1

PAUL SCHERRER INSTITUT PAUL SCHERRER INSTITUT

Electronic and ionic conductivity in
metal oxides
Kazimierz Conder
Laboratory for Developments and
Methods, Paul Scherrer Institute,
5232 Villigen PSI, Switzerland
kazimierz.conder@psi.ch
2
1 10 100 1000
10
-11
10
-9
10
-7
10
-5
10
-3
10
-1
10
1
10
3
10
5
10
7
La
0.75
Ca
0.25
MnO
3
Na
2
O*11Al
2
O
3
YBa
2
Cu
3
O
7
Superconductors >10
23
Cu
Pb
Graphite
Ge
Si
Glass
I
n
s
u
l
a
t
o
r
s
S
e
m
i
c
o
n
d
u
c
t
o
r
s
M
e
t
a
l
s
C
o
n
d
u
c
t
i
v
i
t
y

[

-
1
c
m
-
1
]
Temperature [K]
Electrical conductivity
Conductivity of metals decreases
with temperature. Increased
interaction of electrons with
lattice!
Superconductivity: by cooling
resistivity drops to zero
Conductivity of insulators and
semiconductors increases with
temperature. Concentration of
carriers increases!
3
Electrical resistivity of ceramic (oxide) materials
over 20 orders of magnitude
10
-13
10
-8
10
-3
10
2
10
7
Conductivity,
-1
m
-1

Insulators
Semiconductors
Conductors Superconductors
4
18
18!
18
18!
18
18!
18
18!
18
18!
18
18!
Molecular: Ar
1"
18!
1#
18!
1"
18!
1#
18!
1"
18!
1#
18!
1"
18!
1#
18!
1"
1" 1"
1"
1"
1" 1"
1"
$ $ $
$ $ $
Ionic: KCl
Covalent: C (diamond)
Metallic: K
%lectronic charge distribution in the basic solid types
&chemical bond point of view'
(fter ).*. (shcroft+ ).,. -ermin+ .Solid State /hysics0+ /hiladephia+ 1"#1
2
Cl
,elocalized
electrons
5
Metals, semiconductors, insulators
134
5
o
g

-etal
Semiconductor:
intrinsic
e6trinsic
Insulator
4
Semiconductors: electrons are
e6cited over the band gap and
occupy energy levels in
conductivity band. 7oles are
created in valence band. 4he
process is thermally activated!
conductivity increase with
temperature.
( material with an energy gap 89.: e; is an insulator.
Conductivity can be increased by a doping. 4hrough the doping
energy levels within band gap will be created.
6
Energy of
an electron: E = = (k)
2
/2m
k=2/ wave vector
E
k
E ~ k
2
%lectrons with 88a &lattice parameter'
can travel freely through a crystal
For more energetic electrons when a
wavelength
of the electron
Electron in a (1D) solid
7
E
k
E ~ k
2
a
<
9
= sin
9
&>63a' higher energy
,istribution of the electron
densities:
<
9
=cos
9
&>63a' lower energy
?@9a
Electrons which have a
wavelength commensurate
with the lattice are
scattered on the !eriodic
!otential
E
!>3a >3a
Aorbidden band
Electron in a (1D) solid
/otential energy of an electron
in a periodic array of positive ions
*ave functions for ?@9a
8
Band &Bloch!*ilson'
insulators
S
Partially filled energy band metal
Filled energy band insulator
splitted d orbitals
(trigonal prism
coordination)
d
xz,
d
yz
d
xy,
d
x
2
-y
2
d
z
2
insulator
metal
Nb
4+
4d
1
Mo
4+
4d
2
9
)o carriers C no conductivity
-gD
-g
9
9p
1
Es
F
D
9!
9p
1
insulator
)a
9
D
)a

