PHY 4311 SOLID STATE PHYSICS II

1. ELECTRIC PROPERTIES OF METALS

1.1 Free electron theory

In the free electron model, we assume that the valence electrons can be treated as free, or at least moving in a
region constant potential, and non-interacting.
1.1.1 Postulates
i. The valence electrons of metallic atoms are free to move about the whole volume of the metals like
the molecules of a gas in a container. The collection of valence electrons from all the atoms in a given
piece of metal forms electron gas. It is free to move throughout the volume of the metal.
ii. These free electrons move in random directions and make collisions with either positive ions fixed in
the lattice or other free electrons. All the collisions are elastic i.e., there is no loss of energy.
iii. The movements of free electrons obey the laws of the classical kinetic theory of gases.
iv. The velocities of free electrons in a metal obey the classical Maxwell-Boltzmann law of distribution
of velocities.
v. The free electrons move in a completely uniform potential field due to ions fixed in the lattice.
vi. When an electric field is applied to the metal, the free electrons are accelerated in the direction opposite
to the direction of applied electric field (towards positive terminal of the source). The average velocity
acquired by an electron in the presence of electric field is known as ‘drift velocity (vd).
vii. In the absence of the electric field, the distance traveled between two successive collisions is called
mean free path (λ) and the time taken by an electron between two successive collisions is known as
relaxation time (t). The average velocity of free electrons is called ‘root mean square velocity, (vrms)
or thermal velocity of electrons.

1.1.2 Success of theory: It was only able to explain the properties of metals such as
i. Electrical conductivity.
ii. Ohm’s law
iii. Thermal conductivity
iv. Wiedemann-Franz law the Wiedemann–Franz law states that the ratio of the electronic contribution
of the thermal conductivity (κ) to the electrical conductivity (σ) of a metal is proportional to
𝜅
the temperature (T), 𝜎 = 𝐿𝑇 − − − 1.1
The proportionality constant L, known as the Lorenz number.
v. Complete opacity of metals and their high luster.

1.1.3 Failure of the theory

i. It could not explained the difference between conductors, insulators and semiconductors
ii. It is found that divalent and trivalent metals are not good conductors even though the theory say the
conductivity is proportional to the free electron concentration. Rather monovalent metals Cu, Ag, Au,
etc. are good conductors.
iii. Some of the metals exhibit positive Hall coefficients, while the free electron theory predicts a negative
hall coefficients for all the metals.

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1.2 Fermi energy
Fermi energy is defined as the highest occupied energy level of a material at absolute zero temperature. In
other words, all electrons in a body occupy energy states at or below that body's Fermi energy at 0K. The
Fermi energy is the difference in energy, mostly kinetic. In metals this means that it gives us the velocity of
the electrons during conduction. So during the conduction process, only electrons that have an energy that is
close to that of the Fermi energy can be involved in the process. This concept of Fermi energy is useful for
describing and comparing the behaviour of different semiconductors. For example: an n-type semiconductor
will have a Fermi energy close to the conduction band, whereas a p-type semiconductor will have a Fermi
energy close to the valence band.

Fig. 1.1 Fermi energies of different material types.

As a material's temperature rises above absolute zero, the probability of electrons existing in an energy state
greater than the Fermi energy increases, and there is no longer any constant highest occupied level, so while
the material's Fermi energy may be useful as a reference, it is not very useful at real temperatures. Instead, we
can approximate the average energy level at which an electron is present is with the Fermi-Dirac
distribution:

1.3 Density of Energy States

In band theory N atoms with an atomic orbitals formed N molecular orbitals (MO). Each MO can take
2 electrons (opposite spin) so that t h e r e are a total of 2N energy states. These are discrete states but
for large values of N the spacing between them are so small that they can be considered to be continuous,
forming an energy band. Density of states (DOS) is defined as the number of available energy states
per unit energy per unit volume. The units are 𝐽−1 𝑚−3 or 𝑒𝑉 −1 𝑐𝑚−3 and it provides
information on how the energy states are distributed in a given solid. It is typically denoted as 𝑔(𝐸).
The experimental density of states of a material can be measured by photo electron spectroscopy
or Scanning Tunneling Microscopy (STM) or Electron Energy Loss spectroscopy (EELS). These
techniques probe the density of empty or filled states a r o u n d the Fermi energy, called Local DOS
(LDOS). Density functional calculations can also be used to calculate the density of states.

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Fig.1.2 Calculated DOS of Cu around the Fermi level EF. The filled states lie below EF while the empty states
lie above EF. The broad peak below EF corresponds to the filled 3d states.

These model the electron density distribution in a solid and also model the atomic potential within the
solid. Figure 1.2 shows the calculated DOS for Cu around the Fermi energy. The density of states can
be used to calculate the total number of electron in a band. If 𝑔(𝐸) is the DOS, then the total number
of electrons in a band, S(E) is given by

𝑆(𝐸) = ∫ 𝑔(𝐸)𝑑𝐸 − − − 1.2

where the integration is performed over the entire energy band. This Eqn assumes that the probability of
occupation of the state is 1. This is not always true when we look at the conduction band of a
semiconductor, w h e r e the occupation probability i s defined by a Fermi function. An energy expression
for the density of states,𝑔(𝐸), will be useful for evaluation of the integral in Eqn 1.2.

