Energy Bands and Charge Carriers in Semiconductors

Bonding Forces and Energy Bands in Solids

• Electrons are restricted to sets of discrete energy levels within atoms, with large gaps
among them where no energy state is available for the electron to occupy.
• Electrons in solids also are restricted to certain energies and are not allowed at other
energies.
• Difference in the solid, the electron has a range (or band) of available energies.
• The discrete energy levels of the isolated atom spread into bands of energies in the solid
because
i) in the solid, the wave functions of electrons in neighboring atoms overlap, thus, it
affects the potential energy term and the boundary conditions in the
equation, and different energies are obtained in the solution, and
ii) an electron is not necessarily localized at a particular atom.
• The influence of neighboring atoms on the energy levels of a particular atom can be
treated as a small perturbation, giving rise to shifting and splitting of energy states into
energy bands.

Bonding Forces in Solids

Ionic Bonding

• Example: NaCl.
• Na (Z = 11) gives up its outermost shell electron to Cl (Z=17) atom, thus the crystal is
made up of ions with the electronic structures of the inert atoms Ne and Ar.
• Note: the ions have net electric charges after the electron exchange ion has a net
positive charge, having lost an electron, and ion has a net negative charge, having
acquired an electron.
• Thus, an electrostatic attractive force is established, and the balance is reached when this
equals the net repulsive force.
• Note: all the electrons are tightly bound to the atom.
• Since there are no loosely bound electrons to participate in current flow NaCl is a good
insulator.

Metallic Bonding

• In metals, the outer shell is filled by no more than three electrons (loosely bound and
given up easily) great chemical activity and high electrical conductivity.
• Outer electron(s) contributed to the crystal as a whole solid made up of ions with
closed shells immersed in a sea of free electrons, which are free to move about the crystal
under the influence of an electric field.
• Coulomb attraction force between the ions and the electrons hold the lattice together.
 Covalent Bonding

• Exhibited by the diamond lattice semiconductors.

• Each atom surrounded by four nearest neighbors, each having four electrons in the
outermost orbit.
• Each atom shares its valence electrons with its four nearest neighbors.
• Bonding forces arise from a quantum mechanical interaction between the shared
electrons.
• Both electrons belong to each bond, are indistinguishable, and have opposite spins.
• No free electrons available at 0 K, however, by thermal or optical excitation, electrons
can be excited out of a covalent bond and can participate in current conduction
important feature of semiconductors.

Mixed Bonding

• Shown by III-V compounds bonding partly ionic and partly covalent.

• Ionic character of bonding becomes more prominent as the constituent atoms move
further away in the periodic table, e.g., II-VI compounds.

Energy Bands

• As isolated atoms are brought together to form a solid, the electron wave functions begin
to overlap.
• Various interactions occur, and, at the proper interatomic spacing for the crystal, the
forces of attraction and repulsion find a balance.
• Due to Pauli exclusion principle, the discrete energy levels of individual atoms split into
bands belonging to the pair instead of to individual atoms.
• In a solid, due to large number of atoms, the split energy levels for essentially continuous
bands of energy.

Fig.2.1 splitting of individual energy levels to energy bands as atoms is brought closer together.
• Imaginary formation of a diamond crystal from isolated carbon atoms .
• Each atom has two 1s states, two 2s states, six 2p states, and higher states.
• For N atoms, the numbers of states are 2N, 2N, and 6N of type 1s, 2s, and 2p
respectively.
• With a reduction in the interatomic spacing, these energy levels split into bands, and the
2s and 2p bands merge into a single band having 8N available states.
• As the interatomic spacing approaches the equilibrium spacing of diamond crystal, this
band splits into two bands separated by an energy gap , where no allowed energy
states for electrons exist forbidden gap.
• The upper band (called the conduction band) and the lower band (called the valence
band) contain 4N states each.
• The lower 1s band is filled with 2N electrons, however, the 4N electrons residing in the
original n = 2 state will now occupy states either in the valence band or in the conduction
band.
• At 0 K, the electrons will occupy the lowest energy states available to them thus, the
4N states in the valence band will be completely filled, and the 4N states in the
conduction band will be completely empty.

