Solid State Physics

Semiconductor Materials
Dr. rer. nat. Muldarisnur

JURUSAN FISIKA UNIVERSITAS ANDALAS

 Introduction
The name “semiconductor” implies that it conducts somewhere between
the two cases (conductors or insulators)

Category of materials based on range of conductivity

Conductivity : s
s metals ~ 1010/Ω-cm
The conductivity (σ) of a
Semiconductor semiconductor (S/C) lies
between these two extreme
cases.
s insulators ~ 10-22/Ω-cm

Solid State Physics Dr. rer. nat. Muldarisnur 2

 Introduction

Second allowed band

Forbidden band E g F
First allowed band

  k
 0
a a

Category of materials based on electronic structure

1) If the band is partially filled a metal
2) If bandgap is greater than 3.2 eV a insulator (no visible light can
be absorbed)
3) bandgap is less than ~ 2.5 eV a semiconductor

Solid State Physics Dr. rer. nat. Muldarisnur 3

 Periodic Table

Solid State Physics Dr. rer. nat. Muldarisnur 4

 Introduction
Important semiconductor materials are

 Group IV: Si, Ge (diamond structure)

Si, Eg (at RT) ~ 1.12 eV, Indirect bandgap

Ge, Eg (at RT) ~ 0.67 eV

SiC (zincblende structure), Eg (at RT) ~ 2.86 eV,

 Group III-V: GaAs, InSb, GaN, AlP (zincblende structure)

GaAs, Eg (at RT) ~ 1.43 eV, Direct bandgap

InSb, , Eg (at RT) ~ 0.17 eV,
GaN, Eg (at RT) ~ 3.4 eV,
InP, Eg (at RT) ~ 2.45 eV,
Solid State Physics Dr. rer. nat. Muldarisnur 5
 Introduction
The properties of semiconductor is dominated by electrons in states close
to the top of the valence band and the bottom of the conduction band


Conduction band
2
k2
  Eg 
2me

Eg

k
 2k 2
The states near the top of the  
valence band behave like free 2mh
particles of negative mass mh
Valence band
The behavior of a nearly full valence band can be calculated by ignoring the
filled states completely and regarding each empty state as being occupied
by a particle of positive charge lel positive mass mh and energy  2 k 2 / 2mh.
a This fictious particles are referred to as holes.
Solid State Physics Dr. rer. nat. Muldarisnur 6
 Holes
From the conservation of energy, the energy required to create electron in
state k1 and hole in state k
 2 k12   2 k 2    2 k12    2 k 2 
  Eg        E g     
2me  2mh   2me   2mh 

Identified as an energy Identified as an energy
of Electron in state k1 of hole in state k

Hole dispersion relation

a obtained from  Hole has
inverting the dispersion  2k 2
h 
relation of valence band 2mh
 
electron  2k 2 ph  k
h 
2mh

k

Similarly, the removal of an electron momentum k from the valence band

corresponds to the addition of momentum  k to the valence band.
Solid State Physics Dr. rer. nat. Muldarisnur 7
 Holes
The equation of motion for a hole
+ sign

    
 dvh vh 
mh     e( E  vh  B)
 dt  h 

The scattering of a hole from state k1 to state k 2 corresponds to the

scattering of an electron from state k 2 to state k1 so that the scattering
time for holes  h is directly related to that for electrons.

Solid State Physics Dr. rer. nat. Muldarisnur 8

 Band Structure of Semiconductors
4 4
Conduction Conduction
GaAs Si
band band
3 3

2 2
Energy (eV)

Energy (eV)
1 1
Eg Eg

0 0

-1 -1
Valance Valance
band band
-2 -2
[111] 0 [100] k [111] 0 [100] k

Energy band structures of GaAs and Si

Solid State Physics Dr. rer. nat. Muldarisnur 9
 Band Structure of Semiconductors
4
GaAs Conduction Band gap is the smallest energy
band separation between the valence
3
and conduction band edges.

2
Energy (eV)

ΔE=0.31
1
Eg The smallest energy difference occurs
at the same momentum value
0

-1
Valance Direct band gap semiconductor
-2 band
[111] 0 [100] k
Energy band structure of GaAs
Solid State Physics Dr. rer. nat. Muldarisnur 10
 Band Structure of Semiconductors
4
Conduction
Si
band
3
The smallest energy gap is between
2 the top of the VB at k=0 and one of
the CB minima away from k=0
Energy (eV)

1
Eg

0
Indirect band gap semiconductor

-1
Valance
band
-2
[111] 0 [100] k

Energy band structure of Si

Solid State Physics Dr. rer. nat. Muldarisnur 11
Methods of Providing Electrons and Holes
Donor and acceptor impurities

 The conductivity of a pure (intrinsic) s/c is low due to the low number of
free carriers (The number of carriers are generated by thermally or
electromagnetic radiation for a pure s/c)

 To increase the conductivity, one can dope pure s/c with atoms from
column lll or V of periodic table. This process is called as doping and the
added atoms are called as dopants impurities.