1.3.1 DOS in 3-Dimensional uniform solid

To simplify the calculation f o r 𝑔(𝐸) consider a 3D solid with uniform potential. This is a simplification
of a real solid but is a good approximation of the valence band of metals where the electrons are loosely
bound to the atom and are delocalized. We will also use this approximation for electrons and holes near
the edge of the band. For simplicity the uniform potential can be taken to be zero. For this solid the
electron is defined by 3 quantum numbers(𝑛1 , 𝑛2 . 𝑛3 ) and its energy is given by
ℎ2
𝐸= 2
(𝑛12 , 𝑛22 , 𝑛32 ) − − − 1.3𝑎
8𝑚𝑒 𝐿

Eqn 1 . 3 a is for a cubic solid of length L with the 3 quantum numbers for the 3 axes. 𝑚𝑒 is the free
electron mass. We can replace the 3 quantum numbers by a single value n so that Eqn 1.3 a is modified
into

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 ℎ2 𝑛2
𝐸= − − − 1.3𝑏
8𝑚𝑒 𝐿2
For small values of n these energy levels are quantized, but for large values of n the spacing between
them are close so that the energy levels can be considered to be continuous. So n represents t he
radius of a sphere, where the total n u m b e r of states w i t h i n the sphere is given by its volume. This
is shown schematically in figure 1.3. Since the quantum numbers can only be positive the quantum
numbers represent the electron wave function and it can be shown that to avoid exponential increasing
functions the quantum numbers have to be non-zero positive integers) we can only take the first
quadrant of the sphere.

Fig. 1.3 Energy states in a solid with uniform potential. The portion of the sphere corresponds to the constant
energy surface. Only the first quadrant is to be considered since the quantum numbers are non-zero positive
integers

Hence the total number of ‘orbitals’ (energy states), S o r b (n), i s given by the volume of the sphere in the
first quadrant
1 4 1
𝑆𝑜𝑟𝑏 (𝑛) = ( 𝜋𝑛3 ) = 𝜋𝑛3 − − − 1.4
8 3 6
Since each orbital can take two electrons of opposite spin, the total number of energy states (including
spin), 𝑆(𝑛), is given by
1
𝑆(𝑛) = 2𝑆𝑜𝑟𝑏 (𝑛) = 𝜋𝑛3 − − − 1.5
3

We can relate n (quantum number of the electron in the solid) to the energy E using Eqn 1.3b to write
the total number of states in terms of energy, 𝑆(𝐸). This is given by

1 3 𝐿 3
𝑆(𝐸) = 𝜋(8𝑚𝑒 𝐸)2 ( ) − − − 1.6
3 ℎ

Dividing by the volume of the cube will give total number of states per unit volume, 𝑆𝑣 (𝐸). That is
𝑆(𝐸)
= 𝑆𝑣 (𝐸)
𝐿3

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 3
1 𝜋(8𝑚𝑒 𝐸)2
∴ 𝑆𝑣 (𝐸) = − − − 1.7
3 ℎ3

The density of states is the differential of the total number of states, (𝑔(𝐸) = 𝑆𝑣 (𝐸) 𝑑𝐸), so that 𝑔(𝐸) is
given by

3 3 3
1 𝜋(𝑚𝑒 )2 (8)2 (𝐸)2
𝑔(𝐸) = 𝑆𝑣 (𝐸) 𝑑𝐸 = 𝑑𝐸
3 ℎ3
3 3 1
𝜋 3 (𝑚𝑒 )2 (8)2 (𝐸)2
𝑔(𝐸) = ( ) ( )
3 2 ℎ3
3 3 1
𝜋 (𝑚𝑒 )2 (8)2 (𝐸)2
𝑔(𝐸) =
2 ℎ3

3
𝑚𝑒 2
∴ 𝑔(𝐸) = 8𝜋√2 ( 2 ) √𝐸 − − − 1.8
ℎ

Eqn 8 gives the DOS in a solid with a uniform potential. At the bottom of the band, which is normally
chosen as the reference so energy is set to 0, DOS is zero. As the energy increases 𝑔(𝐸) also increases.
The functional form is shown schematically in figure 1.4 𝑔(𝐸) Represents the density of available states.
It does not provide information whether those states are occupied or not. The occupation is given by the
Fermi function and is usually a function of temperature.

Fig. 1.4 Plot of DOS vs. E for a 3D solid using free electron mass. This is a plot of Eqn 1.7 using MATLAB.

1.4 Electron occupation probability

Density of states gives the number of available states for electrons to occupy.
At absolute zero, electrons occupy the lowest energy state. Above 0 K, there is always some thermal energy
for the electrons to occupy the unoccupied energy states. There are different statistics to describe the
occupation of energy levels. The simplest statistics is the Boltzmann statistics which gives the probability of
occupation, 𝑝(𝐸), of a given energy state, E,
𝐸
𝑝(𝐸) = 𝐴 𝑒𝑥𝑝 (− ) − − − 1.9
𝑘𝐵 𝑇

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A is a constant. At 0 K all the particles have energy 0 and at any given T, 𝑝(𝐸) gives the probability of
occupation. For a given temperature, 𝑝(𝐸) reduces as E increases, as shown in figure 1.5. Boltzmann statistics
works for a system of non-interacting particles but electrons have a strong repulsive interaction. By Pauli's
exclusion principle only 2 electrons can occupy a given energy state (of opposite spin). So all electrons cannot
occupy the same energy state, even at absolute zero. The statistics obeyed by electrons is given by the Fermi-
Dirac statistics.

