THE ENERGY LEVELS OF ELECTRONS IN SEMICONDUCTORS

No longer an infinite source/sink of electrons

Electrons occupation- Band gap
Intrinsic and extrinsic materials
Shallow vs deep traps
Surface states
Band bending

Electron energy bands in semiconductors

As discussed in the previous lectures, the electrochemical properties of solids are determined by the
frontier bands. In semiconductors,the valence (bonding) band are filled and the conduction
(antibonding) band are empty at 0 K.

Metal

Insulator
Semiconductor

Si band gap, Eg = 1.1 eV

Recalling from eq. 1.24, the state density distribution near the band edges features a square root
dependence on the energy level,

1 2me 2 3
D(E ) = 2
2 "2

(E E0 )

1.24

Band diagram of Ge
3

The band gap depends on the strength of the chemical bond:

Heat of chemical formation
Shortest distance between atoms
Difference in electronegativities between AB materials

Semiconductor materials are divided in two general groups:

Intrinsic: No energy states within the band gap
Extrinsic: Energy levels in the band gap produced by impurities

Substitution of a Si atom (4 valence electrons) by a P

atom (5 valence electrons) creates an excess of electrons
in the conduction band.
N-type semiconductors.

B (5 valence electrons) atoms in a Si crystal generate

electron vacancies in the valence band.
P-type semiconductors.

Doping semiconductors can be done by:

Introducing another element, e.g. F:SnO2
Altering the stoichiometry of the crystal, e.g. TiOx

p-Type semiconductors

n-Type semiconductors
-

EC

ED
EA

EV

Donor states near the

conduction band which
can be thermally ionized

The dopant energy level is usually located near the band edges, e.g.
P doped Si: EC - ED = 0.041 eV
B doped Si: EA - EV = 0.057 eV
Egap of Si is 1 eV

Acceptor states near the

valence band which can
be thermally occupied

Doping energy levels have a localised character, therefore charge carriers cannot moves freely along
these levels (as they do in the energy bands). Energy level located close enough to the band edges,
so they can be populated or ionised thermally, are commonly referred to as shallow levels. If the
levels are far into the band gap, the population-depopulation is kinetically controlled. These levels are
called deep trap levels. The latter can play a tremendous role in electrochemistry, specially in
illuminated semiconductor/electrolyte interfaces (but well see that later in the course).

Electrons and holes in semiconductors

Intrinsic semiconductors
As the density of thermally excited electrons is considerably smaller that the energy state density in
the conduction band, the concentration of electrons can be approximated by the Boltzmann
distribution,

E EC

n = E DC (E ) f (E)dE = N C exp F
kT
C

3.1

Where NC is the effective density of states at the bottom of the conduction band.
me* kT
N c = 2
2
2"

32

3.2
7

From eqs. 3.1 and 3.2, we obtain that the fermi level is given by,
N
E f = E C kT ln C
n

3.3

Similarly, for holes we can obtain,

p=

EV

E EF

DV (E ) f (E)dE = N V exp V
kT

mh* kT
N V = 2
2
2"

32

3.5

N
E f = EV + kT ln V
p

The effective state density corresponds to the

NC ~ NV ~ 1019 cm-3

E/eV

value near the band edges that can be thermally

populated by electrons and holes.

3.4

1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0.0

3.6

D(E )
D(E ) f (E )

Ef
0.2

0.4
D(E)

0.6

0.8
8

For intrinsic materials, the condition of electroneutrality is given by n = p,

E EC
E EF

= n = N V exp V
p = N C exp F
kT
kT

3.7

It follows that n can be expressed as,

E EV

n = N V N C exp C
2kT

3.8

Ge
Egap = 0.7 eV
n = 2.5 1013 cm-3

Finally, considering that NC = NV in intrinsic materials,

the fermi level is given by,

EF =

1
(EC + EV )
2

3.9

Extrinsic semiconductors
Donor states (n-type) and acceptor states (p-type) are thermally ionised introducing an excess of
electrons and holes in the conduction and valence band respectively.
n-type

