ENERGY BANDS AND

CHARGE CARRIERS IN
SEMICONDUCTORS
Bonding Forces and Energy
Bands in Solids
For an electron in an isolated atoms, discrete energy levels
exist.

In solids, when atoms come closer at an inter atomic
distance, their wave functions overlap, resulting the
formation of energy bands.

Band formation is due to the change in potential energy
term in Schrodingers eq. as well as the boundary
conditions

Bonding forces in Solids
The interaction of electrons in neighboring atoms of a
solid is the most important function of holding the crystal
together.

Electronic structure in the outermost orbit is responsible
for the different types of bonding and the electrical
properties of solids.

Types of Bonding
Ionic Bonding:
Most commonly the alkali halides such as NaCl are bound
through Ionic bonding
The electronic structure of Na(Z=11) is [Ne]3s
1
, and
Cl(Z=17) has the structure [Ne] 3s
2
3p
5
.
In NaCl lattice, each Na atom gives its 3s electron to Cl
atom to complete its outermost orbit as 3s
2
3p
6
.
result is the crystal of ions with the electronic structure
of inert atoms Ne and Ar No electrons for the electrical
conduction are available.
Each Na atom will become Na
+
ion and each Cl atom will
become Cl
-
ion, columbic attraction between the opposite ions is
responsible for the strong bonding force known as IONIC
BONDING
Figure 31
Different types of chemical bonding in solids (a) an example of ionic
bonding in NaCl; (b) covalent bonding in the Si crystal, veiwed along a
<100> direction (see also Figs. 18 and 19).
METALLIC BONDING
Outer electronic shell of metallic atoms is partially filled,
usually with three electrons at maximum.
In alkali atoms, there is only one loosely bonded electron in
the outer orbit.
In solids, atoms at a distance of atomic dimensions,
electrons cannot distinguish between their own core and the core of
neighboring atom, thus all the outermost electrons are not bound to
single atom, but the inner ionic cores are immersed in the sea of free
electrons giving rise to high electrical conductivities.

COVALENT BONDING
Diamond lattice semiconductors mostly exhibit the
Covalent Bonding.
Each atom in Ge, Si or C diamond lattice is surrounded
by four nearest neighbors, each with four electrons in the
outermost orbit.
Each atom shares its valence electrons with its four
neighbors.
Shared electrons are bounded through quantum
mechanical interaction between them.
Shared electrons are indistinguishable except that they
must have opposite spins satisfying the Paulis exclusion
principle.
Figure 19
Diamond lattice unit cell, showing the four nearest neighbor structure. (From
Electrons and Holes in Semiconductors by W. Shockley, 1950 by Litton
Educational Publishing Co., Inc.; by permission of Van Nostrand Reinhold Co., Inc.)
Few Properties of Semiconductors

For elemental semiconductors, no free electrons are
present in the lattice, resulting in an insulator behavior. (The
case at 0
o
K).

An electron can be thermally or optically excited out of a
covalent bond and become available for electrical conduction,
which is the most important feature of semiconductors.

Compound semiconductors like GaAs, a II-VI
compound, have mixed bonding.

Ionic, due to their positions in periodic table.
Covalent due to their atomic structure.
ENERGY BANDS
Isolated atoms have discrete energy levels, which results
due to columbic potential of nucleus seen by the electrons.
Look at fig. 2-8, orbital model of Si atom and the energy
levels of various electrons in the columbic potential well of the
nucleus.
When two atoms come close to each other at atomic
distance their wave functions overlap.
By solving the Schrodingers equation for such an interacting
system we find that the composite two-electron wave function is
the linear combination of the individual atomic orbital (LCAO)

1
: Wave function for isolated atom 1 and
2
: Wave function
for isolated atom 2
= a
1
+ b
2
is the (LCAO)

Figure 28
Electronic structure and energy levels in a Si atom: (a) The orbital model of a Si atom
showing the 10 core electrons (n = 1 and 2), and the 4 valence electrons (n = 3); (b)
energy levels in the coulombic potential of the nucleus are also shown schematically.
Figure 32
Linear combinations of atomic orbitals (LCAO): The LCAO when 2 atoms are brought together
leads to 2 distinct normal modesa higher energy anti-bonding orbital, and a lower energy
bonding orbital. Note that the electron probability density is high in the region between the ion
cores (covalent bond), leading to lowering of the bonding energy level and the cohesion of the
crystal. If instead of 2 atoms, one brings together N atoms, there will be N distinct LCAO, and N
closely-spaced energy levels in a band.
Bonding or Anti-bonding Orbital :