2.
Fig. 1.5 Boltzmann probability distribution vs. energy at 1000 K. The probability drops steeply as energy
increases due to the exponential nature of the function. The plot was generated in MATLAB.

1.5 Fermi-Dirac distribution

In Fermi-Dirac statistics, the probability of electron occupation of a given energy state is represented by 𝑓(𝐸)
and given by
1
𝑓(𝐸) = − − − 1.10
𝐸
1 + 𝐴 𝑒𝑥𝑝 ( )
𝑘𝐵 𝑇

A is a constant,. 𝑓(𝐸) is called the Fermi function. For solids A is related to the Fermi energy (E F) so that
𝑓(𝐸) is given by

1
𝑓(𝐸) = − − − 1.11
𝐸 − 𝐸𝐹
1 + 𝑒𝑥𝑝 ( )
𝑘𝐵 𝑇
2 2
3𝑁 3 𝑁
𝐸𝑓 = (8𝑚) (𝜋𝑉 ) Where N is Number of possible quantum states, V is volume, 𝑉 = 𝑛, m is mass of electron

and ħ is plank's constant. At absolute zero all energy levels below the Fermi level are occupied so that the
occupation probability is 1. Above E the levels are empty so that 𝑓(𝐸) is 0. Also, at any temperature 𝑓(𝐸) at
the Fermi level is 0.5. Figure 1.6 plots the Fermi function as a function of energy. When the energy difference
(𝐸 − 𝐸𝐹 )is much larger than 𝑘𝐵 𝑇 the Fermi function simplifies to the Boltzmann form shown in Eqn 1.9.
If 𝑔(𝐸) is the density of states and 𝑓(𝐸) gives the probability o f occupation of those states at a given
temperature, the number of occupied states, 𝑛(𝐸), is given by
𝑛(𝐸) = ∫ 𝑔(𝐸)𝑓(𝐸)𝑑𝐸 − − − 1.12
If the number of occupied states in an energy band needs to be calculated the integration needs to be performed
over the entire band. This will be a function of temperature, since the Fermi function is temperature dependent.

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Eqn 1.12 can be used to calculate the concentration of electron and holes in semiconductors, which decides
their conductivity.

Fig. 1.6 Fermi function vs. energy at three different temperatures. The probability drops steeply as energy is
increased from the Fermi function. To increase the probability the temperature has to be increased. The plot
was generated using MATLAB using E F= 2:5 eV. T = 0:1 K was used to simulate the 0 K distribution.

1.6 Electrical Conductivity

Electrical conduction is the flow of electric current in a solid specimen when a potential difference is
maintained across its two ends. The relation between current I and potential difference V is governed by
Ohm's law:
𝑉 = 𝐼𝑅 − − − 1.13
With I denoting the electric current, V the potential drop and R the resistance of the wire. Current
density 𝑱 is defined as electric current flowing through unit cross-sectional area, i.e.
𝐼
𝑱 = − − − 1.14
𝐴
Where A is the area of cross-section of the specimen.
Also, we may write the potential difference 𝑉 as
𝑉 = 𝜺𝐿 − − − 1.15
Where 𝜺 = Electric field strength and 𝐿 = Length of the specimen
From Eqn 1.13:
𝑉
𝐼 = − − − 1.16
𝑅
Using Eqn 1.16 in Eqn 1.14 gives:
𝑉
𝑱= − − − 1.17
𝐴𝑅
Using Eqn 1.15 in Eqn 1.17 gives:
𝜺𝑳
𝑱=
𝐴𝑅
Rearranging terns we obtain:
𝐿
𝑱=𝜺 − − − 1.18
𝐴𝑅
If we define a parameter, called resistivity, 𝜌 as:
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 𝐴
𝜌=𝑅 − − − 1.19
𝐿
There for we can write 𝐽 aa:
1
𝑱=𝜺 = 𝜎𝜺
𝜌
∴ 𝑱 = 𝜎𝜺 − − − 1.20
1
Where = 𝜎 and 𝜎 is called the electrical conductivity.
𝜌
Electrical conductivity is is one of the important parameters that enable us to differentiate a metal from an
insulator. The value of 𝜎 is very large (~107 (Ω𝑚)−1 ) for metals and very small (~10−10 (Ω𝑚)−1 ) for
insulators.
Current (𝐼) is defined as amount of charge passing through unit cross-sectional area in time t, i.e.
𝑑𝑞
𝐼= − − − 1.21
𝑑𝑡
Where dq is the amount of charge passing through unit cross-sectional area.
The amount of charge (electron) passing through the cross-sectional area A in time dt is: − 𝑛 𝑒 𝑣𝑑 𝐴 𝑑𝑡
Where, n is the number of electrons per unit volume and 𝑣𝑑 is the drift velocity of the electrons. Thus from
Eqn 1.14 𝐽 becomes:
𝑑𝑞 1
𝑱= − − − 1.22𝑎
𝑑𝑡 𝐴
In vector form, we can write
𝒋 = −𝑛𝑒𝒗𝑑 − − − 1.22𝑏
Under the influence of applied electric field, electron experiences acceleration a n d gets drifted with
velocity 𝑣𝑑 . Thus, we may write, using Newton’s second law of motion we can write