Metals, Semiconductors, and Insulators

• For electrons to move under an applied electric field, there must be states available to
them.
• A completely filled band cannot contribute to current transport; neither can a completely
empty band.
• Thus, semiconductors at 0 K are perfect insulators.
• With thermal or optical excitation, some of these electrons can be excited from the
valence band to the conduction band, and then they can contribute to the current transport
process.
• At temperatures other than 0 K, the magnitude of the band gap separates an insulator
from a semiconductor, e.g., at 300 K, (diamond) = 5 eV (insulator), and (Silicon) =
1.12 eV (semiconductor).
• Number of electrons available for conduction can be increased greatly in semiconductors
by reasonable amount of thermal or optical energy.
• In metals, the bands are either partially filled or they overlap thus, electrons and
empty states coexist great electrical conductivity.

Direct and Indirect Semiconductors

• In a typical quantitative calculation of band structures, the wave function of a single

electron traveling through a perfectly periodic lattice is assumed to be in the form of a
plane wave moving in the x-direction (say) with propagation constant k, also called a
wave vector.
• In quantum mechanics, the electron momentum can be given by
• The space dependent wave function for the electron is
(2.1)
 where the function modulates the wave function according to the periodicity of the
lattice.

• Allowed values of energy, while plotted as a function of k, gives the E-k diagram.
• Since the periodicity of most lattices is different in various directions, the E-k diagram is
a complex surface, which is to be visualized in three dimensions.

Fig.2.2 Direct and indirect transition of electrons from the conduction band to the valence band: (a)
direct - with accompanying photon emission, (b) indirect via defect level.

• Direct band gap semiconductor: the minima of the conduction band and the maxima of
the valence band occur at the same value of k an electron making the smallest energy
transition from the conduction band to the valence band can do so without a change in k
(and, the momentum).
• Indirect band gap semiconductor: the minima of the conduction band and the maxima of
the valence band occur for different values of k, thus, the smallest energy transition for an
electron requires a change in momentum.
• Electron falling from conduction band to an empty state in valence band
recombination.
• Recombination probability for direct band gap semiconductors is much higher than that
for indirect band gap semiconductors.
• Direct band gap semiconductors give up the energy released during this transition (= )
in the form of light used for optoelectronic applications (e.g., LEDs and LASERs).
• Recombination in indirect band gap semiconductors occurs through some defect states
within the band gap, and the energy is released in the form of heat given to the lattice.

Variation of Energy Bands with Alloy Composition

• The band structures of III-V ternary and quaternary compounds change as their
composition is varied.
• There are three valleys in the conduction band: (at k = 0), L, and X.
 • In GaAs, the valley has the minimum energy (direct with = 1.43 eV) with very few
electrons residing in L and X valleys (except for high field excitations).
• In AlAs, the X valley has minimum energy (indirect with = 2.16 eV).

Fig.2.3 The E-k diagram of (a) GaAs and (b) AlAs, showing the three valleys (L, , and X) in the
conduction band.

Charge Carriers in Semiconductors

• In a metal, the atoms are imbedded in a "sea" of free electrons, and these electrons can
move as a group under the influence of an applied electric field.
• In semiconductors at 0 K, all states in the valence band are full, and all states in the
conduction band are empty.
• At T > 0 K, electrons get thermally excited from the valence band to the conduction band,
and contribute to the conduction process in the conduction band.
• The empty states left in the valence band can also contribute to current conduction.
• Also, introduction of impurities has an important effect on the availability of the charge
carriers.
• Considerable flexibility in controlling the electrical properties of semiconductors.

Electrons and Holes

• For T> 0 K, there would be some electrons in the otherwise empty conduction band, and
some empty states in the otherwise filled valence band.
• The empty states in the valence band are referred to as holes.
• If the conduction band electron and the valence band hole are created by thermal
excitation of a valence band electron to the conduction band, then they are called
electron-hole pair (EHP).