Sym LCAO

sym
= (1/\2) 1 + (1/\2) 2 bonding orbital

Non-sym. LCAO

asym
= (1/\2) 1 - (1/\2) 2 anti-bonding orbital

sym Lowest energy state

asym Highest energy state

All other energy state are due to any other LCAO

For the two electrons at inter-atomic distance from
each other, their wave functions overlap, but according to
Paulis exclusion principle, they cannot have same state or
energy level
So there is a splitting of these energy levels in such a
way that only one electron per energy level is available.
In solids, many atoms are brought close to each other
and same phenomenon is seen i.e., splitting of energy level
with such a small difference of energy that they almost form a
continum known as energy band.

Band Types
Lower energy states form valence bands.

Higher energy levels split in the form of conduction
band.

There is a gap between valence band and conduction band
known as band gap or forbidden band.
Special case Si
In Si, outer orbit is 3S
2
3P
2
, allowed states are 2N in 3s
state and 6N in 3P state for N atoms.
In S shell is all states are occupied but in p shell 2N states
are occupied and 4N are available.
At 0K, lowest energy states are occupied valence band
is filled, conduction band empty.
Through thermal or optical excitation we can shift the
electrons from valence to conduction band. effecting
on the electrical properties.
Figure 33
Energy levels in Si as a function of inter-atomic spacing. The core levels (n = 1,2) in Si
are completely filled with electrons. At the actual atomic spacing of the crystal, the 2 N
electrons in the 3 s sub-shell and the 2 Nelectrons in the 3 p sub-shell undergo sp 3
hybridization, and all end up in the lower 4 Nstates (valence band), while the higher lying
4 Nstates (conduction band) are empty, separated by a bandgap.
Metals, Semiconductors and
Insulators
In metals conduction band is partially filled, so
allowed states are available for electrons to hop
from one state to another state
In Insulator e.g., diamond, valence band is
completely filled so there is no place for the
electrons to move and conduction band is
completely empty so there is no electron to move
through allowed states.
Semiconductors also has the same band structure
as of diamond but there is a difference in band gap
Band Gap of Diamond and Silicon
Semiconductors at 0K have same band structure
as of diamond but the Energy gap between valence
and conduction band in Si is 1.1eV, whereas in
diamond gap is 5eV. At room temperature these
gaps become 1eV and 10eV
Due to small band gap, energy could be supplied
to electrons through thermal or optical excitations,
so that they can jump from valence to conduction
band.
Figure 34
Typical band structures at 0 K.
Direct and Indirect semiconductors
In a solid and electron is assumed to travel through a
perfectly periodic lattice. The wave function is assumed to
be in the form of plane wave e.g., in x direction with
propagation constant k also called the wave vector. K also
defines the momentum of the electron.
Space dependent wave function for the electron is

k
(x) = U(k
x
, x) exp (ik
x
x)
Where the U(k
x
, x) modulates the wave function according to
periodicity of the lattice.
For such calculations allowed values of energy could be
plotted as a function of k.
As the periodicity of the crystal is mostly different in
different directions so (E, k) plot in different directions is
different and we can get a complex surface for such a plot.
For example, the band structure of GaAs is such that the
maxima of valence band and minima of conduction band lie at
the same value of k.
For Si, these minima and maxima lie at two different
values of k
Transition of an electron from the conduction band of
GaAs to valence band will result in emission of a photon of
energy equal to band gap without changing the value of k. Such
transition is known as DIRECT TRANSTION


Figure 35
Direct and indirect electron transitions in semiconductors: (a) direct transition
with accompanying photon emission; (b) indirect transition via a defect level.
In Si, transition from conduction to valence band minima
will take place with the change of energy as well as momentum
or k.
Such transition take place through some defect in the
system and known as Indirect Transition.
For indirect transitions, the energy is given up to the
lattice in the form of heat instead of emitting it in the form of
photon.
The remarkable difference in the behavior of direct and
indirect semiconductors makes it possible to select a typical type
for a typical purpose, e.g., direct semiconductors are mostly
used in light emitting devices.
OR we can use the material with vertical transition between the
defect states

Variation of energy Bands with
Alloy Composition
As III-V ternary and quaternary alloys are varied over
their composition ranges, their band structures change.

