devices SiO2
10-18 23

Mobility

velocity
Mobility =
driving force chemical, electric field, mechanical

In a chemical gradient, the absolute mobility given by

velocity (cm / sec) v i vi µ! i (ergs/mole)

Bi = = =
force (ergs / cm) Fi ) 1 # "µ! &,
!+ %
i
( . note: this is the chemical potential, not
N
+* A $ "x ' .- the electrical mobility

The chemical mobility = Bi' = Bi/NA

24

12
Mobility and diffusivity

1 # "µ! i &
Ji = civi = ciBiFi Ji = ! % ( Bc
NA $ "x ' i i

For an ideal solution,

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

Di = kTBi Nernst-Einstein relation

25

Instead of using a chemical potential (hard to measure), put

these expressions in terms of an electric field

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

relating electronic mobility with chemical mobility

26

13
Ionic conductivity

zi eDi
! i = zi e µi c i µi =
kT

zi2e 2Di c i Usually written in (Ω-cm)-1 or S-m-1

!i = where S = Ω-1
kT
e = 1.6 x 10-19 C
D in cm2/sec
c in #/cm3
k in ergs (107ergs = J)
Conductivity depends on At room temperature
carrier concentration
mobility of carrier not many defects
temperature mobility low
27

Diffusion and electrical conductivity

measurements
• Diffusion of a radioactive tracer element Na
was measured
• The electrical conductivity was measured

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

The force on the particle, Fi, is the negative gradient of ηi

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 '

Even a modest electrical field can offset the effect

of the concentration gradient in the opposite
direction

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

The flux of oxygen vacancies must be matched by an

equivalent charge flux of electrons outward, holes inward

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?

Rewrite Fick's first law in terms of ηi acting on the 2 defects

separately, equating the fluxes to solve for the internal field.
2cV DV $ "µ!V "# '
2JV •• = ! O O
&
O
+ 2F ) flux is raised by internal field
O RT &% "x "x )(
$ "µ! e
( µ! = µ! + RT ln c )
"# '
o
nD
Je ' =! e & "x ! F "x ) flux is lowered by internal field
RT % (

Then, rewriting the 2 expressions to get ∂φ/∂x

" !n !cV %
!cV
!" RT ( ) !x $ the concentration gradients, =2 O'
D e
# DV O
$ !x !x '
=
O
$# n = 2cV '&
!x F De + 2DV O
O

$ 3De DV ' !cV 3De DV

JV •• = #& O
)
&% De + 2DV )( !x
O
D! = O

O
O
De + 2DV
O

33

~
If De >> DVO, the D = 3DVO

Ambipolar diffusion rate is controlled by the slower species

Ambipolar coupling causes rate to be enhanced by 3X
~
If DVO>>De, then D = 1.5 D

Slower species is rate controlling

Ambipolar coupling increases effective diffusion coefficient

The ambipolar diffusion coefficient is greater than that

of the slower defect, due to charge-coupling to the
faster one

34

17