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

1
 Electrical conductivity
23
Superconductors >10
Superconductivity: by cooling
10
7 resistivity drops to zero

Metals
Cu
5
10
3 YBa2Cu3O7 Pb Conductivity of metals decreases
10 with temperature. Increased

Semiconductors
La0.75Ca0.25MnO3 Graphite
Conductivity [Ω cm ]

interaction of electrons with

-1

1
10
lattice!
-1

-1
10 Na2O*11Al2O3

-3
10
-5
Ge
10 Si
Conductivity of insulators and
Insulators

-7
10
semiconductors increases with
-9
10 Glass temperature. Concentration of
-11
10 carriers increases!
1 10 100 1000
Temperature [K] 2
 Electrical resistivity of ceramic (oxide) materials –
over 20 orders of magnitude

Insulators Semiconductors Conductors Superconductors

10-13 10-8 10-3 102 107 ∞
Conductivity,Ω-1m-1

3
Electronic charge distribution in the basic solid types
(chemical bond point of view)
K Cl

18+ 18+ 18+ 17+ 19+ 17+ 19+

18- 18- 18- 18-
18- 18- 18-

18+ 18+ 19+ 17+ 19+ 17+

18+
18- 18- 18- 18-
18- 18- 18-

Molecular: Ar Ionic: KCl

4+ 4+ 4+ 19+ 19+ 19+ 19+

Delocalized
electrons
4+ 4+ 4+ 19+ 19+ 19+ 19+

Covalent: C (diamond) Metallic: K

4
After N.W. Ashcroft, N.D. Mermin, „Solid State Physics“, Philadephia, 1976
 Metals, semiconductors, insulators

Metal
Semiconductors: electrons are
excited over the band gap and
Semiconductor:
occupy energy levels in intrinsic
conductivity band. Holes are extrinsic

Log σ
created in valence band. The
process is thermally activated-
conductivity increase with
temperature. Insulator
1/T

Conductivity can be increased by a doping. Through the doping

energy levels within band gap will be created.

A material with an energy gap >2.5 eV is an insulator.

5
 Electron in a (1D) solid

E
Energy of
an electron: E = ħω= (ħk)2/2m E ~ k2
k=2π/λ wave vector
k
λ – wavelength
of the electron

Electrons with λ>>a (lattice parameter)

can travel freely through a crystal

→a ????
For more energetic electrons when λ→

6
 E
Electron in a (1D) solid
E ~ k2

Potential energy of an electron

in a periodic array of positive ions k
Wave functions for λ=2a

Distribution of the electron

densities:
Ψ2~cos2(πx/a) lower energy
a Ψ2~ sin2(πx/a) higher energy

λ=2a
E

Electrons which have a Forbidden band

wavelength commensurate
with the lattice are
scattered on the periodic
potential -π/a π/a 7
 Band (Bloch-Wilson)
insulators
Partially filled energy band metal

S Filled energy band insulator

splitted d orbitals dxz, dyz

(trigonal prism
coordination)
dxy, dx2-y2

dz2

insulator metal

Mo4+ 4d2 Nb4+ 4d1 8

 No carriers – no conductivity

Na2O Na+ 2p63s0 O2- 2p6 Noble gas configuration:

insulator

MgO Mg2+ 2p63s0 O2- 2p6 insulator

O2- 2p6 insulator

TiO2 Ti4+ 3d04s0
Free carriers?
TiO Ti2+ 3d24s0 O2- 2p6 Free d-electrons:
metal

NiO Ni2+ 3d84s0 O2- 2p6 Insulator

But why???

9
 TiO- rutile Ti 3d24s0
Ti

metal

NiO- NaCl structure Ni 3d84s0

Ni
Is insulator!
O
Why not a metal?

