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Metal
Insulator
Semiconductor
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
p-Type semiconductors
n-Type semiconductors
-
EC
ED
EA
EV
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
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).
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
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
NC ~ NV ~ 1019 cm-3
E/eV
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
= n = N V exp V
p = N C exp F
kT
kT
3.7
n = N V N C exp C
2kT
3.8
Ge
Egap = 0.7 eV
n = 2.5 1013 cm-3
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
N D + = D exp D
2
kT
10
n = N D+ + p N D+
3.11
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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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.
13
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
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
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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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