In the name of God

Energy bands and charge carriers

in semiconductors

Chapter 3
Mr. Harriry (Elec. Eng.)
By: Amir Safaei
2006
Outlines
3-1. Bonding Forces and Energy Bands
in Solids
3-1-1. Bonding Forces in Solids
3-1-2. Energy Bands
3-1-3. Metals, Semiconductors & Insulators
3-1-4. Direct & Indirect Semiconductors
3-1-5. Variation of Energy Bands with Alloy
Composition
2
Outlines
3-2. Carriers in Semiconductors
3-2-1. Electrons and Holes
3-2-2. Effective Mass
3-2-3. Intrinsic Material
3-2-4. Extrinsic Material
3-2-5. Electrons and Holes in Quantum
Wells

3
Outlines
3-3. Carriers Concentrations
3-3-1. The Fermi Level
3-3-2. Electron and Hole Concentrations at
Equilibrium

4
3-1. Bonding Forces & Energy
Bands in Solids
In Isolated Atoms
In Solid Materials Core
1st Band
2nd Band
3rd Band

5
3-1-1. Bonding Forces in
Solids
Na (Z=11) [Ne]3s1
Cl (Z=17) [Ne]3s1 3p5

_
Na+ Cl

6
3-1-1. Bonding Forces in
Solids

Na+
_
e

7
3-1-1. Bonding Forces in
Solids

8
 3-1-1. Bonding Forces in
Solids

<100> Si

9
 3-1-2. Energy Bands
Pauli Exclusion Principle

C (Z=6) 1s2 2s2 2p2

2 states for 1s level
2 states for 2s level
6 states for 2p level
For N atoms, there will be 2N, 2N, and 6N states
of type 1s, 2s, and 2p, respectively.
10
 3-1-2. Energy Bands
Conduction
band
4N States
2p
Energy

2p

Eg 2s-2p

2s
2s
4N States
Valence
Diamond band
lattice 1s
1s
spacing
Atomic separation 11
3-1-3. Metals, Semiconductors
& Insulators
For electrons to experience acceleration in an
applied electric field, they must be able to
move into new energy states. This implies
there must be empty states (allowed energy
states which are not already occupied by
electrons) available to the electrons.
The diamond structure is such that the
valence band is completely filled with
electrons at 0K and the conduction band is
empty. There can be no charge transport
within the valence band, since no empty
states are available into which electrons can
move.
12
 3-1-3. Metals, Semiconductors
& Insulators
Empty
The difference bet-
ween insulators and Empty
semiconductor mat- Eg
erials lies in the size Eg
of the band gap Eg, Filled
which is much small-
er in semiconductors Filled
than in insulators.
Insulator Semiconductor
13
 3-1-3. Metals, Semiconductors
& Insulators
In metals the bands
either overlap or are Overlap
only partially filled.
Thus electrons and
empty energy states Metal
Partially are intermixed with-
Filled in the bands so that
electrons can move
Filled freely under the infl-
uence of an electric
Metal field. 14
3-1-4. Direct & Indirect
Semiconductors
A single electron is assumed to travel
through a perfectly periodic lattice.
The wave function of the electron is assumed
to be in the form of a plane wave moving.
k ( x ) U ( k x , x )e jk x x

x : Direction of propagation
k : Propagation constant / Wave vector
: The space-dependent wave function for
the electron
15
3-1-4. Direct & Indirect
Semiconductors
U(kx,x): The function that modulates the
wave function according to the periodically of
the lattice.
Since the periodicity of most lattice is
different in various directions, the (E,k)
diagram must be plotted for the various
crystal directions, and the full relationship
between E and k is a complex surface which
should be visualized in there dimensions.
16
3-1-4. Direct & Indirect
Semiconductors
E E

Eg=h
Eg Et
k k

Direct Indirect
Example 3-1
17
 3-1-4. Direct & Indirect
Semiconductors

Example 3-1:
Assuming that U is constant in k ( x) U (k x , x)
e for an essentially free electron, show
jk x x

that the x-component of the electron

momentum in the crystal is given by

Px h k x
Example 3-2
18
 3-1-4. Direct & Indirect
Semiconductors
Answer: h jkx x

2 jk x x
U e (e )dx
j x
Px

U 2 dx

h k x U 2 dx


h kx

U 2 dx
The result implies that (E,k) diagrams such as shown
in previous figure can be considered plots of electron
energy vs. momentum, with a scaling factor h . 19
 3-1-4. Direct & Indirect
Semiconductors
Properties of semiconductor materials
Eg(eV) n p Lattice
Si 1.11 1350 480 2.5E5 D 5.43
Ge 0.67 3900 1900 43 D 5.66
GaAs 1.43 8500 400 4E8 Z 5.65
AlAs 2.16 180 0.1 Z 5.66
Gap 2.26 300 150 1 Z 5.45
20
 3-1-5. Variation of Energy
Bands with Alloy Composition
E E
3.0