• After excitation to the conduction band, an electron is surrounded by a large number of

empty states, e.g., the equilibrium number of EHPs at 300 K in Si is , whereas
the Si atom density is .
• Thus, the electrons in the conduction band are free to move about via the many available
empty states.
• Corresponding problem of charge transport in the valence band is slightly more complex.
• Current transport in the valence band can be accounted for by keeping track of the holes
themselves.
• In a filled band, all available energy states are occupied.
• For every electron moving with a given velocity, there is an equal and opposite electron
motion somewhere else in the band.
• Under an applied electric field, the net current is zero, since for every electron j moving
with a velocity , there is a corresponding electron moving with a velocity - .
• In a unit volume, the current density J can be given by

(filled band) (2.2)

where N is the number of in the band, and q is the electronic charge.

• Now, if the electron is removed and a hole is created in the valence band, then the net
current density

• Thus, the current contribution of the empty state (hole), obtained by removing the jth
electron, is equivalent to that of a positively charged particle with velocity .
• Note that actually this transport is accounted for by the motion of the uncompensated
electron having a charge of q and moving with a velocity .
• Its current contribution (- q)(- ) is equivalent to that of a positively charged particle
with velocity + .
• For simplicity, therefore, the empty states in the valence band are called holes, and they
are assigned positive charge and positive mass.
• The electron energy increases as one moves up the conduction band, and electrons
gravitate downward towards the bottom of the conduction band.
• On the other hand, hole energy increases as one moves down the valence band (since
holes have positive charges), and holes gravitate upwards towards the top of the valence
band.
 Effective Mass

• The "wave-particle" motion of electrons in a lattice is not the same as that for a free
electron, because of the interaction with the periodic potential of the lattice.
• To still be able to treat these particles as "free", the rest mass has to be altered to take into
account the influence of the lattice.
• The calculation of effective mass takes into account the shape of the energy bands in
three-dimensional k-space, taking appropriate averages over the various energy bands.
• The effective mass of an electron in a band with a given (E,k) relation is given by

(2.4)

EXAMPLE 2.1: Find the dispersion relation for a free electron, and, thus, observe the relation
between its rest mass and effective mass.

SOLUTION: For a free electron, the electron momentum is . Thus,

. Therefore, the dispersion relation, i.e., the E-k relation is
parabolic. Hence, . This is a very interesting relation, which states that for
a free electron, the rest mass and the effective mass are one and the same, which is due to the
parabolic band structure. Most materials have non-parabolic E-k relation, and, thus, they have
quite different rest mass and effective mass for electrons.

Note: for severely non-parabolic band structures, the effective mass may become a function of
energy, however, near the minima of the conduction band and towards the maxima of the
valence band, the band structure can be taken to be parabolic, and, thus, an effective mass, which
is independent of energy, may be obtained.

• Thus, the effective mass is an inverse function of the curvature of the E-k diagram: weak
curvature gives large mass, and strong curvature gives small mass.
• Note that in general, the effective mass is a tensor quantity, however, for parabolic bands,
it is a constant.
• Another interesting feature is that the curvature is positive at the conduction band
minima, however, it is negative at the valence band maxima.
• Thus, the electrons near the top of the valence band have negative effective mass.
• Valence band electrons with negative charge and negative mass move in an electric field
in the same direction as holes with positive charge and positive mass.
• Thus, the charge transport in the valence band can be fully accounted for by considering
hole motion alone.
• The electron and hole effective masses are denoted by and respectively.
Intrinsic Material

• A perfect semiconductor crystal with no impurities or lattice defects.

• No carriers at 0 K, since the valence band is completely full and the conduction band is
completely empty.
• For T > 0 K, electrons are thermally excited from the valence band to the conduction
band (EHP generation).
• EHP generation takes place due to breaking of covalent bonds required energy = .
• The excited electron becomes free and leaves behind an empty state (hole).
• Since these carriers are created in pairs, the electron concentration ( ) is always
equal to the hole concentration ( ), and each of these is commonly referred to as the
intrinsic carrier concentration ( ).
• Thus, for intrinsic material n = p = .
• These carriers are not localized in the lattice; instead they spread out over several lattice
spacings, and are given by quantum mechanical probability distributions.
• Note: ni = f(T).
• To maintain a steady-state carrier concentration, the carriers must also recombine at the
same rate at which they are generated.
• Recombination occurs when an electron from the conduction band makes a transition
(direct or indirect) to an empty state in the valence band, thus annihilating the pair.
• At equilibrium, = , where and are the generation and recombination rates
respectively, and both of these are temperature dependent.
• (T) increases with temperature, and a new carrier concentration ni is established, such
that the higher recombination rate (T) just balances generation.
• At any temperature, the rate of recombination is proportional to the equilibrium
concentration of electrons and holes, and can be given by (2.5)
where is a constant of proportionality (depends on the mechanism by which
recombination takes place).