𝜕𝒗𝑑 𝑓𝑜𝑟𝑐𝑒 𝑒
( ) = = 𝜀 − − − 1.23
𝜕𝑡 𝑓𝑖𝑒𝑙𝑑 𝑚 𝑚
Eqn. 1 . 2 3 shows that for a given electric field, the drift velocity o f an electron continuously increases
w i t h time. This inference, h o w e v e r , i s not in agreement with experimental observations (expressed
a s Ohm’s law). At a given temperature, electrical conductivity of a m e t a l is constant. Thus, from Eqn.
1 . 2 0 we may conclude that for a given electric field, the current density should be constant suggesting
that drift velocity of the electron cannot increase infinitely and must obtain a steady value.
Recall from elementary mechanics that when a body falls through a viscous medium, its accelerated
motion becomes uniform with a constant limiting velocity. Here, an accelerating electron suffers
collisions with ions (and impurities) a n d attains a steady drift velocity. Thus, the effect of collisions i s
analogous t o a viscous (or frictional) for ce, F which is proportional to mass and drift velocity o f
electrons:
𝐹 ∝ 𝑚𝑣𝑑
𝑚𝑣𝑑
∴𝐹= − − − 1.24
𝜏
1
Where, 𝜏 is the proportionality constant, known as collusion time or relaxation time for collision b e t w e e n
electron a n d ions.
Relaxation time is assumed to be independent of energy and direction of motion of electrons. It refers to the
average time interval between two successive collisions. You may now ask: Is there some experimental
evidence in favour of the existence of such a viscous force in a metal? Well, so far as Drude-Lorentz theory

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 is concerned, it was simply assumed that such a force does exist and can be represented in terms of relaxation
time. They did not elaborate upon the nature of such processes. Let us see how this assumption influences
electrical conductivity does. The change in drift velocity due to collisions can be expressed, using Newton's
second law of motion, as
𝜕𝒗𝑑 𝐹 𝒗𝑑
( ) = =− − − − 1.25
𝜕𝑡 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛 𝑚 𝜏
The negative s i gn indicates t h at drift velocity d e c r e a s e s due to collisions.
Under the influence of two competing processes, a steady state is obtained and electrons m ove with a
constant dr i f t velocity. That is, in the steady state, we must have
𝑑𝒗𝑑
=0
𝑑𝑡

This may be expressed as a sum of two terms:

𝜕𝒗𝑑 𝜕𝒗𝑑
( ) +( ) = 0 − − − 1.26
𝜕𝑡 𝑓𝑖𝑒𝑙𝑑 𝜕𝑡 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛
Using Eqns. 1.23 and (9.5), in Eqn 1.26 gives:
𝑒 𝒗𝑑
𝜺− =0
𝑚 𝜏
𝑒𝜏
𝒗𝑑 = 𝜀 − − − 1.27
𝑚
This expression shows that drift velocity of electrons is linearly proportional to the electric field. To see
whether or not this conclusion about 𝑣𝑑 is consistent with Ohm's law, let us equate Eqn 1.20 and 1.22b:
∴ 𝜎𝜺 = −𝑛𝑒𝒗𝑑
𝜎
∴ 𝒗𝑑 = − 𝜺 − − − 1.28
𝑛𝑒

Thus, Ohm's law also predicts linear dependence of drift velocity on the applied electric field, and is consistent
with Drude-Lorentz theory. Further, on comparing Eqns 1.27 and 1.28, we get
𝑛𝑒 2 𝜏
𝜎= − − − 1.29
𝑚
Eqn 1.29 expresses electrical conductivity in terms of microscopic characteristics of an electron. If the value
of o given by Eqn 1.29 is in agreement with the experimental value, we can conclude that Drude-Lorentz
theory successfully explains Ohm's law - qualitatively as well as quantitatively. However, for calculating
electrical conductivity, 𝜎, we will need a precise value of the relaxation time 𝜏.

Exercises 1
1. Determine the density of state (DOS) in 1 and 2-Dimensional uniform solids
2. The experimentally observed value of electrical conductivity of a metal is of the order of
107 Ω−1 𝑚−1Calculate relaxation time for the electron-ion collisions. Given e = 1.6 x 10-19 C, m = 9.1 x10-
31
kg and n = 1028 m-3.
3. A gold crystal has an FCC lattice with one gold atom per lattice point and a lattice constant of 4.08Å. Every
gold atom has one valence electron. Estimate the electron Fermi energy in a gold crystal.
4. A copper crystal has an FCC lattice with one Cu atom per lattice point and a lattice constant of 3.61 Å. Every
copper atom has one valence electron. Estimate the electron Fermi energy, Fermi velocity and electron
wavelength in a copper crystal.