 This impurities takes up a substitutional rather than an interstitial

position.

 After forming four covalent bonds demanded by the structure, there is

an extra valence electron (hole) leading occupied states in the
conduction band (empty states in the valence band)

Solid State Physics Dr. rer. nat. Muldarisnur 12

Methods of Providing Electrons and Holes
Donor and acceptor impurities
 n-type doped semiconductor
 Si + Column V impurity atoms

Si Weakly bound
electron

Si V Si

Normal
Si bond with
two
electrons

Solid State Physics Dr. rer. nat. Muldarisnur 13

Methods of Providing Electrons and Holes
Donor and acceptor impurities
 p-type doped semiconductor
 Si + Column III impurity atoms

Si Weakly bound
hole

Si III Si

Normal
Si bond with
two
electrons

Solid State Physics Dr. rer. nat. Muldarisnur 14

Methods of Providing Electrons and Holes
Donor and acceptor impurities
 The extra electron from dopant is not completely free since escape of
electron to large distances leaves the impurity atoms with a net positive
charge; at finite separations the positive charge exerts an attractive
force on the electron and leads to the existence of a bound state for the
electron.
 The strength of binding between charged impurity and electron can be
estimated by employing standard result for the energy levels of the
hydrogen atom
 The energy level of hydrogen atom given by :

mee 4 13.6eV Ry
En   2 2    2 Ry is Rydberg
2  4 0  constant
2
n n
4 0n 2 2 
and Bohr radius is a0  2
 0.529 A
me e
Solid State Physics Dr. rer. nat. Muldarisnur 15
Methods of Providing Electrons and Holes
Donor and acceptor impurities
In medium with dielectric constant 
m * e4
En   2 2 2  n2 2

rn  4 0
2 n  4 0 
2
2
m*e
For germanium, the effective mass is m*  0.2me , and dielectric constant is
  15.8
 m*   me  o o
E1    13.6eV  -0.01eV, r1  
2 
  0.53 A  40 A
 me   m* 
a the combination of small effective mass and large dielectric constant
gives very weak binding of the extra electron to the impurity and a very
extended wavefunction for the bound state.

Note E1 is less than k BT at room temperature (0.026 eV)

a most of electrons provided by doping free to move through the crystal
Solid State Physics Dr. rer. nat. Muldarisnur 16
Methods of Providing Electrons and Holes
Donor and acceptor impurities
At T = 0, all extra electrons
Occupy at donor level. 

Conduction band
At finite T, thermal energy
can ionize extra electrons
into the conduction bands
ED
EG  ED Donor level
Eg
EA EA Acceptor level
k

Valence band

Solid State Physics Dr. rer. nat. Muldarisnur 17

Methods of Providing Electrons and Holes
Thermal excitation of carriers
The probability of occupation of a state of energy  is given by

1
f ( , T ) 
e (    ) / k BT  1
At T = 0, electron occupy up to  , so that Fermi energy is referred to
 F   (T  0)

At finite T, we define Fermi level as    (T )

Solid State Physics Dr. rer. nat. Muldarisnur 18

Methods of Providing Electrons and Holes
Thermal excitation of carriers
The density of states for conduction and valence band are given from
dispersion relation
V
Conduction band: g ( )  ( 2 m ) 3/ 2
(  E )1/ 2

2 2  3
e g

V
Valence band: g ( )  ( 2 m ) 3/ 2
(  )1/ 2

2 2  3 e

g ( ) NA ND

g ( )
The Fermi level
is somewhere
f ( )
in the band gap.