9p
1
Es
F
D
9!
9p
1
)oble gas configuration:
insulator
4iD
9
D
9!
9p
1
4i
$
Ed
F
$s
F
insulator
Aree d!electrons:
metal
4iD
4i
9
Ed
9
$s
F
D
9!
9p
1
)iD
)i
9
Ed
8
$s
F
D
9!
9p
1
Insulator
But whyGGG
Aree carriersG
10
TiO- rutile
Ti
O
4i Ed
9
$s
F
metal
NiO- NaCl structure )i Ed
8
$s
F
Is insulator!
Why not a metal?
Ni
O
11
CuD Cu
9
Ed
"
$s
F
CoD Co
9
Ed
#
$s
F
-nD -n
9
Ed
:
$s
F
Cr
9
D
E
Cr
E
Ed
E
$s
F
Ddd number of d electrons!
all this o6ides should be
metals but are insulators
*hatever is the crystal
field splitting the orbitals
are not fully occupied!!!
Why not metal?
Ed
#
$s
9 Ed
:
$s
9
Ed
"
$s
9
Ed
$
$s
9
%lectron configurations
of elements
12
H4he d!levels in most of the transition metal
o6ides are partially filled+ therefore+ the band
theory predicts electron delocalization and
metallic properties.
H(ccording to band structure calculations half
of the Inown binary compounds should be
conducting.
HIn reality+ many o6ides show insulating
behavior+ implying that the d!electrons are
localized.
HShort!range Coulomb repulsion of electrons
can prevent formation of band states+
stabilizing localized electron states.
Mott-Hubbard insulators
The Nobel Prize in Physics
1977: Philip Warren
Anderson, Sir Nevill
Francis Mott and John
Hasbrouck van Vleck
"for their fundamental
theoretical investigations
of the electronic structure
of magnetic and
disordered systems".
13
-ott considered the idealized metal!insulator transition for )a
crystal by changing the
interatomic spacing.
After: Feng Duan, Jin Guojun,
Introduction to Condensed Matter
Physics, Vol.1, World Scientific 2005
7ubbard J ! energy penalty for transferring an
electron between two adKacent sites !assumed to
be independent on a
)a )a )a
"
)a
#
$
Bandwidth or band dispersion:
energy difference between the highest
and lowest level. Bandwidth increases
with better orbital overlap. Localization
of electrons narrow bands.
%lectron hopping
between atoms
during conduction
13a
a

c
o
n
d
u
c
t
i
v
i
t
y
%
$
)a )a )a )a
)a
"
)a
#
14
U ~I -A
ionization energy
(a few eV)
electron
affinity
Coulomb repulsion is described in
terms of a correlation energy,
%u&&ard#$, which is the energy
penalty for transferring an electron
between two adKacent sites.
Ni
2+
+ Ni
2+
Ni
3+
+ Ni
+
d
8
+ d
8
d
7
+ d
9
Mott-Hubbard insulators
$
15
At the !oint where ' (
$, the &ands overla!)
*eyond this !oint, there
is no energy ga! and the
material is metallic)
I+ $ , ', the d &and o+ the
transition metal is s!litted into
su&#&ands) For an electron
trans+er an energy &arrier $
must &e overcome and the
material is insulating)
Mott#%u&&ard (M%) insulator)
U
E
U=1/2(B
1
+B
2
)
Bandwidth W
E
f
Upper Hubbard band
Lower Hubbard band
4he effect of the electron repulsion maIes even the half!filled band
insulating when the interaction between atoms &band width *' is small.
16
Pressure and temperature dependence
H%very material under high
pressure will have metallic
properties
HInsulator!-etal transition can
be achieved increasing
temperature &thermally
induced carriers' or doping
13a

metal
insulator
13a
c
17
/hase diagram of ;
9
D
E
,.B. -c*han et al.+ /L5+ 9E &1"1"' 1E8$
H-i6ed o6ides &chemical pressure'
-i
."
/)0123 4
."
/)50 23 Cr
."
/)566 2
H/ressure e6periments for ;
9
D
E
and &;
F."1
Cr
F.F$
'
9
D
E
18
;
9
D
E
metal!insulator transition
,.B. -c*han et al.+ /L5+ 9E &1"1"' 1E8$
J. Feinleib and W. Paul, Phys. Rev. 155(1967) 841
=1$:2
c
o
n
d
u
c
t
i
v
i
t
y

&
o
h
m

c
m
'
!
1
134+ 1F
E
32
19
5arger d orbitals
Hlow o6idation state &more electrons' for early 4- &good -!- overlap'
Hhigh o6idation state for late 4- &good -!D!- overlap: covalent
bond'
Hfor covalent bonds: low electronegativity anions
halides+ D+ S+ Se+ 4e+ phosphides.....
*
* J
J
Helectron configuration e.g. -n
9
Ed
:
has half!filled shell
Hother cations in the structure &as e.g. in perovsIites (BD
E
'
Meneral rules
)iS+ CoS and CuS!metals
)iD+ CoD and CuD! (M%) insulators
4ransition metals 4-
20
Mott-Hubbard models
assumes that the band
gap is within d-band.
In many cases one has
to consider ligands- e.g.
oxide anions in oxides.
Additionally to W and U a
third parameter has to be
considered: gap.
Oxygen p bands
Metal d bands
is a gap between
2p oxygen band
and the d-band of
the metal.
21
LaCuO
3
is a metal
Cu 3d-band and O 2p-band
overlap.
o6ygen p
band
metal d
bands
E
gap