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2 BAND THEORY OF SOLIDS
2.1 Origin of Energy Bands
In a single isolated atom, the electrons in each orbit have definite energy associated with it. But in case of
solids all the atoms are close to each other, so the energy levels of outermost orbit electrons are affected by
the neighboring atoms. When two single or isolated atoms are bring close to each other then the outermost
orbit electrons of two atoms are interact or shared with each other. i.e, the electrons in the outermost orbit of
one atom experience a attractive force from the nearest or neighboring atomic nucleus. Due to this the energies
of the electrons will not be in same level, the energy levels of electrons are changed to a value which is higher
or lower than that of the original energy level of the electron.
The electrons in same orbit exhibits different energy levels. The grouping of this different energy levels is
called energy band. However, the energy levels of inner orbit electrons are not much affected by the presence
of neighboring atoms.
2.1.1 Important energy bands in solids
There are number of energy bands in solids but three of them are very important. These three energy bands
are important to understand the behavior of solids. These energy bands are: Valence band, Conduction band
and Forbidden band or forbidden gap

Fig. 2.1 Different energy bands

 Valence band
The energy band which is formed by grouping the range of energy levels of the electrons or outermost orbit
electrons is called as valence band. Valence band is present below the conduction band as shown in figure 2.1.
Electrons in the valence band have lower energy than the electrons in conduction band.
The electrons present in the valence band are loosely bound to the nucleus of atom.
 Conduction band
The energy band which is formed by grouping the range of energy levels of the free electrons is called as
conduction band. Generally, the conduction band is empty but when external energy is applied the electrons
in the valence band jumps in to the conduction band and becomes free electrons. Electrons in the conduction
band have higher energy than the electrons in valence band. The conduction band electrons are not bound to
the nucleus of atom.
 Forbidden gap
The energy gap which is present between the valence band and conduction band by separating these two
energy bands is called as forbidden band or forbidden gap. In solids, electrons cannot stay in forbidden gap
because there is no allowed energy state in this region. Forbidden gap is the major factor for determining the
electrical conductivity of a solid. The classification of materials as insulators, conductors and semiconductors
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is mainly depends on forbidden gap. The energy associated with forbidden band is called energy gap and it is
measured in unit electron volt (eV).
1 eV = 1.6 × 10-19 J
The applied external energy in the form of heat or light must be equal to the forbidden gap in order to push an
electron from valence band to the conduction band.

2.2 One Electron Approximation

Most of the physical and chemical properties of condensed matter systems are governed by the conduction
electrons. One is often interested in finding the eigen states of these electrons as most of the properties can be
understood through them. Electrons are lighter than the nuclei and hence respond much faster. Therefore, for
any instantaneous position of the nuclei, the electrons can be considered to be in stationary states. The
dynamics of electrons and nuclei can thus be treated independently. This is the Born–Oppenheimer
approximation. Now the problem at hand is the evaluation of the eigen states of an N-electron system. The
Schrodinger equation of an N-electron system is written as
𝑁
ħ2 2
∑ ∇ 𝜓 + 𝑉𝜓 = 𝐸𝜓 − − − 2.1
2𝑚 𝑖
𝑖=1

Solving this equation is highly impractical and hence it immediately calls for further approximations. An
important approximation that reduces the N-electron Schrodinger equation to one electron Schrodinger
equation is the one electron approximation. The density functional formalism of Kohn and Sham in the local
density approximation is an important scheme for obtaining a one electron Schrodinger-like equation. The one
electron Schrodinger equation (in atomic units) that results from the formalism is written as
(−∇2 + 𝑉)𝜓𝑖 = 𝐸𝑖 𝜓𝑖 − − − 2.2

Here V is the effective one electron potential and it consists of the field from the nuclei and the field due to
the charge cloud of all the other electrons including the exchange and correlation contribution.

2.3 Electron in One Dimensional Periodic Potential (Kronig-Penney model)

Electron in a crystal experiences a periodic potential which is along a line of the ionized atoms. Assuming
one-dimensional lattice with the lattice constant a as shown in Figure 2.2 (a), resembling the individual atomic
potentials as the atom is approached closely and flattening off in the region between atoms. We approximate
this by a square periodic potential in Figure 2.2(b) as introduced by Kronig and Penney. The Kronig-Penney
model is a simplified model for an electron in a one-dimensional periodic potential, in the case of the Kronig-
Penney model, the potential U(x) is a periodic square wave. A virtue of this model is that it is possible to
analytically determine the energy eigenvalues and eigenfunctions. It is also possible to find analytic
expressions for the dispersion relation (E vs. k) and the electron density of states.

