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MME 467: Ceramics for Advanced Applications

Lecture 21
Ref: Callister, Section 19.10, Wiley, 5th Ed., 2000.

Prof. A. K. M. B. Rashid
Department of MME, BUET, Dhaka

Topics to discuss .......

Semiconductors and their classifications!
Intrinsic semiconductors!
Extrinsic semiconductors!
Non-stoichiometric semiconductors!
Conducting polymers!


q  Materials that have electrical resistivity between that of

conductors and insulators (~100 – 1012 Ω-cm).!

q  Have small energy band gap (less than 2 eV) which can easily
be overcome by increasing temperature or by applying voltage.!

q  Electrical properties of these materials are extremely

sensitive to the presence of even minute concentrations
of impurities.!

q  Although the conductivity is not as high as that of metals,

nevertheless they have some unique characteristics that
render them especially useful.!

Classifications and Mechanisms

of Semiconduction

q  The mobile charge carriers (electron and hole)

are generated by 3 ways:!
1. !By excitation across the band gap!
! !è Intrinsic semiconductors
2. !By addition of impurities!
! !è Extrinsic semiconductors
3. !By resulting a departure from stoichiometry!
! !è Non-stoichiometric semiconductor

Intrinsic Semiconductors
q  e’ and hŸ are generated by excitation across the
band gap of the material.!
For every electron that is excited into the conduction band, a hole is
left behind in the valance band.

So for an intrinsic semiconductor, n = p.

q  Examples of intrinsic semiconductors:!

1. Pure material semiconductors: Group IVA materials (e.g., Si & Ge)
2. Compound semiconductors: III-V compounds (e.g., GaAs & InSb);
II-VI compounds (e.g., CdS & ZnTe)

As the electronegativity difference between the elements

increases, bonding becomes more ionic and the energy gap
increases – the materials become more insulative.!

q  Electrical conductivity for a semiconductor is:!

# holes/m

σ = n e µe + p e µh hole mobility
3 electron mobility
# electrons/m

q  For intrinsic semiconductor, by definition, n = p,

and the conductivity!

σ = n|e|(µe + µh )

" E %
[ n ] = [ p ] = exp $$ − g '' = K i
# 2kT &

σ = N v N c K i e !"µe + µh #$
Conduc4vity  (arb.  Units)  

High Eg

conductivity increases exponentially

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

Temp  (K)    

Example Problem 19.1 (Callister)

For intrinsic silicon, the room-temperature electrical conductivity
is 4x10–4 (Ω-m)–1; the electron and hole mobilities are,
respectively, 0.14 and 0.048 m2/V-s. Compute the electron and
hole concentrations at room temperature.!

For intrinsic semiconductor,

n= p=
|e| µe + µ p ( )
4x10−4 ( Ω -m) −1
(1.6x10−19 C ) 0.14 + 0.048 m 2/V-s )
=1.33x1016 m −3

Extrinsic Semiconductors

q  Most intrinsic semiconductors do not have low enough

resistivity to be useful at low T in an electric circuit.!

!è Required resistivity ~ 10–2 – 102 Ω-cm!

q  Thus, virtually all commercial semiconductors are extrinsic.!

q  Their electrical behaviour is determined by impurities,

which, when present in even minute concentrations,
introduce excess electrons or holes.!
E.g., an impurity concentration of one atom in 1012 is sufficient
to render silicon extrinsic at room temperature.

with hole

n-type semiconductor p-type semiconductor

P !Si!
→ PSi• + e # B !Si!
→ BSi# + h•
each P donates one e– each B creates one hŸ
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.

q  At room temperature, the thermal energy (kT) available

is sufficient to excite large number of electrons from
donor states!

q  In addition, some intrinsic valence-conduction band

transitions also occur.!

q  Thus, for n-type semiconductor, n >> p. !

q  So, for n-type extrinsic semiconductor, the electronic

conductivity is:!

σ = n|e|µe

p-type semiconductor
acceptor states are created in gap

q  For p-type semiconductor, n << p. !

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

conductivity is:!

σ = p|e|µh
v  Extrinsic semiconductors (both n- and p-type) are produced from
materials of extremely high purity, commonly with a total impurity
content of the order of 10–7 at%.

v  Controlled concentrations of specific donors or acceptors are then

intentionally added (a.k.a. doping) using various techniques.

q  In extrinsic semiconductors, large numbers of charge carriers are created

at RT by the available thermal energy (kT).
q  So relatively high RT electrical conductivities are obtained, which are
suitably used in electronic devices to be operated at ambient conditions.