Fig illustrates the band structure of GaAs and AlAs and the
way in which the bands change with composition x in the
ternary compound Al
x
Ga
1-x
As.
In figure is the minimum of direct conduction band,
whereas two other minima for indirect conduction band are
assigned names X and L

Comparison of Band in GaAs and AlAs

In GaAs is the lowest lying conduction band, so it
behaves as direct semiconductor with band gap of 1.43eV
Whereas in AlAs, direct minimum is much higher as
compared to X and L. X is the lowest lying minima and so
indirect transitions with energy gap of 2.16eV will be more
probable.
Ternary alloy Al
x
Ga
1-x
As, has a completely different band
structure for different compositions, shown in figure
Figure 36
Variation of direct and indirect conduction bands in AIGaAs as a function of composition: (a)
the ( E,k) diagram for GaAs, showing three minima in the conduction band; (b) AIAs band
diagram; (c) positions of the three conduction band minima in AI x Ga 1- x As as x varies over
the range of compositions from GaAs ( x = 0) to AIAs ( x = 1). The smallest band gap, E g
(shown in color), follows the direct band to x = 0.38, and then follows the indirect X band.
Variation of band gap with alloy
composition
From x = 0 to x = 0.38, has lower energy and the
behavior is direct
For x > 0.38, X band has a lowest minima and there will
be indirect transitions
The light emitting diodes and lasers are generally made of
materials capable of direct band to band transition or of
indirect materials with vertical transition between defects
Charge Carriers in
Semiconductors
In conductors or metals, atoms are immersed in the sea of free
electrons, which can individually or as a group can move due
under the influence of an electric field. The valence band is
completely filled and conduction band is partially filled
providing enough states for the electrons to hop.
In semiconductors, valence band is completely filled and
conduction band is completely empty, so no conduction. We
can excite electrons thermally to conduction band so enough
states are available for their movement as well as in valence
band some states are available for electron movement.
Impurities can play a vital role in controlling the conduction.
Electrons and Holes
As we have that due to thermal excitations, electrons move
from valence to conduction band by providing few electron in
conduction band and few empty states in valence band.
an empty state in the valence band is known as Hole
If the hole is created by the thermal excitation then they are
called electron-hole pair (EHP).
After excitation an electron is surrounded bu a large number of
unoccupied energy states, I.e., the eqbm. No. of EHP in pure Si
at room temperature is about 10
10
EHP/cm
3
, compared tp Si
atom density of 5 10
22
EHP/cm
3
.
The problem of charge transport in valence band can be
accounted for by simply tracking the holes.