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Fig. 2.2 One-dimensional periodic potential energy model. (a) Sketch of potential model, and (b) Kronig-Penney model.
The possible states that the electron can occupy are determined by the Schrödinger equation. The
Schrödinger equation for the wave function is;
2
𝜕 2𝜓
− + (𝑈(𝑥) − 𝐸)𝜓 = 0 − − − 2.3
2𝑚 𝜕𝑥 2
The potential distribution is given by:

0 𝑓𝑜𝑟 0 < 𝑥 ≤ 𝑎
𝑈(𝑥) = { − − − 2.4
𝑈𝑜 𝑓𝑜𝑟 − 𝑏 ≤ 𝑥 ≤ 0
Subject to the following periodicity requirement

𝑈(𝑥 + 𝑎 + 𝑏) = 𝑈(𝑥)
The general solution for Eqn 2.3 are
𝜓 = 𝐴𝑒 𝑖𝐾𝑥 + 𝐵𝑒 −𝑖𝐾𝑥 (0 < 𝑥 ≤ 𝑎) − − − 2.5
𝜓 = 𝐶𝑒 𝑄𝑥 + 𝐷𝑒 −𝑄𝑥 (−𝑏 < 𝑥 ≤ 0) − − − 2.6
ħ2 𝐾2 ħ2 𝑄 2
Where 𝐸 = and 𝑈𝑜 − 𝐸 = − − − 2.7
2𝑚 2𝑚

And K and Q are to be determined, from which the eigen energy E of the electron inside such a periodic
potential is to be extracted. Four boundary conditions are needed to determine the unknown coefficient A, B,
C, and D. We can use the continuity of the wavefunction and its derivative at 𝑥 = 0, which gives:
𝐴 + 𝐵 = 𝐶 + 𝐷 − − − 2.8
𝑖𝑘(𝐴 − 𝐵) = 𝑄(𝐶 − 𝐷) − − − 2.9
Two more boundary conditions are necessary to determine the four unknown coefficients. Due to the
periodicity in the potential, the wavefunction at any two points separated by a lattice vector is related
through the Bloch theorem in the x-direction,
𝜓(𝑥 + 𝑎 + 𝑏) = 𝜓(𝑥)𝑒 𝑖𝐾(𝑎+𝑏) − − − 2.10
We should distinguish the wave vector k from the propagation vector of the solution K in Eqn
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2.5. The latter contains the energy of the electrons that we want to find. We want to find a relation between k
and E, which is equivalent to a relation between k and K. The continuity requirements for the wavefunction
and its derivative at x = a are then
𝐴𝑒 𝑖𝐾𝑎 + 𝐵𝑒 −𝑖𝐾𝑎 = (𝐶𝑒 −𝑄𝑏 + 𝐷𝑒 𝑄𝑏 )𝑒 𝑖𝑘(𝑎+𝑏) − − − 2.11
𝑖𝐾(𝐴𝑒 𝑖𝐾𝑎 − 𝐵𝑒 −𝑖𝐾𝑎 ) = 𝑄(𝐶𝑒 −𝑄𝑏 − 𝐷𝑒 𝑄𝑏 )𝑒 𝑖𝑘(𝑎+𝑏) − − − 2.12

Four equations with four unknowns have a solution only if the determinant of the coefficients vanishes,
yielding
𝑄2 − 𝐾 2
= 𝑠𝑖𝑛ℎ(𝑄𝑏)𝑠𝑖𝑛(𝐾𝑎) + 𝑐𝑜𝑠ℎ(𝑄𝑏)𝑐𝑜𝑠(𝐾𝑎) = 𝑐𝑜𝑠(𝑘(𝑎 + 𝑏)) − − − 2.13
2𝐾𝑄
It is rather tedious to obtain this equation. The result is simplified if we represent the potential by the periodic
𝑄 2 𝑏𝑎
delta function obtained when we pass to the limit 𝑏 = 0 and 𝑈𝑜 = ∞ in such a way that = 𝑃, a finite
2
quantity. In this limit Q >> K and Qb <<1. Then, Equation (2.13) reduces to

𝑃
𝑠𝑖𝑛(𝐾𝑎) + 𝑐𝑜𝑠(𝐾𝑎) = 𝑐𝑐𝑜𝑠(𝐾𝑎) = − − −2.14
𝐾𝑎
The range of K for which this equation has solutions are plotted in Figure 2.3, for the case 𝑃 = 3𝜋/2. We can
convert the solution for K into energy, and redraw the graph as a function of ka as shown in Figure 2.3. The
figure shows that, for each wave vector k, there are multiple values for the electron energy E. The relationship
between the energy and the wave vector is the dispersion relation.

Fig. 2.3 Left-hand side of Equation (2.14) as function of Ka. Because the right-hand side is always less than
or equal to one, there are regions (the shaded area) where no solution for Ka exists, and thus no electrons
exist with energy corresponding to the values of K in these regions.