Example Problem 19.2 (Callister)
Phosphorous is added to high purity silicon to give a concentration
of 1023 m–3 of charge carriers at RT. (a) Is this material n-type or
p-type? (b) Calculate the RT conductivity of this material,
assuming that electron and hole mobilities are the same as for the
intrinsic materials.!

P is a group VA element. So it will act as a donor in silicon, and

the material is a n-type extrinsic semiconductor.

The 1023 m–3 charge carriers are virtually all electrons.

(Note that the concentration is greater than that for the intrinsic case
(1.33x1016 m–3)).

( )( )(
σ = n|e|µe = 1023 m −3 1.6x10−19 C 0.14 m 2 /V-s )
= 2240 (Ω -m) −1

Quantification of Conductivity
of Extrinsic Semiconductor

q  Consider a n-type extrinsic semiconductor doped with a

concentration ND of dopant atoms.!

Ionization reaction D ⇔ D • + e" DŸ = concentration of ionized donor

of donor: D = concentration of non-ionized donor

Mass balance: N D ⇔ D + D•

" −Ed % () D • *+()n*+ Ed = energy required to ionized the donor

K = exp $ '= [n] = n/NC, and [DŸ] = DŸ/ND
# kT & (D *
) +

At Low T
v  only few donors are ionized; n = DŸ << ND; [D] ≈1
v  The conductivity
1/2 " −Ed %
σ n = |e| µe ( N c N D ) exp $ '
# 2kT &
At Intermediate T

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

v  The conductivity σ n = |e|N D µe

At High T
v  Number of electrons excited from valence band dominates;
semiconductor behaves intrinsically.
1/2 " −E g %
v  The conductivity σ n = |e| µe ( N c N D ) exp $$ ''
# 2kT &

Slope = –Eg/2k

n = ND

Slope = –Ed/2k

Temperature  Dependency  of  charge  carrier  and  

electronic  conduc5vity  of  extrinsic  semiconductor  

Example Problem 19.3 (Callister)
If the RT (25 C) electrical conductivity of intrinsic germanium
is 2.2 (Ω-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:

1/2 " −E g % " −E g %
σ n = |e| µe ( N c N D ) exp $$ '' = C exp $$ ''
# 2kT & # 2kT &

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

!σ $ E !T $
ln # n & = − g σ T 2 = σ T 1 exp # 1 &
"C % 2kT "T2 %
!σ $ T ! 298 $
ln # T 2 & = 1 σ 423 = σ 298 exp # & = 2.2 ( 2.02)
" σ T 1 % T2 " 423 %
= 4.45 (Ω -m)−1

Non-stoichiometric Semiconductors

q  The band picture of non-stoichiometric semiconductors

is very similar to that of extrinsic semiconductors!

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

doping, but rather by varying the stoichiometry of the

q  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

v  Removal of oxygen atom!

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

OOx + ZnZn
→ 1
O2 ( g ) + Zni• + e "
Perfect Crystal ZnO  @  900  C  

K= pO2 .!"Zni• #$!"n#$ –1/4  

log σ

Zni• = n

σ ∞ n = ( const.) pO−1/4 log pO2


Example: Oxidation of Oxide in Cu2O

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

semiconductor (Cu2-xO)!

O2 ( g ) → OOx + 2VCu
" + 2h• Cu2O  @  1000  C  

! =p log σ


σ ∞ p = ( const.) pO1/8
log pO2

Ceramic Insulators
q  Do not have mobile charge carrier, and do not permit passage
of an electric current when placed in an electric field.!

q  Typical resistivity values (usually > 1014 Ω-cm):!

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

q  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

q  Temperature and impurities have strong effect on the
conductivity of insulating materials!

log σ
99.5%  BeO  
SiO2   1/σ

Al2O3   97%  BeO   99%  BeO  


Conducting Polymers

q  Valance band is full, conduction band is empty;

two bands are separated by a large Eg.!

q  They become conductive when doped with high %

of impurities (e.g., 1 atom for every 15 atoms of C).!

q  Conductivities similar to Cu have been achieved !!!

Next Class

Lecture 22
Application of Ceramics in
Electronic Devices