U is large
(Semi)Metal
Charge-transfer-
insulator
(semiconductor)
Mott-Hubbard-
insulator
E
gap

Different /U ratio!
Conductivity
via holes in
O 2p-band
22
D6ygen p band
-etal bands
U<
Mott-Hubbard
insulator
)iD+ )i/S
E
+
4i
9
D
E
+ ;
9
D
E
+
Cr
9
D
E
<U
Charge transfer
insulator
CuCl
9
+ CuD
<W
Semimetal
5aCuD
E
+ CuS+
CuSe
U<W
Metal
7igh temp.
mod. of 4iD+
CrD
9
Examples
23
D6ygen p
band
metal d
bands
24
CoO
Fe
2
O
3
NiO
Cr
2
O
3
Mn
3
O
4
FeO
VO
2
MoO
2
Ti
2
O
3
ReO
3
TiO
CrO
2
V
2
O
3 VO
Fe
3
O
4
NbO
ReO
2
MnO
2
10
-14
10
-10
10
-6
10
-2
10
2
10
6
C
o
n
d
u
c
t
i
v
i
t
y
,

-
1
m
-
1
1000
800 333 250
200
167
149
125
T, K
1000/T, K
-1
1 2 3
4 5 6 7
8
Cu 5.9 10
7
at RT
metallic
After: Schaumberg, Keramik
25
after I. 7. Inoue+ Semicond. Sci. 4echnol.+ 9F &9FF:' S119
/erovsIites
26
d
1
perovsIites
Sr;D
E
metal
Ca;D
E
metal
5a4iD
E
insulator
gap F.9e;
N4iD
E
insulator
gap 1.F e;
27 27
D6ygen nonstoichiometric Ed o6ides
Does the electrical
conductivity
depend on oxygen
content and cation
doping?
28 28
7attice de+ects
Schott8y# und Fren8el#de+ects in crystals
SchottIy!defeIts:
4he volume of the crystal will increase
ArenIel!defeIts:
4he volume of the crystal stays
constant
4emperature
535
,ilatometer
SchottIy!
defects
29 29
9e+ect concentration n:;
/
4emperature
O
o
CP
(ctivation %nergy e;
1 9 8
1FF EQ1F
!1$
1Q1F
!9#
1Q1F
!1F8
:FF EQ1F
!#
1Q1F
!1E
8Q1F
!:E
1FFF 1Q1F
!$
1Q1F
!8
9Q1F
!E9
1:FF 1Q1F
!E
9Q1F
!1
9Q1F
!9E
9FFF 1Q1F
!E
$Q1F
!:
9Q1F
!18

kT
E
N
n
V
exp
0
30 30
Fe
1#<
= (Fe=
1"<
) semiconductor ty!e !
F( )
%
n
e
r
g
y
E
+
4*
C*
(cceptor level
>Fe
<
Fe
" =
?
Fe=
>Fe

Fe
" ?=
<
=
" ?4
,,
Fe
Fe=
Fe

Fe
Fe
<
Fe
" h

Ae

Ae
ion can trap an electron from the valence band.
In ;B a hole is created.
h

31 31
-i=
?#<
semiconductor ty!e n
F( )
%
n
e
r
g
y
E
+
4*
C*
,onor level
?-i
<
-i
" =
<
=
-i=
?
?-i
@
-i
" 4

=
" /)6 =
?
-i
@
-i
-i=
?
-i
<
-i
" e
@
Ti
4+
,onor level is situated
close to the conductive
band.
4he donor cation 4i
@
4i
&4i
E
'
can inKect an electron into
conducting band.
32 32
9e+ect semiconductor) ;i
1#
=
In )iD nicIel vacancies are created when o6idized with o6ygen. 4he
charge of the additional o6ygen sites is compensated by o6idation
of some nicIel sites to )i
E
. 4hrough the o6idation the volume of
the material increases.
p

+ + +
O Ni Ni
NiO
Ni
O Ni V Ni O 2 2 5 . 0
//
2

+ h Ni Ni
Ni
NiO
Ni

+ + + h Ni h e Ni
Ni
NiO
Ni
/
)i
E
sites are electron acceptors:
33 33
A!!lication ceramic semiconductors
)4C! thermistors &;egative -emperature
Coefficient! thermal resistor'
( )