2.4 Effective Mass

In solid state physics, a particle's effective mass (often denoted m*) is the mass that it seems to have
when responding to forces, or the mass that it seems to have when interacting with other identical particles in
a thermal distribution. But in reality, an electron in a crystal experiences complex forces from the ionized
atoms. We imagine that the atoms in the linear chain form the electrical periodic potential. For electrons or
electron holes in a solid, the effective mass is usually stated in units of the rest mass of an electron, me
(9.11×10−31 kg). In these units it is usually in the range 0.01 to 10, but can also be lower or higher—for
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example, reaching 1,000 in exotic heavy fermion materials, or anywhere from zero to infinity (depending on
definition) in graphene. As it simplifies the more general band theory, the electronic effective mass can be
seen as an important basic parameter that influences measurable properties of a solid, including everything
from the efficiency of a solar cell to the speed of an integrated circuit.
If the free electron mass m is replaced by the effective mass m*, we can treat the motion of electrons
in the conduction band as free electrons. An exact defined value of the wave vector k, however, implies
complete uncertainty about the electron’s position in real space. Mathematically, localization can be described
by expressing the state of the electron as a wave packet, in other words, a group velocity. The group velocity
𝑣𝑔 of electrons in Figure 2.4 is the slope of the dispersion relation.
𝜕𝜔
𝑣𝑔 = − − − 2.15
𝜕𝑘
Since the wavelength is twice the lattice constant a, the boundaries at the zone in k-space is 𝑘 = ± 𝜏⁄𝑎 . The
frequency 𝜔 associated with a wave rector of energy E is

𝑝
𝐸 = 𝜔ħ 𝑎𝑛𝑑 𝑘 = − − − 2.16
ħ
where the two equations are known as the Planck-Einstein relations.

Fig. 2.4 Dispersion relation of a group of electrons with a nearest neighbor interaction. Note that 𝜋 is linear
for small k, and that 𝜕𝜔⁄𝜕𝑘 vanishes at the boundaries of the Brillouin zone ((𝑘 = ± 𝜋⁄𝑎 ).

1 𝜕𝐸
𝑣𝑔 = − − − 2.17
ħ 𝜕𝑘
The derivative of Eqn. 2.17 with respect to time is

𝜕𝑣𝑔 1 𝜕 2 𝐸 1 𝜕 2 𝐸 𝜕𝑘
= = − − − 2.18
𝜕𝑡 ħ 𝜕𝑡𝜕𝑘 ħ 𝜕𝑘 2 𝜕𝑡

𝑚𝜕𝑣𝑔 ħ𝜕𝑘
From Eqn 2.16, we have 𝑚𝑣𝑔 = ħ𝑘 and = . The force acting on the group of electrons is then
𝜕𝑡 𝜕𝑡
𝜕𝑣𝑔 𝜕𝑘
𝐹=𝑚 =ħ − − − 2.19
𝜕𝑡 𝜕𝑡
Combining Eqns 2.18 and 2.19 gives
ħ2 𝜕𝑣𝑔
𝐹= − − − 2.20
𝜕 2 𝐸 𝜕𝑘 2 𝜕𝑡
This indicates that there is an effective mass m*, which will replace the electron mass m.

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 1 1 𝜕 2𝐸
= − − − 2.21
𝑚∗ ħ2 𝜕𝑘 2
The effective mass m* is the second order of derivative of energy with respect to wave vector, which is
representative of the local curvature of the dispersion relation in three dimensional space. The effective mass
is a tensor and may be obtained experimentally or numerically.

2.5 Brillion Zone

A Brillouin zone is a particular choice of the unit cell of the reciprocal lattice. It is defined as the
Wigner-Seitz cell of the reciprocal lattice. Alternatively, it is defined as the set of points closer to the origin
than to any other reciprocal lattice point. The concept of a Brillouin zone was first developed by Léon Brillouin
(1889-1969), a French physicist. During his work on the propagation of electron waves in a crystal lattice, he
introduced the concept of Brillouin zone in 1930. The first Brillouin zone is the smallest volume entirely
enclosed by planes that are the perpendicular bisectors of the reciprocal lattice vectors drawn from the origin.
The concept of Brillouin zone is particularly important in the consideration of the electronic structure of solids.
There are also second, third, etc., Brillouin zones, corresponding to a sequence of disjoint regions (all with the
same volume) at increasing distances from the origin, but these are used more rarely. As a result, the first
Brillouin zone is often called simply the Brillouin zone. In general, the n-th Brillouin zone consist of the set
of points that can be reached from the origin by crossing n − 1 Bragg planes.
The region in k-space (here an imaginary plane whose rectangular coordinates are kx and ky) that low-k
electrons can occupy without being diffracted is called first Brillouin Zone, shown in figure.2.5. The second
Brillouin zone is also shown; it contains electrons with k values from 𝜋/𝑎 to 2𝜋/𝑎 for electrons moving in
the ±𝑥 and ±𝑦 directions, with the possible range of k values narrowing as the diagonal directions are
approached.

Fig. 2.5 The first and second Brillouin zones of a two-dimensional square lattice

The Brillouin zones are used to describe and analyze the electron energy in the band energy structure of
crystals.
2.5.1 Brillouin zones in three dimensions
A simple cubic structure in real space, transforms to a simple cubic structure in reciprocal space.
Further, the Wigner-Seitz cell for a simple cubic lattice is a simple cube as well. Therefore, the first Brillouin
zone for a material that has a simple cubic structure in real space, is the Wigner-Seitz cell corresponding to
its reciprocal lattice, and is therefore also a cube.
Consider a BCC lattice. It consists of a lattice point at the body center, and lattice points at the corners
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of the cubic lattice. Since the body center is conveniently at the center of the unit cell, we choose it as the
central point around which the Wigner Seitz cell is identified. By treating the body center as the origin,
imaginary lines can be drawn to the corner lattice points, which are the nearest neighbors of the lattice point
at the body center. Perpendicular bisectors to these imaginary lines can be drawn, and the region in space
bounded by these perpendicular bisectors will then form the Wigner-Seitz cell of the BCC lattice. The Wigner-
Seitz cell of a BCC lattice is shown in the Figure 2.6.