2.8

2.6

2.4
L
X
L 2.2
X
0.3eV 2.0
X
1.43eV
2.16eV 1.8
L
k 1.6

AlxGaAs
AlAs
Ga1- 1.4
0 0.2 0.4 0.6 0.8 1 21
X
3-2. Carriers in Semiconductors

Ec

1487652309KK
300
18
14
15
20
19
11
12
13
17
16
10 Eg

Ev
Electron H
E Hole P
Pair
22
3-2-1. Electrons and Holes
E
-kj kj
k
j` j

0
NN
(qq))
J J( (VViiq)V(0j q)
q )V j
ii
23
3-2-2. Effective Mass
The electrons in a crystal are not free,
but instead interact with the periodic
potential of the lattice.
In applying the usual equations of
electrodynamics to charge carriers in
a solid, we must use altered values of
particle mass. We named it Effective
Mass.
24
 3-2-2. Effective Mass

Example 3-2:
Find the (E,k) relationship for a free
electron and relate it to the electron
mass.
E

k
25
 3-2-2. Effective Mass
Answer:
From Example 3-1, the electron momentum
is:
p mv h k
1 2 1 p2 h 2 2
E mv k
2 2 m 2m

d 2E h 2
2

dk m
26
 3-2-2. Effective Mass
Answer (Continue):
Most energy bands are close to parabolic at
their minima (for conduction bands) or
maxima (for valence bands).
EC

EV

27
3-2-2. Effective Mass
The effective mass of an electron in a band
with a given (E,k) relationship is given by
h2
m*
d 2E
dk 2

Remember that in GaAs:

E

L
X
m () m ( X
* *
or L)
1.43eV
k
28
3-2-2. Effective Mass
At k=0, the (E,k) relationship near the
minimum is usually parabolic:

h2 2
E *
k Eg
2m
d 2E
In a parabolic band, dk 2 is constant. So,
effective mass is constant.
h2
m*
d 2E
dk 2

Effective mass is a tensor quantity.

29
3-2-2. Effective Mass
2
d E
EV
2
0 m 0
*

dk h2
m*
d 2E
2
d E dk 2

EC 2
0 m 0
*

dk
Table 3-1. Effective mass values for Ge, Si and GaAs.

Ge Si GaAs
*
mn
0.55m0 1.1m0 0.067m0
*
m p 0.37m0 0.56m0 0.48m0

m0 is the free electron rest mass. 30

3-2-3. Intrinsic Material
A perfect semiconductor crystal with no
impurities or lattice defects is called an
Intrinsic semiconductor.
In such material there are no charge
carriers at 0K, since the valence band is
filled with electrons and the conduction
band is empty.
31
 3-2-3. Intrinsic Material

e-

Eg
Si
h+

n=p=ni 32
3-2-3. Intrinsic Material
If we denote the generation rate of EHPs
as g i ( EHP 3 ) and the recombination rate
cm s
as ri ( EHP 3 ) equilibrium requires that:
cm s
ri g i
Each of these rates is temperature depe-
ndent. For example, g (T ) increases when
i
the temperature is raised.
ri r n0 p0 n g i2
r i
33
 3-2-4. Extrinsic Material
In addition to the intrinsic carriers generated
thermally, it is possible to create carriers in
semiconductors by purposely introducing
impurities into the crystal. This process, called
doping, is the most common technique for
varying the conductivity of semiconductors.
When a crystal is doped such that the equilibrium
carrier concentrations n0 and p0 are different from
the intrinsic carrier concentration ni , the material
is said to be extrinsic. 34
 3-2-4. Extrinsic Material

V Ec
Ed
P
50
14
15
20
191487652309KKK
18
11
12
13
17
16
10
As
Ev
Sb Donor
35
 3-2-4. Extrinsic Material

Ec
B
50
14
15
20
191487652309KKK
18
11
12
13
17
16
10
Al
Ea
Ga Ev
In Acceptor
36
3-2-4. Extrinsic Material

e- Sb
h+
Al Si

37
3-2-4. Extrinsic Material
We can calculate the binding energy
by using the Bohr model results,
consider-ing the loosely bound
electron as ranging about the tightly
bound core electrons in a
hydrogen-like orbit.
4
mq
E 2 2
; n 1 , K 4 0 r
2K h 38
 3-2-4. Extrinsic Material

Example 3-3:
Calculate the approximate donor binding
energy for Ge(r=16, mn*=0.12m0).

39
 3-2-4. Extrinsic Material
Answer:
* 4
mq
E n
8( 0 r ) h
2 2

31 19 4
0.12(9.1110 )(1.6 10 )
12 34 2
8(8.85 10 16) (6.63 10 )
2

21
1.02 10 J 0.0064eV
Thus the energy to excite the donor electron from
n=1 state to the free state (n=) is 6meV. 40
3-2-4. Extrinsic Material
When a -V material is doped with Si
or Ge, from column IV, these impurities
are called amphoteric.
In Si, the intrinsic carrier concentration
ni is about 1010cm-3 at room tempera-
ture. If we dope Si with 1015 Sb Atoms/cm3,
the conduction electron concentration
changes by five order of magnitude.
41
 3-2-5. Electrons and Holes in
Quantum Wells

One of most useful applications of MBE

or OMVPE growth of multilayer compou-
nd semiconductors is the fact that a
continuous single crystal can be grown
in which adjacent layer have different
band gaps.
A consequence of confining electrons
and holes in a very thin layer is that
42
3-2-5. Electrons and Holes in
Quantum Wells
these particles behave according to the
particle in a potential well problem.
Al0.3Ga0.7As GaAs Al0.3Ga0.7As
50
E1
0.28eV

1.85eV 1.43eV
0.14eV
Eh 43
3-2-5. Electrons and Holes in
Quantum Wells
Instead of having the continuum of states
as described by En
n
2 2 2
h , modified for
2
2mL
effective mass and finite barrier height.

