Chapter

ELECTRONS IN
SEMICONDUCTORS

In this chapter we present gures discussing the behavior of electrons in crystalline solids.
 ELECTRONS IN PERIODIC STRUCTURES:
ELECTRONIC BANDSTRUCTURE (E vs. k relation)

To examine electrons inside a solid we need to use

quantum mechanics, i.e., the Schrödinger equation

–h2
[ 2mo ]
2 + V(r) ψ(r) = E ψ(r)

ψ(r): electronic state or wavefunction.

E : electronic allowed energy or eigenvalue.
V(r) : background potential which is periodic in
crystals.

In general the problem is extremely complex to

solve:
There are ~1023 atoms cm–3!

The problem becomes tractable because there is

periodicity in the system. The entire crystal is
produced by a repetition of a few atoms. This
allows us to rewrite the problem in terms of just
a unit cell problem.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 BLOCH THEOREM:
The general form of an electronic state
(wavefunction) in a periodic structure is:
ψk(r) = uk(r)eik•r
uk(r) = uk(r+R): uk(r) has the same periodicity
as the crystal.

NON-PERIODIC POTENTIAL

U(r)
r

|ψ(r)|2
r
(a)

PERIODIC
POTENTIAL

U(r)
r

|ψ(r)|2 = u(r)eik•r
|ψ(r)|2
r

(b) |ψ(r)|2 has the same periodicity as the potential

Note that the wavefunction is not periodic.

k is called the crystal momentum.
uk(r) is called the cell periodic part of the wavefunction.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 ELECTRONS IN AN ATOM
Before examinig electrons in a solid, let us examine
electronic states in an atom. Let us examine the
hydrogen atom.

Electron in an attractive potential of an atom

Free states

E = 0 : Vacuum energy
Bound states

E5
E4 For hydrogen atom
E3 E1 = –13.6 eV
E2 = –3.4 eV
E2
E3 = –1.11 eV

E1

Bound states: Allowed energies separated by "gaps"

Allowed energy levels:

En = –me4 = 13.6 eV
2(4πε0)2h2n2 n2
Wavefunctions:
ψn m: n: principle quantum number.
: orbital quantum number; angular momentum
of the electron = h.
m: magnetic quantum number; projection of the
angular momentum; m lies between – and + .

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 FROM ATOMIC LEVELS TO ENERGY BANDS

As atoms are brought closer and closer to each other to form a crystal, the
discrete atomic levels start to broaden to form bands of allowed energies
separated by gaps. The electronic states in the allowed bands are Bloch states,
i.e., they are plane wave states (~eik•r).

Free states Free states

Evac Evac
...
E
E8 9
}
E7
} Allowed
E6 }
Bandgaps bands
E5 }
Bound states

}
E4 }

E3

E2

E1

Isolated atoms Crystal: Atomic spacing ~1-2 Å

• Low lying core levels are relatively unaffected.

• Higher levels are broadened significantly to form bands.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 ELECTRONS IN A (SOLID) CRYSTAL

Inside a crystal electrons respond to outer forces as if they have an

effective momentum hk. Near the bandedges they respond as if they
have an effective mass m*.

ELECTRON WAVE IN A PERIODIC CRYSTAL

Energy solutions of
Schrödinger equation: Series of allowed bands and series of
bandgaps.
Properties of the bandgap: In the perfect crystal, electrons are
forbidden from occupying energies in
the bandgap.
Properties of an
allowed band: Electrons behave as if they are in free
space with a certain wavevector k. They
respond to the outside world as if they
have a new mass called the effective
mass.
hdk
Response to outside forces: = Force
dt
2 2
E = h k*
2m

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 FILLING OF ENERGY BANDS: FERMI DISTRIBUTION

At equilibrium electrons fill up the allowed energy states in a way that the
free energy is a minimum

Free energy (F) = Internal energy (U) – TS

T = Temperature in Kelwin
S = Entropy = k nW
W = Total degeneracy of the electron system.
For electrons (which obey Pauli exclusion principle, i.e., one electron per
state) the electron occupaton is

f(E) = 1
1 + exp E – EF
kBT

At E = EF: f(E) = 0.5

OCCUPATION PROBABILITY f(E)

T=0K

1.0
T1

T2 > T1
0.5

T2

0.0 E
0 EF

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 METALS, INSULATORS, AND SEMICONDUCTORS
METALS: Electron density is such that highest occupied band is
partially (say, half) filled.
INSULATORS/SEMICONDUCTORS: Highest occupied band is completely
filled at low temperature.

Vacuum energy

Work Electron affinity

function (eχ) Conduction band
(eφ) EC

EV
EF Valence band
EC

AAAA AAA Core level

AAAA AAA
AAAA AAA Core level

Metal Semiconductor
Highest occupied Highest occupied band is
band is partially filled completely filled at T = 0

• A completely filled band does not carry any current Pauli exclusion
principle. Electrons need an empty state to move.
Insulators and semiconductors have very low conductivity.
Metals have a high conductivity.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 EXAMPLE OF ELECTRONS IN A METAL

Evac

#5

Electrically
active band EF
#4
Electrically
inert bands
#3

#2

(a) #1
DENSITY OF ALLOWED STATES

Band #1

Band #5
Band #2

Band #3

Band #4

f(E)

FERMI FUNCTION f(E)

1.0

0.5

EF Evac
(b) ELECTRON ENERGY

(a) Allowed energy bands and filling of bands by electrons in metals. (b) A
schematic of allowed bands and density of states in a metal. In the example
shown Band #4 is the conduction band.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh

 EXAMPLE OF ELECTRONS IN A SEMICONDUCTOR
Evac
Conduction
band #6 Band becomes electrically active if
some electrons are excited into it

EF
Valence
band #5 Band becomes electrically active if
some empty states are present

#4

#3
Electrically
inert bands
#2

(a) #1
DENSITY OF ALLOWED STATES

Empty Occupied

FERMI FUNCTION f(E)

states states

1.0
#1 #2 #3 #4 #5 #6
0.5

EF Evac
(b) ELECTRON ENERGY

(a) Allowed energy bands and filling of bands in a semiconductor. (b) Density of
allowed states in a semiconductor. Here, Band #5 is the valence band and Band #6
is the conduction band.

© Prof. Jasprit Singh www.eecs.umich.edu/~singh