Physics of Semiconductors

Antonio Agresti

CHOSE – Center for Hybrid and Organic Solar Energy

• University of Rome «Tor Vergata» (Italy)

[email protected]
AA 2022-2023
 Semiconductors
Semiconductors are the materials which have a conductivity between
conductors (generally metals) and non-conductors or insulators (such ceramics).
Semiconductors can be compounds such as gallium arsenide or pure elements, such
as germanium or silicon.

Semiconductor
materials
 Silicon-based Semiconductors
• Carriers
 When a Si-Si bond is broken and the associated electron is free to wander, the
released electron is a carrier
 In terms of the band model, excitation of valence band electrons into the conduction
band creates carriers; electrons in the conduction band are carriers
Completely filled valence band : no current
The breaking of a Si-Si bond creates a missing bond or void
 Missing bond in the bonding scheme, the empty state in the valence band, is the
second type of carrier– the hole
 Both electrons and holes participate in the operation of most semiconductor devices
The most important parameters of a
semiconductor material for solar cells are:
• the band gap;
• the number of free carriers available for
conduction;
• the "generation and recombination"
processes of free carriers in response to
light-matter interaction.
 Semiconductors: Energy Bandgap
The semiconductor band gap is the minimum energy needed to move an electron away
from its bound state, to a free state where it can participate in conduction.

The lower energy level of a semiconductor is called "valence band" (VB) and the energy
level at which an electron can be considered free is called "conduction band" (CB).

The band gap (EG) is the energy jump between the conduction band and valence band.
 Direct and Indirect Band Gap
• A semiconductor is direct if the • A semiconductor is indirect if the maximum
maximum of the valence band and the of the valence band and the minimum of
minimum of the conduction band do the conduction band do not have the same
have the same k value k value

Figure 3
Direct and indirect
electron transitions
in semiconductors:
(a) direct transition
with accompanying
photon emission;
(b) indirect transition
via a defect level.

Direct semiconductors are suitable for making light-emitting devices,

whereas the indirect semiconductors are not.
 Free carriers in a semiconductor
Once the electron is in the conduction band, it is free to move in the semiconductor through
the crystal structure and participate in conduction. However, the movement of an electron to
the conduction band causes a further conduction process to take place: an empty space
remains for the other electrons in the valence band. An electron from a neighboring atom can
move into this empty space. When this electron moves, it leaves another space ...

The continuous movement of this space for an electron, called «hole», can be described as
the movement of a particle positively charged through the crystalline structure.
Consequently, the displacement of an electron to the conduction band leads to having not
only an electron participating in the conduction, but also a hole in the valence band.

Both the electron and the hole can participate in the

conduction and are called "carriers".
 Intrinsic Semiconductor

Intrinsic Semiconductor is a perfect semiconductor crystal with no impurities or lattice defects

n  conduction band electron concentration
(electrons per cm3)
p  valence band hole concentration

n=p=ni N

4
Ng ( E )  3 (2m*)3/ 2 E State density
Intrinsic h
CB 3/ 2 Nc (or Nv) is a constant
 2m  KT
*
 called the effective density
N c ,v  2 n, p

 h 2 of states at the conduction
Ei (Fermi level)
  (or valence) band edge.
It gives the total number of available states per unit
VB volume at the bottom of the conduction band (or at the top
of valence band) for electrons (or for holes) to occupy.
 Intrinsic Semiconductor
Ei = Ef

T=0°K
Fermi distribution 1
T=300°K
1
f (E) 
1  exp  E - EF  / KT  0
E
VB CB

The thermal excitation of a carrier from the valence band to the conduction band
creates free carriers in both bands: intrinsic carrier concentration, ni.
 Electron and Hole Concentrations at Equilibrium
The Fermi distribution function can be used to calculate the concentrations of electrons and
holes in a semiconductor if the densities of available states in the valence and conduction
bands are known. The concentration of electrons in the conduction band is

