Fundamentals and Definitions

 Historically ceramics are used as ideal insulating

materials for their good electrical insulating properties
and chemical and thermal stability
Example: power line, resistors

 Today, besides the above-mentioned applications,

ceramics are used in many other fileds:
 Electrode  Photoelectrode
 Catalytes  Varistor
 Fuel cell  Sensor

Here comes the term “Electronic Ceramics”

Electrical Conductivity
 The response of ceramics to the application of a constant electric
field and the nature and magnitude of the steady-state current is
identified by a material property, called electrical conductivity.

 Mathematically, the ratio of the current to the applied electric

field is called conductivity, s.

Current Carrier
Metals : Free electrons
Semiconductors : Electrons and electron-holes
Ceramics : Electrons and/or ions

Mixed conduction does occur and this conduction is represented as:

s = selec+ sionic
Characteristics of Metals, Semiconductors
and Insulators in terms of Energy Band

n = carrier density, cm-3

n=1022 n=1010 n=1 @500K
Energy Unoccupied
conduction band
partially occupied

Occupied
valence band

Electronic: metal semiconductor insulator relative occupancy of valence

and conduction bands

Ionic: fast ion solid insulator relative occupancy of

conductor electrolyte ionic sublattice
Some Definitions

 Electric current density, j

electrical charge transported through a unit area in unit time

n = carrier density or, no. of charged particle

j = nqv (mobile carrier) per unit volume
q= charge per particle
v = drift velocity under an applied electric field, E

 Electrical conductivity, s
proportionality constant between j and E

j nqv
s= E = -1cm-1 or S/cm
E
 The drift velocity is directly proportional to the locally
acting electrical field strength, and their ratio is defined
as the mobility, m (i.e., velocity per unit field)
v n (q) v
m= cm-1V-1s-1
s=
E E
s = n (q) m

 Absolute mobility, B
drift velocity per unit of applied force F (the virtual force which
acts on a diffusing carrier)

v v s = n (q)2 B
B= =
F (q)E m = (q)B
 Ionic Conductivity

 Carrier of electrical charge – charged ionic defects

vacancy, interstitials
moves under the influence of an electric field
based on random ion hopping

 Ionic ceramics exhibit this behaviour

assuming that empty sites or vacancy are always available .
 For an ion to move through the lattice, it must have sufficient thermal
energy to pass over the energy barrier

The absolute mobility and hence s is directly related to the diffusion

coefficient D through the Nearnst- Einstein equation

D=kBT
Hence

nq  D
2
s 
kT
Size
Charge
lattice
 q=ze

activation energy
for ion motion
u or, Hm
Energy a (ze)Ea = Fa

No field E applied E applied

Distance
 Forward jump rate
(ze)Ea
-u+ kT q = probability of a site
e
2
f+ = q is available for a jump

 Backward jump rate

(ze)Ea
-u- kT
f– = q e
2

 The net jump rate

u
f = f + – f- = 2 q e kT
sinh (ze)Ea
2kT
 u
f = f + – f- = 2 q e kT
sinh (ze)Ea
2kT

 For typical values of E, a, and T

(ze)Ea << kT and sinh [ ] terms becomes very small.

(ze)Ea (ze)Ea
sinh 
2kT
2kT

 Then, the net jump rate

u
f = qe kT (ze)Ea
kT
 Total net flux

na2(ze)E - u / kT n = carrier concentration

naf = q e af = drift velocity
kT

 Electric current density

j = n(ze)v = n(ze)af

na2(ze)2E - u / kT
j = q e
kT
 Ionic conductivity
j na2(ze)2 - u / kT
s = E = q e
kT
n(ze)2 n = cion (vacancy mechanism)
s = D n = cint (interstitial mechanism)
kT s
Nernst-Einstein (N-E) Relation

 Ionic diffusivity

Ds = a2 qe -u / kT
 depends
only on D0
Ds Low T
s0 = conductivity of
Extrinsic pure material