Extrinsic Material

• In addition to thermally generated carriers, it is possible to create carriers in the

semiconductor by purposely introducing impurities into the crystal doping.
• Most common technique for varying the conductivity of semiconductors.
 • By doping, the crystal can be made to have predominantly electrons (n-type) or holes (p-
type).
• When a crystal is doped such that the equilibrium concentrations of electrons (n0) and
holes (p0) are different from the intrinsic carrier concentration (ni), the material is said to
be extrinsic.
• Doping creates additional levels within the band gap.
• In Si, column V elements of the periodic table (e.g., P, As, Sb) introduce energy levels
very near (typically 0.03-0.06 eV) the conduction band.
• At 0 K, these levels are filled with electrons, and very little thermal energy (50 K to 100
K) is required for these electrons to get excited to the conduction band.
• Since these levels donate electrons to the conduction band, they are referred to as the
donor levels.
• Thus, Si doped with donor impurities can have a significant number of electrons in the
conduction band even when the temperature is not sufficiently high enough for the
intrinsic carriers to dominate, i.e., >> , n-type material, with electrons as
majority carriers and holes as minority carriers.
• In Si, column III elements of the periodic table (e.g., B, Al, Ga, In) introduce energy
levels very near (typically 0.03-0.06 eV) the valence band.
• At 0 K, these levels are empty, and very little thermal energy (50 K to 100 K) is required
for electrons in the valence band to get excited to these levels, and leave behind holes in
the valence band.
• Since these levels accept electrons from the valence band, they are referred to as the
acceptor levels.
• Thus, Si doped with acceptor impurities can have a significant number of holes in the
valence band even at a very low temperature, i.e., >> , p-type material, with
holes as majority carriers and electrons as minority carriers.
• The extra electron for column V elements is loosely bound and it can be liberated very
easily ionization; thus, it is free to participate in current conduction.
• Similarly, column III elements create holes in the valence band, and they can also
participate in current conduction.
• Rough calculation of the ionization energy can be made based on the Bohr's model for
atoms, considering the loosely bound electron orbiting around the tightly bound core
electrons. Thus,

(2.6)where is the relative permittivity of Si.

EXAMPLE 2.2: Calculate the approximate donor binding energy for Si ( r = 11.7, = 1.18
).

SOLUTION: From Eq.(2.6), we have =

1.867 x J = 0.117 eV.
Note: The effective mass used here is an average of the effective mass in different
crystallographic directions, and is called the "conductivity effective mass" with values of 1.28
(at 600 K), 1.18 (at 300 K), 1.08 (at 77 K), and 1.026 (at 4.2 K).

• In III-V compounds, column VI impurities (e.g., S, Se, Te) occupying column V sites act
as donors. Similarly, column II impurities (e.g., Be, Zn, Cd) occupying column III sites
act as acceptors.
• When a column IV material (e.g., Si, Ge) is used to dope III-V compounds, then they
may substitute column III elements (and act as donors), or substitute column V elements
(and act as acceptors) amphoteric dopants.
• Doping creates a large change in the electrical conductivity, e.g., with a doping of
, the resistivity of Si changes from 2 x -cm to 5 -cm.

Carrier Concentrations

• For the calculation of semiconductor electrical properties and analyzing device behavior,
it is necessary to know the number of charge carriers/cm3 in the material.
• The majority carrier concentration in a heavily doped material is obvious, since for each
impurity atom, one majority carrier is obtained.
• However, the minority carrier concentration and the dependence of carrier concentrations
on temperature are not obvious.
• To obtain the carrier concentrations, their distribution over the available energy states is
required.
• These distributions are calculated using statistical methods.

The Fermi Level

• Electrons in solids obey Fermi-Dirac (FD) statistics.