p-type

Let us consider a n-type semiconductor with a ND concentration of donors. The density of

ionised states is given by
N
E EF
3.10

N D + = D exp D

2
kT

10

The electroneutrality is given by,

n = N D+ + p N D+

3.11

Recalling eq. 3.1 and 3.10,

N
E EC
E EF

= N D + = D exp D
n = N C exp F
kT
kT
2

Then, it follows

n=

NC N D
E ED

exp C

2
kT

E ED

N D = N C exp C

kT

EF =

1
kT 2 N C
EC + ED )
ln
(

2
2 ND

3.12

3.13

3.14

3.15

Expression 3.15 tell us that the higher is the doping density, the closer will be the fermi level to
the conduction band. Consequently, for the same material, the fermi level will be higher in ndoped than in the intrinsic case. Exactly the opposite occurs with p-type materials (you can
work it out at home).
N-type: Majority carriers are electron
Minority carriers are holes
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Semiconductors surfaces
In addition to the energy levels associated with the conduction, valence and doping levels, twodimensional states located at the surface can play an important role in the electrochemical
behaviour of semiconductors. These surface states generate levels in the band gap region.

Surface states can also be divided into intrinsic and extrinsic states. The former are associated
with lattice defects (e.g. dangling bonds), ionisaton of surface lattice atoms and reconstruction
forces. Extrinsic states are generated by adsorbed species.
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Shockley Surface States

These states are associated with dangling bonds at the surface of covalently bonded semiconductors,
eg. Si.

At the surface, dangling bonds tend to combine forming bonding (donor) levels or antibonding
(acceptor) levels. The former are located closer to the valence band while the latter are closer to the
conduction band.
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Tamm Surface States

Let us consider an ionic semiconductor such as ZnO. Surface lattice oxygen generate a energy state
higher than the bulk valence band due to an excess of negative charge, i.e. surface state with a donor
character. Similarly Zn surface lattice forms empty states with energies lower than the conduction
band (states with acceptor character).

Surface states can exhibit densities in the range

of 1010 to 1014 cm-2, while typical density of
surface atoms are of the order of 1015 cm-2

Extrinsic Surface States

Lewis sites - surface states able to donate or accept electrons from species in solution
Adsorbed species - e.g. S2- on CdS surfaces
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THE SPACE CHARGE LAYER

In the presence of surface states, the Fermi level at the surface is different from the bulk. At
equilibrium, the Fermi level should be equal, therefore the electron density will vary across a region
near the surface. The thickness of this space charge layer, typically in the range of 10 to 1000 nm,
depends on the density of majority carriers (doping density) as well as the dielectric properties of the
semiconductor.

As in eq. 3.15, the Fermi level at the surface in the presence of donor and acceptor states is given by
E Fs =
s

EF =

1
kT N C
EC + ES )
ln
(

2
2 N S

3.16

1
kT N
(E V + ES ) + ln V
2
2 N S

3.17

Where is volume to surface conversion factor.

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When EF = Efs, the bands are bent at the surface generating the space charge region.

Flat band
potential

Accumulation
layer

Depletion
layer

Inversion
layer

The space charge region involves a potential difference between the bulk and the surface of the
semiconductor,

S
SC = E C E C e

3.18

16

The space charge potential difference establishes a potential barrier for the transfer of electrons
outside the semiconductor surface. This is the reason why these materials can rectify the flux of carrier
in one direction only. The concentration of electrons and holes at the space charge region is given by

E CS E C
e SC
=

nexp
nS = nexp

kT
kT

E SV E V
e SC

pS = pexp
= p exp
kT
kT

3.19

3.20

The potential drop in the space charge region can be effectively controlled electrochemically. The
space charge layer and the properties of surface states are vitally important in the electrochemical
behaviour of these materials. In summary, some of the most interesting properties of semiconductors
are developed from the surface towards inside the material.

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