n0   f ( E ) N ( E )dE
Ec
where N(E)dE is the density of states (cm-3) in the energy range dE. The subscript 0 used
for the electron and hole concentration symbols (n0, p0) indicates equilibrium conditions.
The number of electrons per unit volume in the energy range dE is the product of the density
of states and the probability of occupancy f(E). Thus the total electron concentration is the
integral over the entire conduction band. The function N(E) can be calculated by using
quantum mechanics and the Pauli exclusion principle.
N(E) is proportional to E1/2, so the density of states in the conduction band increases with
electron energy. On the other hand, the Fermi function becomes extremely small for large
energies. The result is that the product f(E)N(E) decreases rapidly above Ec, and very few
electrons occupy energy states far above the conduction band edge.
Similarly, the probability of finding an empty state (hole) in the valence band [1 - f(E)]
decreases rapidly below Ev, and most holes occupy states near the top of the valence band.
 Intrinsic Carrier Concentration

n  ni   f ( E ) g ( E )dE

If Ec-Ef >> KT

f ( E )  exp(( E  EF ) / KT )........( Boltzmann)

ni  N c exp(( Ec  Ei ) / KT )  N v exp(( Ei  Ev ) / KT )
n  ni exp(( E f  Ei ) / KT )
p  ni exp(( Ei  E f ) / KT )
  KT 
3

np  n  4  2  (mn* m*p )3/ 2 exp( Egap / KT )

2
i
 h 

Mass action law

At a fixed T (thermal equilibrium conditions) np = costant = ni2 does not depend on Fermi level position
in the gap also in presence of impurity such as dopant.
c-Si ni = 1.1010 cm-3
 Semiconductor Doping
Silicon crystal Silicon crystal
Extra
electron

Conduction
Conduction
Band
Band (partially filled)
(Unfilled)

Valence
Valence Band
Band (filled)
(partially filled)
Boron atom (5) hole
IIIA IVA VA VIA Arsenic atom (33)
ACCEPTOR DOPING:
P-type Semiconductor DONOR DOPING
Dopants: B, Al N-type Semiconductor
Dopants: As, P, Sb

Image in the
Public Domain
 Extrinsic Material – donation of electrons
An impurity from column V introduces an energy
level very near the conduction band in Ge or Si.
n-type material
This level is filled with electrons at 0 K, and very
little thermal energy is required to excite these
electrons to the conduction band. Thus, at about
50-100 K nearly all of the electrons in the impurity
level are "donated" to the conduction band.

Such an impurity level is called a donor level, and

the column V impurities in Ge or Si are called
donor impurities. From figure we note that the
material doped with donor impurities can have a
considerable concentration of electrons in the
conduction band, even when the temperature is
too low for the intrinsic EHP concentration to be
Donation of electrons from appreciable. Thus semiconductors doped with a
a donor level to the significant number of donor atoms will have
conduction band n0>>(ni,p0) at room temperature.

This is n-type material.

 Extrinsic Material – acceptance of electrons

P-type material Atoms from column III (B, Al, Ga, and In)
introduce impurity levels in Ge or Si near the
valence band.
These levels are empty of electrons at 0 K. At
low temperatures, enough thermal energy is
available to excite electrons from the
valence band into the impurity level, leaving
behind holes in the valence band.
Since this type of impurity level "accepts"
electrons from the valence band, it is called
an acceptor level, and the column III
impurities are acceptor impurities in Ge and
Acceptance of valence band Si. As figure indicates, doping with acceptor
electrons by an acceptor level, impurities can create a semiconductor with a
and the resulting creation of hole concentration p0 much greater than the
holes. conduction band electron concentration n0
(this is p-type material).
 Band gap in doped materials
m*n < m*p  mn > mp 1100 , 420 cm2/Vs
Ef
n-type mn = qtn/m*n
T=0°K
CB 1
Ef (Fermi level) ND T=300°K

0
E
VB
VB CB
Ef
p-type mp = qtp/m*p Excess of carriers
T=0°K
CB 1
T=300°K

Ef (Fermi level) 0
NA
E
VB
VB CB
Band diagram, density of states, Fermi-Dirac distribution, and the
carrier concentrations at thermal equilibrium