=
T
B
T exp
0

k E B
A
/ =
-60 -40 -20 0 20 40 60 80 100120
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
7
10
8
50
500
500 k
50 k
5 k
R
e
s
i
s
t
i
v
i
t
y

[

]
Temperature [
o
C]
Conductivity is
thermally activated
4ill EFF
o
C spinels:
-n
E
D
$
)i-n
9
D
$
CoAe
9
D
$
4ill ca. 1FFF
o
C rare earth
o6ides eg.:#FRSm
9
D
E
EFR4b
9
D
E
34
E<trinsic ionic conductors
134
5
o
g

,
o
p
i
n
g
intrinsic
e6trinsic
Conductivity
increase by a
doping.
D6ides with fluorite structure &SrD
9
+ 4hD
9
+
CeD
9
' doped with CaD+ -gD+ N
9
D
E
+ Sc
9
D
E
and
5a
9
D
E
A
?
=
.
Br=
?
?A
,
Ce
" .=
<
=
" 4

=
Aluorite structure &CaA
9
!type'
Br
=
35 35
Intrinsic su!erionic conductor)
#aluminum o<ide# )a

ionic conductor
!aluminum o6ide )a
9
D11(l
9
D
E
Al
=
;a
5ayered structure of !aluminum
o6ide
36 36
#Aluminiumo<id II
7e6agonal unit cell.
Aor larger cations &2

+ 4l

'
lower conductivity is observed
173 373573
1E-7
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
K
Tl
Ag
Na
C
o
n
d
u
c
t
i
v
i
t
y

[

-
1
c
m
-
1
]
Temperature [K]
L
e
i
t
f

h
i
g
k
e
i
t
37
7igh energy density+ high
efficiency of charge3discharge
&8"C"9R' and long cycle life+
and is fabricated from
ine6pensive materials.
The sodium is separated by a
beta-alumina solid electrolyte
(BASE) cylinder from the
container of molten sulfur.
Sodium Sulfur Cell
+
+ e Na Na
l
2 2 2
) (
) ( 5 2 ) (
2 5 2
l l
S Na e S Na + +
+
+ Cathode
- Anode
) ( 5 2 ) ( ) (
5 2
l l l
S Na S Na +
Discharging
Charging
) ( ) ( ) ( 5 2
5 2
l l l
S Na S Na +
7igh operating
temperatures of EFF to
E:F TC and the highly
corrosive sodium
polysulfides and sodium.
+
38 38
Solid =<ide Fuel Cells (S=FC)
F.:D
9
9e
!
$
9e
!
Cathode Anode
%
?
7
9
D
D
9-
D
9-
D
9-
D
9-
D
9-
%lectrochemical conversion device that produces
electricity directly from o6idizing a fuel.
U D
9
7
9
7
9
D
4emperature range: 8FF!1FFF
o
C
39 39
Solid electrolyte# Solid =<ide Fuel Cells
40 40
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
-3
-2
-1
0
1
2
3
400 500 600 700 800 900
T [C]
10
3
/T [K
-1
]
l
o
g
(

t
)

[
S
/
m
]
intermediate
temperature
SOFC
Z
r
O
2-
b
a
s
e
d
G
a
O
3
-
b
a
s
e
d
B
i
2O
3-
b
a
s
e
d
C
e
O
2
-
b
a
s
e
d
S=FC) Solid Ele8trolyte
H7igh stability in air and also
strongly reduced atmosphere
at high temperature
4etragonal or cubic stabilized
SrD
9
&E+ resp. 8 molR N
9
D
E
in
SrD
9
'. 4hicIness = 9FFm.
Stability other materials &e.g.
doped CeD
9
' in reduced
atmosphere is not sufficient.
/artial reduction gives
electronic conductivity!
41
42 42
C
m
7
n
&mn3$'D
9
mCD
9
n397
9
D

=
exhaust
O
Air
O
p
p
F
RT
E
2
2
ln
4
V1 fuel e6cess
@1 stoichiometric combustion
81 o6ygen e6cess
,elivered amount of D
9
Stoichiometic amount of D
9
@
Oxygen sensor (lambda sensor)
exhaust
O
p
2
Signal
lambda
sensor

43
Oxygen sensor (lambda sensor)
44
Summary
Itinerant and localized electrons &holes' in solids
H-ott!7ubbard transition
HStructure influence
H,oping &stoichiometry'
e
Ions in solids as charge carriers