10
Why not metal?
Whatever is the crystal
field splitting the orbitals
are not fully occupied!!!
CuO Cu2+ 3d94s0

CoO Co2+ 3d74s0 Odd number of d electrons-

all this oxides should be
MnO Mn2+ 3d54s0 metals but are insulators

Cr2O3 Cr3+ 3d34s0

Electron configurations
3d44s2 3d94s2 of elements
3d54s2 3d74s2

11
 Mott-Hubbard insulators

•The d-levels in most of the transition metal

oxides are partially filled, therefore, the band
theory predicts electron delocalization and
metallic properties.
•According to band structure calculations half
of the known binary compounds should be The Nobel Prize in Physics
conducting. 1977: Philip Warren
Anderson, Sir Nevill
•In reality, many oxides show insulating Francis Mott and John
behavior, implying that the d-electrons are Hasbrouck van Vleck
localized. "for their fundamental
theoretical investigations
•Short-range Coulomb repulsion of electrons of the electronic structure
can prevent formation of band states, of magnetic and
stabilizing localized electron states. disordered systems".

12
Mott considered the idealized metal-insulator transition for Na
crystal by changing the
interatomic spacing.
E
uct ivity
cond Electron hopping
between atoms
during conduction
U
Na + Na Na+ + Na-
Na+ Na-
U Bandwidth or band dispersion:
energy difference between the highest
and lowest level. Bandwidth increases
with better orbital overlap. Localization
Na Na Na Na of electrons – narrow bands.

ψ ψ

1/a
Hubbard U - energy penalty for transferring an
electron between two adjacent sites -assumed to After: Feng Duan, Jin Guojun,
13 Matter
“Introduction to Condensed
be independent on a Physics”, Vol.1, World Scientific 2005
 Mott-Hubbard insulators

Coulomb repulsion is described in

terms of a correlation energy,
Hubbard-U, which is the energy
penalty for transferring an electron U
between two adjacent sites.

U ~I -A

ionization energy electron

(a few eV) affinity
Ni2+ + Ni2+ → Ni3+ + Ni+
d8 + d8 → d7 + d9

14
 E

Upper Hubbard band

U Ef
Lower Hubbard band

Bandwidth W
U=1/2(B1+B2)
If U > W, the d band of the
At the point where W ~
transition metal is splitted into
U, the bands overlap.
sub-bands. For an electron
Beyond this point, there
transfer an energy barrier U
is no energy gap and the
must be overcome and the
material is insulating. material is metallic.
Mott-Hubbard (MH) insulator.

The effect of the electron repulsion makes even the half-filled band
insulating when the interaction between atoms (band width W) is small.
15
 Pressure and temperature dependence

•Every material under high δ

pressure will have metallic
properties insulator
•Insulator-Metal transition can
metal
be achieved increasing
temperature (thermally
induced carriers) or doping 1/a
1/ac

16
Phase diagram of V2O3

•Mixed oxides (chemical pressure)

Ti3+ 0.81Å; V3+ 0.78 Å; Cr3+ 0.755 Å

•Pressure experiments for V2O3

and (V0.96Cr0.04)2O3

D.B. McWhan et al., PRL, 23 (1969) 1384

17
 V2O3 metal-insulator transition

~145K

conductivity (ohm cm)-1

1/T, 103/K

D.B. McWhan et al., PRL, 23 (1969) 1384 J. Feinleib and W. Paul, Phys. Rev. 155(1967)
18 841
 Transition metals TM
General rules

↑W ↓U Larger d orbitals

↑W •low oxidation state (more electrons) for early TM (good M-M overlap)
•high oxidation state for late TM (good M-O-M overlap: covalent
bond)
•for covalent bonds: low electronegativity anions
halides, O, S, Se, Te, phosphides.....

NiS, CoS and CuS-metals

NiO, CoO and CuO- (MH) insulators

•electron configuration e.g. Mn2+ 3d5 has half-filled shell

↑U •other cations in the structure (as e.g. in perovskites ABO3)

19
•Mott-Hubbard models
assumes that the band Oxygen p bands
gap is within d-band. Metal d bands
• 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.
∆ is a gap between
2p oxygen band
and the d-band of
the metal.