Intrinsic
semiconductor

n-type
semiconductor

p-type
semiconductor
 Doped Semiconductors: Summary

Intrinsic semiconductors

Doped semiconductors n 0 p0  n 2
i
n-type p-type

n0  ni exp( EF  Ei ) / kT  p0  ni exp( Ei  EF ) / kT 
 Quasi -Equilibrium Carrier Concentration
• The number of carriers in the conduction and valence band can be altered due to an injection
by contacts or absorption of incident photons, bringing the carriers to a quasi-equilibrium
concentration of carriers.
• We speak of quasi-equilibrium because in a very short time the carriers assume an energy
distribution which is that of Fermi, referred to a quasi-equilibrium level called Fermi quasi-
level
• Out-of-equilibrium concentration is described by the difference between the quasi-Fermi
levels. The processes that bring the system into balance are recombinations and generations
(absorptions)
 Recombination and Generations

The equilibrium in the semiconductor is governed by the continuity equations

  
 J  
t
in which the effects of current, generations (absorptions) and recombinations are
considered.

Any electron in the conduction band is in a metastable state and eventually returns to a
lower energy position in the valence band.

There are three basic types of recombination in a monocrystalline semiconductor

material:

• Radiative ricombination.
• Recombination mediated by Defects / trap states (SHR)
• Auger ricombination
 Radiative recombination
In the case of radiative recombination,
- an electron recombines directly with a hole and loses energy in the form of a photon;
- the emitted photon has an energy similar to the band gap energy and is therefore absorbed
only weakly, and can exit from the semiconductor material.

In optical processes
total energy and
wave vector must be
preserved

• Radiative recombination is the recombination mechanism that dominates in devices such

as LEDs and lasers.
• For photovoltaic devices largely based on silicon, it is not important since the silicon band
gap is "indirect".
 Indirect band gap and indirect optical transitions
In indirect gap semiconductors, radiative transitions can occur only if assisted by a phonon
that guarantees the conservation of the momentum.

The transition takes place as a sequence of two virtual processes in which first an electron
from the valence band is excited in the conduction band (conserving momentum but not
energy) from the photon, and then it is brought into the final state through the absorption or
emission of a phonon. Equally one can have a transition with the two inverted processes.

Indirect processes
are always less
probable than direct
ones

The probability of an indirect transition is obtained from the extension of Fermi's golden rules
2
2
ind
Wabs   


kc , kv n
f H n n H i
Ei  E n

 E f  Ei 
 Non-radiative recombination

A foreign interstitial
B dislocation
C self interstitial
D precipitate
E extrinsic stacking fault and partial dislocation
F foreign substitutional
G vacancy
H intrinsic stacking fault and partial dislocation
I foreign substitutional
 Non-radiative recombination

Recombination through energy levels associated with defects

Recombination through defects, also known as

Shockley-Read-Hall or SRH recombination, does not
occur in perfectly pure and non-defective materials.
SRH recombination is a 2-step process.

The two phases or stochastic events can be

distinguished as follows:

1) An electron (or a hole) is trapped in an energetic

state introduced into the forbidden semiconductor Rnr  A N
gap by a crystal defect. These defects can be random
or deliberately introduced, for example to dope the
A1 t nr
material;
The simultaneity of the two
2) A hole (or an electron) arrives in that same events determines the SHR
energetic state before the electron (or the hole) is re- recombination.
emitted thermally towards the conduction band (or
valence), and recombines with the electron.
 Non-radiative recombination

Auger Recombination
• An Auger Recombination involves three carriers. It is the inverse process of impact
ionization.
• An electron and a hole recombine, but rather than emitting the energy as heat or as a
photon, the energy is given to a third carrier, an electron in the conduction band.
This electron then thermalizes back down to the conduction band edge.
• Auger recombination is most important in heavily doped or heavily excited material.

Rauger  C n3;
Cn n2 p  C p np2)

Auger recombinations are dominant in concentration solar

 Non-radiative recombination
Surface Recombination
Any defects or impurities within or at the surface of the semiconductor promote recombination. A
parameter called the "surface recombination velocity", in units of cm/sec, is used to specify the
recombination at a surface.
The defects at a semiconductor surface are caused
by the interruption to the periodicity of the crystal
lattice, which causes dangling bonds at the
semiconductor surface.
The reduction of the number of dangling bonds, and
hence the recombination, is achieved by growing a
layer on top of the semiconductor surface which ties
up some of these dangling bonds. This reduction of
dangling bonds is known as surface passivation.