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 So
lids

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 Comp
2
osition

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

3-1. Bonding Forces &

Energy Bands in Solids

In Isolated Atoms
In Solid Materials

Core
1st Band
2nd Band
3rd Band

3-1-1. Bonding Forces in

Solids

Na (Z=11) [Ne]3s1
Cl (Z=17) [Ne]3s1 3p5

Na+ Cl

3-1-1. Bonding Forces in

Solids

Na+
e

_
7

3-1-1. Bonding Forces in

Solids

3-1-1. Bonding Forces in

Solids

<100>

Si

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

Energy

4N States

Conduction
band
2p

Eg

2s-2p

2s
4N States

Diamond
lattice
spacing

2p

2s

Valence
band
1s

Atomic separation

1s
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

The difference between

insulators
and semiconductor
mat-erials lies in
the size of the
band gap Eg, which
is much small-er in
semiconductors
than in insulators.

Empty

Empty
Eg

Eg
Filled

Filled
Insulator

Semiconductor
13

3-1-3. Metals,
Semiconductors &
Insulators
In metals the bands
either overlap or are
only partially filled.
Thus electrons and
empty energy states
Partially
Filled
Filled
Metal

Overlap

Metal

are intermixed within the bands so that

electrons can move
freely under the
infl-uence of an
electric 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

Eg=h

Eg

Et
k

Direc
t

Indirect

Example 3-1
17

3-1-4. Direct & Indirect

Semiconductors

Example 3-1:

Assuming that U is constant ink ( x) U (k x , x)

jk x x
e for an essentially free electron, show
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:

Px

h jk x x
(e )dx
j x

2 jk x x

U e

U 2 dx

h k x U 2 dx

U dx

h kx

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 factorh .
19

3-1-4. Direct & Indirect

Semiconductors
Properties of semiconductor materials
Eg(eV)

Si
Ge
GaAs
AlAs
Gap

Lattice

1.11 1350
480 2.5E5
0.67 3900 1900
43
1.43 8500 400 4E8
2.16
180
0.1
2.26
300
150
1

D 5.43
D 5.66
Z 5.65
Z 5.66
Z 5.45
20

3-1-5. Variation of Energy

Bands with Alloy
3.0
E
Composition

E
2.8
2.6

L
0.3eV

2.4

2.2
X

2.0

1.43eV
2.16eV
AlxGaAs
AlAs
Ga1-xAs

X
1.8

k 1.6
1.4
0

0.2

0.4

0.6

0.8

121

3-2. Carriers in
Semiconductors
E
c

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

E
g

E
v

Electron H
Hole P
Pair
E
22

3-2-1. Electrons and Holes

E
-kj

kj

j`

j
0

NN

(qq))
q )V j
J J(
(VViiq)V(0j q)
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

m*

h2
d 2E

dk 2

Remember that in
GaAs: E
L

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.
m*

h2
d 2E

dk 2

Effective mass is a tensor quantity.

29

3-2-2. Effective Mass

EV

d E
0
2
dk
2

EC

d E
0
2
dk

m 0
*

m*

h2
d 2E

dk 2

m 0
*

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

Ge
*

m
m

n
*
p

Si

GaAs

0.55m0

1.1m0

0.067 m0

0.37 m0

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

eEg

Si

h+

n=p=ni

32

3-2-3. Intrinsic Material

If we denote the generation rate of

EHPs
as
g ( EHP

and the

cm3 s
recombination
rate as
EHP
ri (
3 )
cm s
i

equilibrium requires that:

ri g i

Each of these rates is temperature dependent. For example,

g i (T )

increases when

the temperature is raised.

ri r n0 p0 n g i
2
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

E

V
P

50
18
14
15
20
19
11
12
13
17
16
1487652309KKK
10

As
Sb

Donor

v
35

3-2-4. Extrinsic Material

E
c

B
Al

50
18
14
15
20
19
11
12
13
17
16
1487652309KKK
10

Ga
In

E
E

Acceptor

v
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
; n 1 , K 4 0 r
2 2
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:

*
n

mq
E
2 2
8( 0 r ) h
31

19 4

0.12(9.11 10 )(1.6 10 )

12
2
34 2
8(8.85 10 16) (6.63 10 )
1.02 10

21

J 0.0064eV

Thus the energy to excite the donor

electron from n=1 state to the free state

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

GaA
s
50

E1

1.85e
V

1.43e
V

Eh

Al0.3Ga0.7As

0.28e
V
0.14e
V 43

3-2-5. Electrons and Holes

in Quantum Wells

Instead of having the continuum of states

n 2 2 h 2 , modified for
En
2
effective mass and finite
barrier height.
2mL
as described by

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 conduction 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 properties and analyzing device behavior, it is

often necessary to know the number of
charge carriers per cm 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.
3

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 distribution 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 )
kT
1 e

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

distribution

Ef : Fermi level
48

3-3-1. The Fermi Level

f (E f )

1
1 e

( E f E f )

kT

1
1

11 2

f(E)
1

T=0K
T
>0K
12>T
1

1/2
Ef

E
49

3-3-1. The Fermi Level

E
f(Ec
)

f(Ec
)

E
Ef
[1f(Ec)
]

f(E)

1/2

Intrinsic
p-type
n-type

50

3-3-2. Electron and Hole

Concentrations at
Equilibrium
The concentration of electrons
in

the conduction band

n0 is f ( E ) N ( E )dE
E

N(E)dE : is the density of states

(cm ) in the energy range dE.
-3

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 N C f ( EC )

51

3-3-2. Electron and Hole

Concentrations at
Equilibrium
E
Electrons

N(E)f(E)

EC
Ef
EV

N(E)[1-f(E)]
Holes
Intrinsic
p-type
n-type

52

3-3-2. Electron and Hole

Concentrations at
Equilibrium
f ( EC )

1
1 e

( EC EF )

n0 N C e

kT

( EC EF )

( EC EF )

kT

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 f ( EV ) 1

1
1 e

p0 N V e
N V 2(

( EV EF )

( EF EV )

2 m*p kT
h2

kT

( EF EV )

kT

kT

54

3-3-2. Electron and Hole

Concentrations at
Equilibrium
p N e
n N e
( Ec Ei )

kT

n0 p0 N c N v e
ni pi N c N v e

Eg

( Ei Ev )

( Ec Ev )

kT

kT

kT

Eg

N c N v e kT
Eg
ni N c N v e 2 kT

n0 p0 n

2
i

n0 ni e

( EF Ei )

kT

p0 ni e

( Ei EF )

kT

55

3-3-2. Electron and Hole

Concentrations at
Equilibrium

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

56

3-3-2. Electron and Hole

Concentrations at
Equilibrium
Answer:
Since Ndni, we can approximate
n0=Nd and

ni2 2.25 10 20
3
3
p0

2
.
25

10
cm
17
n0
10

n0 ni e

( EF Ei )

kT

n0
1017
E F Ei kT ln 0.0259 ln
0.407eV
10
ni
1.5 10

57

3-3-2. Electron and Hole

Concentrations at
Equilibrium
Answer (Continue) :

1.1eV

0.407eV

Ec
EF
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