• This statistics accounts for the indistinguishability of the electrons, their wave nature, and
the Pauli exclusion principle.
• The Fermi-Dirac distribution function f(E) of electrons over a range of allowed energy
levels at thermal equilibrium can be given by

(2.7)where k is Boltzmann's constant (= 8.62 x eV/K = 1.38 x

J/K).

• This gives the probability that an available energy state at E will be occupied by an
electron at an absolute temperature T.
• is called the Fermi level and is a measure of the average energy of the electrons in the
lattice an extremely important quantity for analysis of device behavior.
• Note: for (E - ) > 3kT (known as Boltzmann approximation), f(E) exp[ - (E-
)/kT] this is referred to as the Maxwell-Boltzmann (MB) distribution (followed by gas
atoms).
• The probability that an energy state at will be occupied by an electron is 1/2 at all
temperatures.
• At 0 K, the distribution takes a simple rectangular form, with all states below
occupied, and all states above empty.
• At T > 0 K, there is a finite probability of states above to be occupied and states
below to be empty.
• The F-D distribution function is highly symmetric, i.e., the probability f( + ) that a
state E above is filled is the same as the probability [1- f( - )] that a state E
below is empty.
• This symmetry about EF makes the Fermi level a natural reference point for the
calculation of electron and hole concentrations in the semiconductor.
• Note: f(E) is the probability of occupancy of an available state at energy E, thus, if there
is no available state at E (e.g., within the band gap of a semiconductor), there is no
possibility of finding an electron there.
• For intrinsic materials, the Fermi level lies close to the middle of the band gap (the
difference between the effective masses of electrons and holes accounts for this small
deviation from the mid gap).
• In n-type material, the electrons in the conduction band outnumber the holes in the
valence band, thus, the Fermi level lies closer to the conduction band.
• Similarly, in p-type material, the holes in the valence band outnumber the electrons in the
conduction band, thus, the Fermi level lies closer to the valence band.
• The probability of occupation f(E) in the conduction band and the probability of vacancy
[1- f(E)] in the valence band are quite small, however, the densities of available states in
these bands are very large, thus a small change in f(E) can cause large changes in the
carrier concentrations.
 Fig.2.4 The density of states N(E), the Fermi-Dirac distribution function f(E), and the carrier
concentration as functions of energy for (a) intrinsic, (b) n-type, and (c) p-type semiconductors at
thermal equilibrium.

• Note: since the function f(E) is symmetrical about , a large electron concentration
implies a small hole concentration, and vice versa.
• In n-type material, the electron concentration in the conduction band increases as
moves closer to ; thus, ( - ) gives a measure of n.
• Similarly, in p-type material, the hole concentration in the valence band increases as
moves closer to ; thus, ( - ) gives a measure of p.

Electron and Hole Concentrations at Equilibrium

• The F-D distribution function can be used to calculate the electron and hole
concentrations in semiconductors, if the densities of available states in the conduction
and valence bands are known.
• In equilibrium, the concentration of electrons in the conduction band can be given by

(2.8)

where N(E)dE is the density of available states/cm3 in the energy range dE.

• Note: the upper limit of is theoretically not proper, since the conduction band does not
extend to infinite energies; however, since f(E) decreases rapidly with increasing E, the
contribution to this integral for higher energies is negligible.
• Using the solution of 's wave equation under periodic boundary conditions, it
can be shown that

(2.9)

• Thus, N(E) increases with E, however, f(E) decreases rapidly with E, thus, the product
f(E)N(E) decreases rapidly with E, and very few electrons occupy states far above the
conduction band edge, i.e., most electrons occupy a narrow energy band near the
conduction band edge.
• Similarly, the probability of finding an empty state in the valence band [1 - f(E)]
decreases rapidly below , and most holes occupy states near the top of the valence
band.
• Thus, a mathematical simplification can be made assuming that all available states in the
conduction band can be represented by an effective density of states NC located at the
conduction band edge and using Boltzmann approximation.

Thus, (2.10)

where .

• Note: as ( - ) decreases, i.e., the Fermi level moves closer to the conduction band,
the electron concentration increases.
• By similar arguments,

(2.11)

where is the effective density of states located at the valence band edge .

