MME 467: Ceramics for Advanced Applications

Lecture 12
Electrical Conduction
in Ceramic Materials 2
Ref: Kingery, Introduction to Ceramics, Section 17.3, Wiley, 1991
Topics to discuss....
 Electronic conductivity
 Electron and electron hole concentrations
 Electron and electron hole mobility
 Polarons
 Hall effects and Seeback effects
 Electronic Conductivity
 Within most solid materials, a current arises from the flow
of electrons, which is termed electronic conductivity.

 Two charge carrying mechanisms:

Electron – negative charge

Hole – equal and opposite
(positive) charge

Move at different speeds – drift velocity

 Higher temperature promotes more electrons into the

conduction band and enhances electronic conductivity
 Electronic conductivity, like ionic conductivity, is given
by the equation
n = carrier density (number/cm3)
s = n|e|m m = carrier mobility (cm2/V.s)
and is proportional to
 the concentration of the mobile electronic carriers (n)
(i.e., electrons and electron holes), and
 their mobility (m)

 Thus, the total electronic conductivity is

s = |e| (neme + nhmh)
 When mobile electrons or (electron) holes are present
(even in small concentrations),

 their high mobility (several order of magnitude than ionic

mobility) gives appreciable contribution to electrical
conductivity

 in some cases, metallic levels of conductivity results, while in

other cases, electronic conductivity becomes vanishingly small

 The many order of magnitude difference in conductivity

distinguishes three different types of electronic
conductivity (principally for n, not m)
 Metals (e.g., for half-filled band of Na, n = 1022 cm-3)
 Semiconductor (n = 1010 cm-3)
 Insulator (n = 1 cm-3)
Electron and Electron-Hole Concentrations

 In a few cases (transition metals oxides e.g., CrO2, TiO, etc.) there is
an overlap of electron orbitals which resulted 1022 or more electrons
in the conduction band and essentially a metallic conduction.

 In most cases, however, there exist an energy gap Eg between filled

valence band and the empty conduction band, which is appreciably
greater than kT.

 To predict the number of electrons that are excited across the band
gap from valence to conduction band at a given temperature, one
must know

 the density-of-states functions (which describes the number of

states per unit energy interval in the vicinity of the band edge),
and
 the probability of their occupancy
 The density of electron, n, in the conduction band, and
the density of electron-hole, p, in the valence band are:

-( E g – E f )/kT
n = Nc e Eg = band gap energy
Ef = Fermi energy
– E f /kT
p = Nv e Nc = effective density of state in the conduction band
Nv = effective density of state in the valence band

3/2
æ 2p kT ö
me*
N c = 2 çç 2
÷÷
è h ø
3/2 m* = effective mass of migrating species
æ 2p kT ö
m*h h = Plank’s constant
N v = 2 çç 2
÷÷
è h ø
 Taking products of n and p

æ -E g ö
n p = N c N v exp çç ÷÷ ( independent of Ef )
è kT ø

which is similar to the equilibrium constant of

the defect reaction

Null e + h

æ -E g ö é n ùé p ù
K = exp çç ÷÷ = [ e ].[ h ] = ê ú.ê ú
è kT ø ë Nc û ë Nv û
Intrinsic semiconductor æ Eg ö
[ n ] = [ p ] = exp çç - ÷÷ = K i
è 2kT ø

s = N v N c K i e éëme + mh ùû
Conductivity (arb. Units)

High Eg

conductivity increases exponentially

Low Eg
with temperature because the number
of carriers increase exponentially with
temperature.

Temp (K)
Electron and Electron-Hole Mobility

 The general mobility of any carrier i

mi = vi / Ei vi = drift velocity of carrier i

Ei = local electric field

scattering
 The motion of electron and holes is E events
affected by two types of scattering:

 Lattice scattering
due to thermal vibration
(T dependent)
 

 Presence of impurity
distorts the periodicity of lattice net electron motion
 Resulted drift mobility due to lattice scattering
e te
me = ti = characteristic relaxation time between collision
me* between the carrier and phonon (lattice vibration)
e th (e/m*) = effective acceleration of charge carrier
mh =
mh*

 The overall mobility of carrier i is then

-1
é 1 1 ù
mi = ê + ú mt = mobility due to lattice scattering
êë mi,t mi,I úû mI = mobility due to presence of impurity

 And the overall electronic conductivity

én n ù
s = e t ê e* + h* ú
2

ë me mh û
 Temperature dependence of ti determines the
temperature dependence of the mobility
 Temperature dependence of mobility can be
represented as

mt  mt0 . T –3 / 2
m0 = constant
mi  mi0 . T 3 / 2
 Thus, the T dependence of mobility of electron and hole is much smaller
than that for their concentrations.
 T dependence of conductivity is mostly determined by the
concentration term
Polarons
 When electron moves through ionic crystals (MgO, Al2O3,
NaCl, etc.), cations are attracted and anions are repelled.
 this leads to polarised ions, and the position of ions become
distorted (lattice distortion)
 the association of electronic carrier with its polarised field is
called polaron
 so instead of electron moving through the lattice, one gets
polaron (electron plus lattice distortion) motion