Figure 37
Electron-hole pairs in a
semiconductor.
Charge transport in the valence band
In a filled band, all available energy states are occupied.
For every electron moving with a given velocity, there
must be another electron somewhere moving with the
opposite velocity.
By applying electric field, net current is zero because for
every electron j moving with velocity v
j
there is a
corresponding electron j` with v
j
.(effect shown in fig 3.8).
With N electrons/cm
3
in the band we express the current
densityusing a sum over all of trhe electron velocities, and
having charge q on each electron. In a unit volume
J = (-q)
i
N
v
i
= 0 (filled band)
For a hole, which is created by removing the jth electron,
the net current density in the valence band involves the sum
over all the velocities minus the contribution of the removed
electron
J = (-q)
i
N
v
i
- (-q) v
j
(jth electron missing)
The first term is zero so net current is qv
j
.
The contribution of current due to missing electron is as
due to a positively charged particle with velocity v.
We shall treat the empty states in valence band as positive
charge carrier with mass m.
Figure 38
A valence band with all states filled, including states j and j9, marked for
discussion. The jth electron with wave vector k j is matched by an electron
at j9 with the opposite wave vector 9k j . There is no net current in the
band unless an electron is removed. For example, if the jth electron is
removed, the motion of the electron at j9 is no longer compensated.
Comparison of energies in the two bands
In valence band hole energy increases oppositely to
electron energy in conduction band, as the two carriers
have opposite charge.
For the valence band energy minima is at the top of the
band and energy increases downward.
In conduction band, energy minima lies at the bottom of
band and increases upward.
Fig 3.9 shows the simplified version of band diagrams and
used for routine devices. E(K) diagram is a plot pf the total
electron energy (KE + PE) as a function of the crystal
direction dependent electron wave vector or momentum
The bottom of the conduction band correspond to zero
electron velocity or KE and simply gives us the potential
energy at that point
For the valence band, top is only the potential energy.
In simplified diagram we plot the edges (PE) of the two
bands as a function of position in the device.
The higher energies correspond to additional kinetic energy
of the electron.
Band edge correspond to the potential energies, so with
applied electric potential, potential energy edges have slope
as a function of device position.
Figure 39
Superimposition of the ( E,k) bandstructure on the E-versus-position simplified band
diagram for a semiconductor in an electric field. Electron energies increase going up,
while hole energies increase going down. Similarly, electron and hole wavevectors point
in opposite directions and these charge carriers move opposite to each other, as shown.
Explanation of figure 3-9:
an electron at position A sees an electric field given by the slope
of the band edge (PE).
Moving to point B, gains kinetic energy at the expense of electric
potential energy.
Electron starts through k and then gained momentum by reaching
at k
b

The elctron loses KE by scattering mechanism and returns to the
botton of the band at B.
The slope of the E(x) diagram represent the local electric field at
those points.
Effective mass
If we treat the electron in the periodic lattice as free, then
to consider the electrodynamics in the system we have to
consider the different mass as compared to the actual mass,
e.g., in the motion of hole, actually the mass of electron is
involved but its energy states shows it to be negative.
By considering the effective mass, we can approximate
the motion of electron in periodic lattice as a free electron,
having kinetic energy as
2
k
2
/ 2m
*
, where m
*
is the
effective mass.
The effective mass of an electron in a band with a given
(E,k) relation is found to be
m
*
=
2
/ (d
2
E/dk
2
)

Last eq. shows that the curvature of the band determines
the electron effective mass.
consider fig. 3-6a, we cans see that the electron effective
mass in GaAs is much smaller in the direct I conduction
band (strong curvature) than in L or X minima (weaker
curvature).
Curvature of conduction band minima is positive and
curvature of valence band maxima is negative
Thus the electrons near the top of the valence band have
negative mass.
Valence band electrons with negative charge and negative
mass move in an electric field in the same direction as a
positive charge hole with positive mass.
Intrinsic Material
a perfect semiconductor crystal with no impurities or
lattice defects is called an intrinsic semiconductor.
No charge carriers at 0
o
K. (filled VB and empty CB)
At high temperature EHP creates, which are the only
charge carriers in the Intrinsic material.
The generation of EHP is due to the breaking of covalent
bonds in the crystal lattice.
the energy required to break the bond is the band gap
energy. (fig.3-11)
fig. 3-11 is a qualitative representation of EHP creation.
Quantitative analysis could be done by the band theory.

It seems that electron and hole are confined in the lattice.
In actual they are few lattice spacing from each other and
they can hop too.
Since they are created in pairs so concentration of electrons
in the CB is the same as the concentration of the holes in the
VB. Thus for intrinsic material
n = p = n
i

At a particular temperature, there is a particular
concentration of EHP, So for a continuous EHP formation
there should be a continuous regeneration of EHP. These tw
rates should be equal to each other r
i
= g
i