0 EA EG 

EG  ED

The Fermi function is very close to the unity in the valence band and very
small in the conduction band.
Solid State Physics Dr. rer. nat. Muldarisnur 19
Methods of Providing Electrons and Holes
Thermal excitation of carriers
The analytic expressions for the # of electrons in the conduction band and
the # of holes in the valence band
For the electron energy  in the conduction band,     k BT
f ( )  e (   ) / k BT
The # of electron per unit volume in the conduction band
1  1 
n  E f ( ) g ( )d   2 3 E (2me )3/2 (  EG )1/2 e(   )/ k T d 
B

V G
2 G

(2me )3/2 (   E )/ k T  1/2  / k T

 e G B
  e B
d   N e (   E )/ k T
G B

2 2 3 0 C

3/ 2

 2me k BT 
n  N C e (   EG ) / k BT N C  2
where 
 h 
2

Nc is the effective number of states per unit volume in the conduction band
if we imagine them concentrated at the bottom of the band,   EG
n  N C f ( EG )
Solid State Physics Dr. rer. nat. Muldarisnur 20
 Gamma Function - Reminder
 (n  1)
0
x n e  ax dx 
a n 1
,

(n  1)  n!
(1 / 2)  
1 3  5    (2m  1)
(m  1 / 2)  m
, m  1,2,3,....
2

Solid State Physics Dr. rer. nat. Muldarisnur 21

Methods of Providing Electrons and Holes
Thermal excitation of carriers
The probability that a state in the valence band is occupied by a hole is , 1  f ( )
1 e (    ) / k BT 1
1  f ( )  1   (    ) / k BT  (   ) / k B T
e (    ) / k BT 1 e 1 e 1
For (    )  k BT , 1  f ( )  e (   ) / k BT
1 0
p   [1  f ( )]g ( )d
V 
(2mh )3 / 2 0
2 3  
1 / 2 (    ) / k BT
 (  ) e d
2 
(2mh )3 / 2   / k BT  1/ 2  / k BT

2 
2 3
e  0
 e d

 NV e   / k B T , 3/ 2

 2mh k BT 
p  NV e   / k BT
where N V  2 
 
2
h
Nv is the effective number of states per unit volume in the valence band if
they were all concentrated at the top of the band,   0 p  NV [1  f (0)]
Solid State Physics Dr. rer. nat. Muldarisnur 22
Methods of Providing Electrons and Holes
Thermal excitation of carriers

n  N C e (   EG ) / k B T
p  NV e   / k BT

The product of hole and electron concentration

np  N C NV e  EG / k BT Law of mass action

Independent of  and impurity concentration, but it depends on the

temperature

Solid State Physics Dr. rer. nat. Muldarisnur 23

Methods of Providing Electrons and Holes
For Intrinsic Semiconductor
For pure semiconductor, the electron and hole concentrations are equal
since a hole in the valence band can only be created by the excitation of an
electron into the conduction band.
n  N C e (   EG ) / k B T
The intrinsic carrier concentrations are   / k BT
p  N e
ni  pi  N C NV  e  EG / 2 k BT
1/ 2 V

The typical intrinsic carrier concentration at RT for Si: (2×1016m-3)

Ge: (2×1019m-3)
The chemical potential of an intrinsic semiconductor can be expressed
n / p  N C e (   EG ) / k BT / NV e   / k BT  1
( 2   EG ) / k BT
a e  NV / N C
1 1 1 3
a   E G  k B T ln( N V / N C )  EG  k BT ln( mh / me )
2 2 2 4
Typically, the Fermi level (chemical potential) is essentially in the middle of
the band gap since k BT  EG
Solid State Physics Dr. rer. nat. Muldarisnur 24
Methods of Providing Electrons and Holes
Intrinsic behavior

The product of electron and hole concentrations in any semiconductor is

often expressed as
np  ni2 (T )

Practically, it is impossible to have ideally pure semiconductor, there will

be always some impurities

The criterion for intrinsic semiconductor is The content of impurities

should be less than

ND < 2×1016m-3 for Si 1 in 1012 for Si

ND < 2×1019m-3 for Ge 1 in 109 for Ge

The atomic concentration is 5×1028

Solid State Physics Dr. rer. nat. Muldarisnur 25

Methods of Providing Electrons and Holes
Extrinsic behavior
When acceptors and donors are present, chemical potential changes

We determine chemical potential based on the electrical neutrality of the

whole crystal.

The condition for electrical neutrality requires the densities of negative

and positive charge associated with should be equal.
n  N A  p  N D

N A : concentrations of ionized acceptors

N D : concentrations of ionized donors

N A  N A f ( E A ) N D  N D [1  f ( EG  ED )]