20
 Charge-transfer- Mott-Hubbard-
insulator insulator
(semiconductor)
(Semi)Metal

oxygen p metal d
band bands

Conductivity
via holes in
O 2p-band

Different ∆/U ratio!

Egap ≈ ∆ Egap ≈ ∆
LaCuO3 is a metal U is large
Cu 3d-band and O 2p-band
overlap.
21
Examples
Metal bands

Oxygen p band

U<W
U<∆ Metal

∆<U Mott-Hubbard
insulator High temp.
Charge transfer mod. of TiO,
insulator
NiO, NiPS3, CrO2
CuCl2, CuO Ti2O3, V2O3,
∆<W Cr2O3
Semimetal
LaCuO3, CuS,
CuSe
22
Oxygen p metal d
band bands

23
 1000 800 333 250 200 167 149 125 T, K
Cu 5.9 107 at RT
ReO3 CrO2 metallic
106 TiO
V2O3
Ti2O3 VO
ReO Fe3O4
Conductivity,Ω-1m-1 NbO 2 MnO
102 2
NiO MoO2

10-2 VO2

FeO

10-6
Cr2O3
CoO
10-10 Mn3O4

Fe2O3
10-14

1 2 3 4 5 6 7 8 1000/T,24K-1
After: Schaumberg, Keramik
Perovskites

after I. H. Inoue, Semicond. Sci. Technol., 20 (2005) S112

25
 d1 perovskites

YTiO3 insulator
LaTiO3 insulator gap 1.0 eV
gap 0.2eV

CaVO3 metal
SrVO3 metal 26
Oxygen nonstoichiometric 3d oxides

Does the electrical

conductivity
depend on oxygen
content and cation
doping?

27
 Lattice defects
Schottky- und Frenkel-defects in crystals

Schottky-defekts:
The volume of the crystal will increase

Frenkel-defekts:
The volume of the crystal stays
constant

∆L/L

Dilatometer

Schottky-
defects
28
Temperature
 Defect concentration n/N0
n  − EV 
≅ exp 
N0  kT 

Temperature Activation Energy eV

[oC] 1 2 8
100 3·10-14 1·10-27 1·10-108

500 3·10-7 1·10-13 8·10-53

1000 1·10-4 1·10-8 2·10-32

1500 1·10-3 2·10-6 2·10-23

2000 6·10-3 4·10-5 2·10-18

29
 Fe1-xO (FeO1+x) semiconductor type p
FeO ,,
4Fex + O2 4Fe•Fe + 2OxO + 2V Fe
Fe

Fe•Fe ion can trap an electron from the valence band.

In VB a hole is created.
FeO
Fe•Fe FexFe + h•
h•

CB

Ef Acceptor level

Energy
VB

F(εε) 30
 TiO2-x semiconductor type n
TiO2
2TixTi + OxO 2Ti‘Ti + V••O + 0.5 O2

Ti4+ Ti‘Ti
TiO2
TixTi + e‘

Donor level is situated

CB close to the conductive
Ef band.
The donor cation Ti‘Ti (Ti3+)

Energy
Donor level
can inject an electron into
VB conducting band.

F(εε)

31
 Defect semiconductor. Ni1-δδO
p
In NiO nickel vacancies are created when oxidized with oxygen. The
charge of the additional oxygen sites is compensated by oxidation
of some nickel sites to Ni3+. Through the oxidation the volume of
the material increases.