These rates are proportional to the equilibrium concentration
of electrons n
o
and holes p
o

r
i
= o
r
n
o
p
o
= o
r
n
i
2
= g
i

Extrinsic Material
In addition to the intrinsic carriers, it is possible to create
carriers in semiconductors by purposely introducing
impurities in the crystal. This process is called doping.
When a crystal is doped such that the equilibrium
concentration n
o
and p
o
are different from the intrinsic
carrier concentration n
i
, the material is called extrinsic
material
By doping, a crystal can be altered so that it has a
predominance of either electrons or holes.
There are two types of doped semiconductors, n-type
(extra electrons) and p-type (extra holes)
N-Type Material:
when impurities are added to a pure crystal, additional level are
created in the energy band structure, usually within the band gap.
impurity from column V (P, As, Sb) introduces an energy level
just below the conduction band in Si or Ge.
This level is filled at electrons at 0K and very little thermal
energy is required to excite them to conduction band. See figure.
at about 50 100K virtually all of the electrons in the impurity
level are donated to the CB.
Such impurity level is called donor level.
Such materials are called donor impurities.
In such materials n
o
>> (n
i
, p
o
), at room temperature.
This is n-type material
P-Type Material:
Impurities are form column III (B. Al, Ga, In) introduces a
level in Ge or Si near the valence band.
These levels are empty at 0K.
At low temperature enough energy is available to excite the
electrons from the VB to the impurity level, thus enough holes
created in VB.
This impurity level accepts electrons from the VB, so known
as acceptor level.
columns III impurities are called acceptor impurities.
fig 3-12b indicates, doping with acceptor impurities.
p
o
>> (n
o
, p
i
), known as P-Type.
Figure 312
Energy band model and chemical bond model of dopants in semiconductors: (a)
donation of electrons from donor level to conduction band; (b) acceptance of valence
band electrons by an acceptor level, and the resulting creation of holes; (c) donor and
acceptor atoms in the covalent bonding model of a Si crystal.
Binding energy of donors
We can calculate the energy required to excite the fifth
electron of the donor atom to CB.
For example, As atom has four out of five covalent
bonding electrons and one loosely bounded electron.
We can make a picture like H atom as a loosely bounded
electron revolving around a tight bounded core.
Magnitude of the energy for ground state n = 1, can be
given by Bohrs theory as
E = mq
4
/ 2K
2.
K =4tc
o
c
r

column V donor levels lie approximately 0.01eV below
the CB in Ge, and the column III acceptor levels lie about
0.01eV above the VB.
In Si, the usual donor and acceptor levels lie about 0.03
0.06eV from a band edge.

Charge Carrier in compound semiconductors
In III-V compounds, column VI impurities occupying column V
sites serves as donors.
Impurities from column II occupying column III sites can accept
an electron and will serve as a donor.
Impurities from columns IV have a very interesting behavior and
called amphoteric, meaning that Si or Ge from column IV can
serve as donor or acceptor depending on weather they reside on
the column III or V sub lattice of the crystal.
By doping, the resistance of the semiconductor materials
changes drastically, in return changing its electronic properties
e.g, in Si, the n
i
is about 10
10
cm
-3
at room temperature.
In doped Si with 10
15
As atoms/cm
3
, the conduction electron
concentration changes by five orders of magnitude.
The resistivity of Si changes from 2 x 10
5
-cm to 5 -cm with
the doping.
Electrons and Holes in Quantum Well
In a solid there are two continuum region of energies
known as CB and VB.
In doped semiconductors there is another type of discrete
levels arising due to the presence of the energy levels of
doping materials.
A third possibility is the formation of discrete levels for
electrons and holes due to quantum mechanical
confinement.
We can get such confinement in the multilayer compounds
semiconductors.
MBE and OMVPE are the good methods to create such
hetero junction materials.
Fig. 3-13 shows multilayer structure of AlGaAs and GaAs,
where a this layer of GaAs is grown between the two layers of
AlGaAs, which has a larger energy gap as compared to GaAs.
we cans see that energy difference created a potential well.
Electrons in the CB and holes in the VB are confined in the
potential and now have discrete levels as compared to a
continuum.
Transition of an electron from E1 in CB to level Eh in VB will
emit a photon of larger energy as compared to a band gap of
GaAs.
Semiconductor lasers have been made in which such a quantum
well is used to raise the energy of the transition from the
infrared, typical of GaAs to the red portion of the spectrum.
Figure 313
Energy band discontinuities for a thin layer of GaAs sandwiched between
layers of wider band gap AIGaAs. In this case, the GaAs region is so thin that
quantum states are formed in the valence and conduction bands. Electrons in
the GaAs conduction band reside on particle in a potential well states such a
E 1 shown here, rather than in the usual conduction band states. Holes in the
quantum well occupy similar discrete states, such a E h .