Solid State Physics Dr. rer. nat. Muldarisnur 26

Methods of Providing Electrons and Holes
Extrinsic behavior
Typically, both types of impurities (donors and acceptors) present in actual
semiconductor materials
Consider n doped semiconductor a # of donors exceed # of acceptors
i) At T = 0,
a All acceptor levels are fully occupied by electrons from the donor impurities
a N D  N A donor levels un-ionized
a Fermi energy,  F   (T  0)  EG  ED
ii) At low T ( k BT  ED ),
a Donors are started to be ionized but its number have changed much yet.
a The Fermi level still close to the Fermi energy  (T )  EG  ED n  N C e (   EG ) / k BT
a The electron concentration at conduction band p  NV e   / k BT
 ni  N C NV  e  EG / 2 k BT
 E D / k BT 1/ 2
n  NC e
since ED  EG
a From law of mass action, p  pi
a Electron is majority carrier, hole is minority carrier (n-type materials)
Solid State Physics Dr. rer. nat. Muldarisnur 27
Methods of Providing Electrons and Holes
Extrinsic behavior
Typically, both types of impurities (donors and acceptors) present in actual
semiconductor materials
Consider n doped semiconductor, a # of donors exceed # of acceptors
i) As T increase
a The # of ionized donors becomes comparable to the total # of donors
a The probability of occupation of donor level becomes low
a Fermi level lies below the donor level
a For some range of T, all the donors and acceptors are ionized
n  ND  N A n  N C e (   EG ) / k B T
a Then the Fermi level can be obtained as p  N e   / k BT
V
 NC 
  EG  k BT ln  
 ND  N A 
For a good semiconductor device operation, all the impurities should be
ionized at room temperature.
Solid State Physics Dr. rer. nat. Muldarisnur 28
Methods of Providing Electrons and Holes
Extrinsic behavior
Typically, both types of impurities (donors and acceptors) present in actual
semiconductor materials
Consider n doped semiconductor, a # of donors exceed # of acceptors

i) As T increase further,
a The # of carriers induced by the thermal activation exceed the doping
a Hole concentration increases towards the electron concentration
a Fermi level falls towards the centre of the gap
a Eventually, it behave like intrinsic semiconductors

Solid State Physics Dr. rer. nat. Muldarisnur 29

Methods of Providing Electrons and Holes

1/T (K-1)
n,p
(m-3)

1/T (K-1)
Solid State Physics Dr. rer. nat. Muldarisnur 30
Methods of Providing Electrons and Holes
Extrinsic behavior
Typically, both types of impurities (donors and acceptors) present in actual
semiconductor materials
Consider p doped semiconductor, a # of acceptors exceed # of donors
i) At T = 0,
a All donor levels are empty by acceptor impurities
a N A  N D Empty acceptor levels
a Fermi energy, F   (T  0)  E A
ii) At low T (k BT  ED ),
a Acceptors are started to be ionized but its number haven’t changed
much yet. n  N C e (   EG ) / k B T
a The Fermi level still close to the Fermi energy  (T )  E A   / k BT
a The hole concentration at valence band p  N V e
p  N C e  E A / k BT  pi  N C NV 1/ 2 e  EG / 2 k BT
a From law of mass action, n  ni since E A  EG
a Hole is majority carrier, electron is minority carrier (p-type materials)
Solid State Physics Dr. rer. nat. Muldarisnur 31
Methods of Providing Electrons and Holes
Extrinsic behavior
Typically, both types of impurities (donors and acceptors) present in actual
semiconductor materials
Consider p doped semiconductor, a # of acceptors exceed # of donors
i) As T increase
a The # of occupied acceptors becomes comparable to the total # of
acceptors
a The probability of occupation of acceptor level becomes high
a Fermi level lies above the acceptor level n  N e (   EG ) / k B T
C
a For some range of T, all the acceptors are ionized p  NV e   / k BT
p  N A  ND
a Then the Fermi level can be obtained as
 NV 
  k BT ln  
 N A  ND 
For a good semiconductor device operation, all the impurities should be
ionized at room temperature.
Solid State Physics Dr. rer. nat. Muldarisnur 32
Methods of Providing Electrons and Holes
Extrinsic behavior

Typically, both types of impurities (donors and acceptors) present in actual

semiconductor materials
Consider p doped semiconductor, a # of acceptors exceed # of donors

i) As T increase further,
a The # of carriers induced by the thermal activation exceed the doping
a electron concentration increases towards the hole concentration
a Fermi level rise towards the centre of the gap
a Eventually, it behave like intrinsic semiconductors

Solid State Physics Dr. rer. nat. Muldarisnur 33

Absorption of Electromagnetic Radiation
Sharp increase of

Absorption coefficient (cm-1)

The absorption absorption occur at two
coefficient for place
electromagnetic
radiation of germanium
a this is due to the fact
vs photon energy at
that germanium has
temperature 77 and
300 K. indirect band-gap
structure

Photon energy (eV)

The increase in absorption occur when the photons have sufficient energy
to excite a valence band electron into the conduction band
a the photon energies at the onset of absorption therefore provide a
measure of the energy gap in semiconductors
Solid State Physics Dr. rer. nat. Muldarisnur 34
Absorption of Electromagnetic Radiation