× •
0.5O2 + 2 NiNi NiO
→
 VNi// + 2 NiNi + OO×

• ×
NiNi NiO
→
 NiNi + h•

Ni3+ sites are electron acceptors:

•
Ni Ni + e / + h • NiO
 ×
→ NiNi + h•

32
 Application ceramic semiconductors
NTC- thermistors (Negative Temperature
Coefficient- thermal resistor)

B
ρ (T ) = ρ 0 exp  B = − E A / k 8
10
T  7
10
Conductivity is
thermally activated
6
10
500 kΩ

Resistivity [Ω]
5
10
Till 300oC spinels: 4
5 kΩ
50 kΩ
10
Mn3O4 3
500 Ω
10 50 Ω
NiMn2O4 2
10
CoFe2O4 1
10

Till ca. 1000oC rare earth 0

10
-60 -40 -20 0 20 40 60 80 100 120
oxides eg.:70%Sm2O3 o
Temperature [ C]
30%Tb2O3
33
 Extrinsic ionic conductors

intrinsic
extrinsic Conductivity
increase by a

Doping
Log σ

doping. Zr
O

1/T

Oxides with fluorite structure (ZrO2, ThO2,

CeO2) doped with CaO, MgO, Y2O3, Sc2O3 and
La2O3
ZrO2 ,
Y2O3 2Y Ce + 3OxO + V••O
Fluorite structure (CaF2-type)

34
 Intrinsic superionic conductor.
β-aluminum oxide- Na+ ionic conductor
Al

O
Na

β-aluminum oxide Na2O⋅11Al2O3

Layered structure of β-aluminum
oxide
35
 β-Aluminiumoxid II

0.1

Conductivity [Ω cm ]
-1
0.01

-1
1E-3

Leitfähigkeit
1E-4

1E-5 Na K

Ag
1E-6
Tl
1E-7
173 373573

Temperature [K]

For larger cations (K+, Tl+)

Hexagonal unit cell. lower conductivity is observed

36
Sodium Sulfur Cell
High energy density, high
efficiency of charge/discharge
(89–92%) and long cycle life,
and is fabricated from
inexpensive materials.
+
High operating
temperatures of 300 to
350 °C and the highly
corrosive sodium
polysulfides and sodium.

- Anode
2Na(l ) → 2Na+ + 2e− Discharging

+ Cathode 2Na(l ) + 5S(l ) → Na2 S5(l )

2Na+ + 5S(l ) + 2e− → Na2 S5(l )

The sodium is separated by a Charging

beta-alumina solid electrolyte
(BASE) cylinder from the Na2S5(l ) → 2Na(l ) + 5S(l )
container of molten sulfur.

37
 Solid Oxide Fuel Cells (SOFC)

Electrochemical conversion device that produces

electricity directly from oxidizing a fuel.
½ O2 + H2 → H2O

Temperature range: 800-1000oC

Cathode Anode

0.5O2 O2- O2- H2O

O2-
O2- O2-

2e-
2e- H2
U

38
Solid electrolyte- Solid Oxide Fuel Cells

39
 SOFC. Solid Elektrolyte
•High stability in air and also
strongly reduced atmosphere
T [°C] at high temperature
900 800 700 600 500 400
3

2
Bi
2O
3 -b
Tetragonal or cubic stabilized
ase
1
d GaO ZrO2 (3, resp. 8 mol% Y2O3 in
3-base
log(σt) [S/m]

0
d ZrO2). Thickness ~ 200µm.
CeO
2 -bas
ed Stability other materials (e.g.
-1
ZrO
2 -b
doped CeO2) in reduced
intermediate ase
-2 temperature d atmosphere is not sufficient.
SOFC
Partial reduction gives
-3
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6 electronic conductivity!
103/T [K-1]

40
41
 Oxygen sensor (lambda sensor)
CmHn + (m+n/4)O2 → mCO2 + n/2H2O

Delivered amount of O2
λ=
Stoichiometic amount of O2

λ<1 fuel excess

λ=1 stoichiometric combustion
λ>1 oxygen excess

Signal pOexhaust
2
lambda
sensor

RT  p OAir 
E= ⋅ ln  exhaust
2 
4F  pO 
 2 
λ 42
Oxygen sensor (lambda sensor)

43
 Summary
Itinerant and localized electrons (holes) in solids

e
•Mott-Hubbard transition

•Structure influence

•Doping (stoichiometry)

Ions in solids as charge carriers

44