This polarisation traps or

e– slows down the electronic
defect as it moves through
the lattice
Large polaron
 When the association is weak
 Moves like quasi-free electron, with a higher effective mass than a free electron
 mobility , m  T –1/2 (m = 1 – 100 cm2/V-s)

Small polaron
 When the association is strong and over a small distance
 e – along with its lattice distortion hops from ion to ion over lattice distance
 mobility is severely affected by lattice distortion
 mobility , m = m0 e –Em/kT (m = 10–2 – 10–4 cm2/V-s, Em = 0.1 – 0.2 eV)
 Extrinsic Semiconductor Silicon
Extra
with hole
electron

n-type semiconductor p-type semiconductor

P ¾¾
® Si
PSi· + e¢ ® BSi¢ + h·
B ¾¾ Si

each P donates one e– each B creates one h

to the conduction band to the valence band
 n-type semiconductor
Donor states are created in gap

Since each donor electron is excited from an impurity level,

no corresponding hole is created within the valence band.
p-type semiconductor
acceptor states are created in gap
 So, for n-type extrinsic semiconductor, the
electronic conductivity is:

s  n | e | me
 For p-type semiconductor, n << p.

 So, for p-type extrinsic semiconductor, the electronic

conductivity is:

s = p|e|mh
Quantification of Conductivity
of Extrinsic Semiconductor

 Consider a n-type extrinsic semiconductor doped with a

concentration ND of dopant atoms.

Ionization reaction D Û D· + e¢ D = concentration of ionized donor

D = concentration of non-ionized donor
of donor:
·
Mass balance: ND Û D + D

æ -Ed ö éë D · ùûéënùû Ed = energy required to ionized the donor

K = exp ç ÷= [n] = n/NC, and [D] = D/ND
è kT ø éDù
ë û
At Low T
 only few donors are ionized; n = D << ND; [D] ≈1
 The conductivity
æ -Ed ö
s n = |e|me ( N c N D )
1/2
exp ç ÷
è 2kT ø
At Intermediate T

 Here kT ≅ Ed; most of the donors are ionized; n = ND;

 The conductivity s n = |e|N D me

At High T
 Number of electrons excited from valence band dominates;
semiconductor behaves intrinsically.
æ -E g ö
s n = |e|me ( N c N D )
1/2
 The conductivity exp çç ÷÷
è 2kT ø
Temperature Dependency of electronic
conductivity of extrinsic semiconductor
Example Problem 19.3 (Callister)
If the RT (25 C) electrical conductivity of intrinsic germanium is 2.2
(W-m)–1, estimate its conductivity at 150 C.
Use Eg = 0.67 eV, k = 8.62x10–5 eV/K

The electrical conductivity of intrinsic semiconductor is:

æ -E g ö æ -E g ö
s n = |e|me ( N c N D )
1/2
exp çç ÷÷ = C exp çç ÷÷
è 2kT ø è 2kT ø

where C is a T independent constant. Then taking ln in both sides

æs n ö Eg æ T1 ö
ln ç ÷ = - s T 2 = s T 1 exp ç ÷
èC ø 2kT èT2 ø
æ s T 2 ö T1 æ 298 ö
ln ç ÷=
è s T 1 ø T2
s 423 = s 298 exp ç
è 423 ø
(
÷ = 2.2 2.02 )
= 4.45 (W -m)-1
Non-stoichiometric Semiconductors

 The band picture of non-stoichiometric semiconductors is very

similar to that of extrinsic semiconductors

 But the electronic defects are formed not as a result of

doping, but rather by varying the stoichiometry of the crystal.

 The electrons and holes are excited to the conduction and

valence bands as a result of reduction or oxidation.
 Example: Reduction of Oxide in ZnO

 Removal of oxygen atom

 Leave e– behind to maintain electroneutrality
 These electrons are responsible for conduction and result
n-type semiconductor (Zn1+xO)

OOx + ZnZn
x
® 1 2 O2 ( g ) + Zni· + e ¢
Perfect Crystal ZnO @ 900 C

K= pO2 .éëZni· ùûéënùû log s

–1/4

Zni· = n
s ¥ n = ( const.) pO-1/4 log pO2
2
Example: Oxidation of Oxide in Cu2O

 Addition of oxygen atom creates hole, forming p-type

semiconductor (Cu2-xO)

·
1
2
O2 ( g ) ®OO
x
¢ + 2h
+ 2VCu Cu2O @ 1000 C

¢ =p
VCu log s
1/8

s ¥ p = ( const.) 1/8
pO
2
log pO2
 Ceramic Insulators
 Do not have mobile charge carrier, and do not permit passage of an
electric current when placed in an electric field.

 Typical resistivity values (usually > 1014 W-cm):

SiO2, Al2O3, Si3N4, MgO – 1014
Polystyrene – 1018

 High resistivity resulted from

1. the way the electrons are tied up during bonding (covalently or
ionically) with a full outer shell of electrons, and
2. have a large Eg value
Norton’s book
MgO is very difficult to reduce