High T

Intrinsic
depends on D0
and vacancy site 1/T

Temperature dependence of diffusivity

 Fast Ion Conductors (FICs)
 Many ceramic compound shows exceptionally high
ionic conduction, similar to those of molten salts
(s  10-2 s/cm).
These are known as fast ion conductors
(sometimes also referred to as solid electrolytes)

 Major structural features of FICs:

 Framework
a highly ordered, immobile sublattice which provides
continuous open channels for ion transport

 Mobile carrier sublattice

a randomly distributed carrier over an excess number of
equioptional sites
 Other important fast ion conduction parameters:

 High ionic conductivity (s > 10-2 S/cm)

well below the melting point

 Low activation energies (Q  0.05-0.50 eV)

 Low pre-exponentials (s0  100-104 S/cm.K)

 Fast Ion Conductors (FICs)
 Many ceramic compound shows exceptionally high
ionic conduction, similar to those of molten salts
(s  10-2 s/cm).
These are known as fast ion conductors
(sometimes also referred to as solid electrolytes)

 Major structural features of FICs:

 Framework
a highly ordered, immobile sublattice which provides
continuous open channels for ion transport

 Mobile carrier sublattice

a randomly distributed carrier over an excess number of
equioptional sites
 Other important fast ion conduction parameters:

 High ionic conductivity (s > 10-2 S/cm)

well below the melting point

 Low activation energies (Q  0.05-0.50 eV)

  3 groups of FICs:

 Silver ion conductor

 halides and chalcogenides of Ag and Cu
metal atoms are disordered over several
INTRINSIC


structurally alternate sites
disorder  example: a-AgI
solid
 Alkali metal conductor
 nonstoichiometric aluminate
 example: b-Al2O3 i.e. Na2O.11Al2O3
EXTRINSIC

 Oxygen ion conductor

highly  oxides with fluorite structure, doped with
defective lower valence cation oxides to create large
solids
oxygen vacancy
 example: CaO-ZrO2, Y2O3-ZrO2
 CUBIC STABILIZED ZIRCONIA
(CSZ)

Monoclinic(1170℃)tetragonal(2370℃)cubic
(2680℃)

A total of 5% volume contraction can be overcome by

stabilizing the cubic form down to room temperature by
substituting lower valency cations for the Zirconia.

The vacancies that stabilize the structure also

lead to high mobility in the oxygen sub-lattice

Fig: The ideal fluorite structure showing

CaO  Ca Zr  V  O 
O
x
O
half a unit cell including a dopant cation and
a charge-compensating oxygen vacancy.

ZrO 2
 β-alumina 11 Al2O3 - x Na2O
The crystal is made of parallel thin layers of dense alumina separated from each other by scarcely
occupied planes where all sodium ions are confined.

COMPOSITIONAL Na2O·11Al2O3(β-alumina),Na2O·8Al2O3(β’-alumina),Na2O·5Al2O3(β’’-alumina)
VARIATION
β-alumina is alternate layer of
alumina and Na2O

conductivity is high within

these planes but negligible in
the perpendicular direction.

Conductivity parallel to planes

is 1 Sm-1:room temperature,30
Sm-1:300℃
 Na2O·11Al2O3(β- Increasing
alumina) conductivity
due to loose
Na2O·8Al2O3(β’- spinel
alumina) packing

Na2O·5Al2O3(β’’-

Molten Na

Electrode
Electrode

Molten S
alumina)

Alumina has a close packed spinel structure and as

the number of alumina decreases, the packing
density of spinel layers also decreases

Na/S battery
Battery

Limited Application:
Aerospace and satellite
 Fuel Cell
The ceramics used in SOFCs do not
become electrically and ionically active until
they reach very high temperature
As a consequence the stacks have to run
at temperatures ranging from 500 to 1,000
°C.
 Reduction of oxygen into oxygen ions
occurs at the cathode. These ions can then
diffuse through the solid oxide electrolyte to
the anode where they can electrochemically
oxidize the fuel.
In this reaction, a water byproduct is given
off as well as two electrons. These electrons
then flow through an external circuit where
they can do work.