• Note: the only terms separating the expressions for and are the effective masses of
electrons ( ) and holes ( ) respectively, and since , hence, .
 • Thus, as ( - ) decreases, i.e., the Fermi level moves closer to the valence band
edge, and the hole concentration increases.
• These equations for and are valid in equilibrium, irrespective of the material being
intrinsic or doped.
• For intrinsic material lies at an intrinsic level (very near the middle of the band
gap), and the intrinsic electron and hole concentrations are given by
and (2.12)
• Note: At equilibrium, the product is a constant for a particular material and
temperature, even though the doping is varied,

i.e., (2.13)

• This equation gives an expression for the intrinsic carrier concentration ni as a function of
, , and temperature:

(2.14)

• These relations are extremely important, and are frequently used for calculations.
• Note: if were to be equal to , then would have been exactly at mid gap (i.e., -
= - = /2).
• However, since , is displaced slightly from mid gap (more for GaAs than that
for Si).
• Alternate expressions for and :
and (2.15)

• Note: the electron concentration is equal to ni when is at , and n0 increases

exponentially as moves away from towards the conduction band.
• Similarly, the hole concentration varies from to larger values as moves from
towards the valence band.

EXAMPLE 2.3: A Si sample is doped with B . What is the equilibrium electron

concentration n0 at 300 K? Where is relative to ? Assume for Si at 300 K = 1.5 x

SOLUTION: Since B (trivalent) is a p-type dopant in Si, hence, the material will be
predominantly p-type, and since >> , therefore, will be approximately equal to , and
= . Also,
 . The resulting band diagram is:

Temperature Dependence of Carrier Concentrations

• The intrinsic carrier concentration has a strong temperature dependence, given by

(2.16)
• Thus, explicitly, ni is proportional to T3/2 and to e 1/T, however, Eg also has a
temperature dependence (decreasing with increasing temperature, since the interatomic
spacing changes with temperature).

Fig.2.5 The intrinsic carrier concentration as a function of inverse temperature for Si, Ge,
and GaAs.
 • As changes with temperature, so do and .
• With and T given, the unknowns are the carrier concentrations and the Fermi level
position with respect to one of these quantities must be given in order to calculate the
other.
• Example: Si doped with donors ( ).
• At very low temperature, negligible intrinsic EHPs exist, and all the donor electrons are
bound to the donor atoms.
• As temperature is raised, these electrons are gradually donated to the conduction band,
and at about 100 K (1000/T = 10), almost all these electrons are donated this
temperature range is called the ionization region.

Once all the donor atoms are ionized, the electron concentration , since for each donor
atom, one electron is obtained.

Fig.2.6 Variation of carrier concentration with inverse temperature clearly showing the three
regions: ionization, extrinsic, and intrinsic.

• Thus, remains virtually constant with temperature for a wide range of temperature
(called the extrinsic region), until the intrinsic carrier concentration ni starts to become
comparable to .
• For high temperatures, >> , and the material loses its extrinsic property (called the
intrinsic region).
• Note: in the intrinsic region, the device loses its usefulness => determines the maximum
operable temperature range.

Compensation and Space Charge Neutrality

• Semiconductors can be doped with both donors ( ) and acceptors ( ) simultaneously.

• Assume a material doped with > predominantly n-type lies above
acceptor level Ea completely full, however, with above , the hole concentration
cannot be equal to .
• Mechanism:
o Electrons are donated to the conduction band from the donor level
o An acceptor state gets filled by a valence band electron, thus creating a hole in the
valence band.
o An electron from the conduction band recombines with this hole.
o Extending this logic, it is expected that the resultant concentration of electrons in
the conduction band would be instead of .
o This process is called compensation.
• By compensation, an n-type material can be made intrinsic (by making = ) or even
p-type (for > ).

Note: a semiconductor is neutral to start with, and, even after doping, it remains neutral
(since for all donated electrons, there are positively charged ions ( ); and for all
accepted electrons (or holes in the valence band), there are negatively charged ions ( ).
• Therefore, the sum of positive charges must equal the sum of negative charges, and this
governing relation,
given by (2.17) is referred to as the equation for space charge neutrality.
• This equation, solved simultaneously with the law of mass action (given by )
gives the information about the carrier concentrations.
Note: for , .