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.
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.
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
-( 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
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
Temp (K)
Electron and Electron-Hole Mobility
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*
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
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
P ¾¾
® Si
PSi· + e¢ ® BSi¢ + h·
B ¾¾ Si
s n | e | me
For p-type semiconductor, n << p.
s = p|e|mh
Quantification of Conductivity
of Extrinsic Semiconductor
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
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
OOx + ZnZn
x
® 1 2 O2 ( g ) + Zni· + e ¢
Perfect Crystal ZnO @ 900 C
Zni· = n
s ¥ n = ( const.) pO-1/4 log pO2
2
Example: Oxidation of Oxide in Cu2O
·
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.