Similarly, the states in the valence band

available for holes are restricted to discrete
levels in the quantum well.

44
3-2-5. Electrons and Holes in
Quantum Wells
An electron on one of the discrete condu-
ction band states (E1) can make a transition
to an empty discrete valance band state in
the GaAs quantum well (such as Eh), giving
off a photon of energy Eg+E1+Eh, greater
than the GaAs band gap.

45
3-3. Carriers Concentrations
In calculating semiconductor electrical pro-
perties and analyzing device behavior, it is
often necessary to know the number of
charge carriers per cm3 in the material. The
majority carrier concentration is usually
obvious in heavily doped material, since
one majority carrier is obtained for each
impurity atom (for the standard doping
impurities).
The concentration of minority carriers is not
obvious, however, nor is the temperature
dependence of the carrier concentration. 46
 3-3-1. The Fermi Level
Electrons in solids obey Fermi-Dirac statistics.
In the development of this type of statistics:
Indistinguishability of the electrons
Their wave nature
Pauli exclusion principle
must be considered.
The distribution of electrons over a range of
these statistical arguments is that the distrib-
ution of electrons over a range of allowed
energy levels at thermal equilibrium is
47
 3-3-1. The Fermi Level
1
f (E) ( E E f )
1 e kT

k : Boltzmanns constant
f(E) : Fermi-Dirac distribution function
Ef : Fermi level

48
3-3-1. The Fermi Level
1 1 1
f (E f ) ( E f E f )
1 e kT 11 2

f(E)
1
T >T1
T=0K
1>0K
2
1/2
E
Ef
49
 3-3-1. The Fermi Level
E
f(Ec) f(Ec)

Ec

Ef
[1-f(Ec)]
Ev

f(E) Intrinsic
p-type
n-type
1 1/2 0 50
3-3-2. Electron and Hole
Concentrations at Equilibrium
The concentration of electrons

in the
conduction band is n0 f ( E ) N ( E )dE
EC

N(E)dE : is the density of states (cm-3)

in the energy range dE.
The result of the integration is the
same as that obtained if we repres-
ent all of the distributed electron
states in the conduction band edge
EC.
n0 NC f ( EC )
51
 3-3-2. Electron and Hole
Concentrations at Equilibrium
E
Electrons
N(E)f(E)
EC
Ef

N(E)[1-f(E)] EV
Holes

Intrinsic
p-type
n-type
52
3-3-2. Electron and Hole
Concentrations at Equilibrium

1 ( EC EF )
f ( EC ) ( EC EF ) e kT

1 e kT

( EC EF )
n0 NC e kT

2 mn* kT 3 2
N C 2( 2
)
h

53
3-3-2. Electron and Hole
Concentrations at Equilibrium

p0 NV [1 f ( EV )]

1 ( EF EV )
1 f ( EV ) 1 ( EV EF ) e kT

1 e kT

( EF EV )
p0 NV e kT

2 m*p kT
NV 2(
3
) 2

h2
54
 3-3-2. Electron and Hole
Concentrations at Equilibrium
( Ec Ei ) ( Ei Ev )
ni NC e kT
pi NV e kT

( Ec Ev ) Eg
n0 p0 N c N v e kT
Nc Nve kT

Eg Eg

ni pi N c N v e kT
ni Nc Nv e 2 kT

n0 p0 n 2
i

( EF Ei ) ( Ei EF )
n0 ni e kT
p0 ni e kT

55
 3-3-2. Electron and Hole
Concentrations at Equilibrium

Example 3-4:
A Si sample is doped with 1017 As Atom/cm3.
What is the equilibrium hole concentra-
tion p0 at 300K? Where is EF relative to
Ei?

56
 3-3-2. Electron and Hole
Concentrations at Equilibrium
Answer:
Since Ndni, we can approximate n0=Nd
and
ni2 2.25 1020 3
p0 17
2.25 10 3
cm
n0 10
( EF Ei )
n0 ni e kT

n0 1017
EF Ei kT ln 0.0259 ln 0.407eV
ni 1.5 1010

57
 3-3-2. Electron and Hole
Concentrations at Equilibrium
Answer (Continue) :

Ec
EF
0.407eV
1.1eV Ei

Ev

58
References:
Solid State Electronic Devices
Ben G. Streetman, third edition

Modular Series on Solid State Devices,

Volume I: Semiconductor Fundamentals
Robert F. Pierret

59