The absorption and emission of

photon (or phonon) should satisfy
1) conservation of energy Eg E g'
2) conservation of momentum

   ph k  k ph k[111]

Photon has sufficient energy to overcome bandgap but has small momentum
For visible light, 2   ph  3eV k  h /   ~ 103 nm
For conduction electron,  ~ R
Phonon has low energy but has momentum comparable to conduction
 phonon ~ k B  k phonon  h / R
Solid State Physics Dr. rer. nat. Muldarisnur 35
Absorption of Electromagnetic Radiation

The absorption and emission of

photon (or phonon) should satisfy photon   Eg'
1) conservation of energy
k 0
2) conservation of momentum

   ph k  k ph k[111]

Photon has sufficient energy to overcome bandgap but has small momentum
For visible light, 2   ph  3eV k  h /   ~ 103 nm

For conduction electron,  ~ R

Phonon has low energy but has momentum comparable to conduction
 phonon ~ k B  k phonon  h / R
Solid State Physics Dr. rer. nat. Muldarisnur 36
Absorption of Electromagnetic Radiation

The absorption and emission of

photon (or phonon) should satisfy phonon  ~ 0 photon   E g'
1) conservation of energy k  k0 k 0
2) conservation of momentum

   ph k  k ph k[111]

Photon has sufficient energy to overcome bandgap but has small momentum
For visible light, 2   ph  3eV k  h /   ~ 103 nm

For conduction electron,  ~ R

Phonon has low energy but has momentum comparable to conduction
 phonon ~ k B  k phonon  h / R
Solid State Physics Dr. rer. nat. Muldarisnur 37
 Transport Properties
The equation of motion for the carriers in the presence of electric and
magnetic fields
 dv v   dv v 
me  e  e   e( E  ve  B ) mh  h  h   e( E  vh  B )
 dt  e   dt  h 
e e e e
Electrical conductivity ve   E   e E  e

me me
In steady state, e h e h
vh  E  h E h 
mh mh
 ne 2 e pe 2 h 
j  neve  pevh     E  (nee  peh ) E  s E
 me mh 
s  nee  peh
 In the intrinsic region, contribution of electrons and holes to the
conductivity are usually similar
 In the extrinsic region, conductivity is normally dominated by the majority
carrier
Solid State Physics Dr. rer. nat. Muldarisnur 38
 Transport Properties
Extrinsic region: all donors
are excited

Conductivity (W-1m-1)
a s  10 3
W 1 1
m

The dashed line a e  1m 2 V 1s 1 from e  10 19 C

indicate steep increase
a  e  10
12
s me  10 31 kg
associated with the from
transition to the
intrinsic behavior Thermal activation of
donor
Scattering with 1/T (K)
phonon

Conductivities for arsenic-doped n-type germanium.

Arsenic donor impurities with the approximate
concentrations indicated.

Solid State Physics Dr. rer. nat. Muldarisnur 39

 Hall effect

In steady state, the Lorentz force  ev  B on the

electrons is just balanced by the force EH

due to the Hall field  eEH
EH  RH B  j

v i j k
 eE  ev  B
e   vx 0 0
me
  
mevx /   eEx  0 0 Bz 

a 0  e( E y  v x B )

a E y  v x B  j x B /(ne)  RH j x B

RH  1 / ne and   RH s
Solid State Physics Dr. rer. nat. Muldarisnur 40
 Hall effect
The Hall Effect in Semiconductor The Hall measurement
1 1 determine the majority
RH   RH 
ne pe carrier, carrier concentration,
in n-type in p-type and mobility
semiconductor (n>>p) semiconductor (p>>n)
  RH s
1 1
Consider arsenic-doped n-type germanium RH    22 19  103 WmT 1
ne 10 10
in previous section
Since resistivity is 1 / s  103 Wm
a the Ohmic and Hall electric fields are equal in a field of 1T
a the total electric field is 45 degree to the current flow, (Hall angle = 45°)
a We define this magnetic field as Hall field B0 (Hall field is B0 
1

1
useful measure of the strength of the Hall effect) RH s 
The Hall effect in semiconductors is much larger than in
metals due to smaller carrier density
Solid State Physics Dr. rer. nat. Muldarisnur 41
 Questions? Discussion?

Dosen : Dr.rer.nat. Muldarisnur

Ruangan : Jurusan Fisika

E-mail : [email protected]

Telpon : 081378971***

The best way to handle exams is to be well-prepared.

Push yourself, because nobody else will do that for you…

Solid State Physics Dr. rer. nat. Muldarisnur 42