Fig. 2.6 Wigner-Seitz cell of a BCC lattice. The central lattice point of the BCC lattice is hidden within the Wigner
Seitz cell.

We can also consider imaginary lines connecting the body center of the unit cell chosen to its adjacent body
centers. The perpendicular bisector to these lines will be the sides of the unit cell, since they will be midway
between the adjacent body centers. These planes will not cut out any portion from the Wigner-Seitz cell we
have identified above. Therefore the Figure 2.6, correctly identifies the Wigner-Seitz cell for a BCC lattice.
Consider now an FCC lattice. Since lattice points are present at the corners of the cube as well as at
the face centers, at first glance it is not possible to identify a convenient central point about which the Wigner-
Seitz cell can be defined. However by taking two adjacent unit cells together it is possible to identify the
shared face center as a common central point about which the Wigner- Seitz cell can be defined. In view of
the symmetry of these structures, the choice of origin is only a matter of convenience. The choice of origin, is
as shown in the Figure 2.7.

Fig. 2.7 Choice of origin for an FCC unit cell, for the purpose of identifying its Wigner- Seitz cell. A face center, shared
between two adjacent FCC unit cells, is the origin of choice.

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The nearest neighbors of the face centered lattice point, are four face centers of the unit cell on top, four face
centers of the unit cell below, and the four shared corner lattice points of the two unit cells. By drawing
imaginary lines to these nearest neighbors and drawing perpendicular bisectors to those lines, the Wigner-
Seitz cell of the FCC lattice is identified, as shown in Figure 2.8.

Fig. 2.8 Wigner-Seitz cell of an FCC lattice. One shared face center lattice point is hidden within the Wigner Seitz cell.

Since a BCC real lattice is represented in reciprocal space by an FCC lattice, the Wigner-Seitz cell of the FCC
lattice becomes the first Brillouin zone of the BCC real lattice. Similarly, since an FCC real lattice is
represented in reciprocal space by a BCC lattice the Wigner-Seitz cell of the BCC lattice become the first
Brillouin zone of the FCC real lattice. These structures are therefore conceptually inversely related as
indicated in Figure 2.9.

Fig. 2.9. The relationship between real lattice structures and their Brillouin zones for FCC and BCC real lattice

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2.6 Distinction between Metals, Insulators and Semiconductors.
The two situations depicted in Figure 2.10 are typical as each atom (site) in a lattice contributes an
integer number of electrons to the system. So we distinguish the case that there is an odd or an even number
of electrons per unit cell. Note that the unit cell may contain more than one atom. Figure 2.10 shows the
condition of half-filling and complete filling are shown, where for half-filling a ground state configuration is
shown (note there are 4 degenerate states). For the completely filled band all k levels are occupied by two
electrons of opposite spin. This means in real space that also all sites are occupied by two electrons. This is a
non-degenerate state.

Fig. 2.10 The condition of half-filling and complete

The bands can be either completely filled or empty when the number of electrons per atom (unit cell)
is even. Thus taking the complete set of energy bands into account, the chemical potential cannot be identified
with a Fermi energy but lies within the energy gap separating highest filled and the lowest empty band (see
Figure.2.11). There is a finite energy needed to add, to remove or to excite an electron. If the band gap 𝐸𝑔 is
much smaller than the bandwidth, we call the material a semiconductor. For 𝐸𝑔 of the order of the bandwidth,
it is an (band) insulator. In both cases, for temperatures 𝑇 ≪ 𝐸 ⁄𝑘𝐵 the application of a small electric voltage
will not produce an electric transport. The highest filled band is called valence band, whereas the lowest empty
band is termed conduction band. Examples for insulators are C as diamond and for semiconductors Si and Ge.
They have diamond lattice structure with two atoms per unit cell. As these atoms belong to the group IV in
the periodic table, each provides an even number of electrons suitable for completely filling bands. Note that
we will encounter another form of an insulator, the Mott insulator, whose insulating behavior is not governed
by a band structure effect, but by a correlation effect through strong Coulomb interaction.

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Fig. 2.11 Material classes according to band filling: left panel: insulator or semiconductor (partially filled bands with
the Fermi level in band gap); center panel: metal (Fermi level inside band); right panel: metal or semimetal (Fermi
level inside two overlapping bands).

If the number of electrons per unit cell is odd, the uppermost non-empty band is half filled (see
Figure.2.11) .Then the system is a metal, in which electrons can move and excitations with arbitrary small
energies are possible. The election remain mobile down to arbitrary low temperatures. The standard example of
a metal are the Alkali metals in the first column of the periodic table (Li, Na, K, Rb, Cs) as all of them have the
configuration [noble gas] (𝑛𝑠)1 i.e., one mobile electron per ion. In general, band structures are more complex. Different
bands need not to be separated by energy gaps, but can overlap instead. In particular, this happens, if different orbitals
are involved in the structure of the bands. In these systems, bands can have any fractional filling (not just filled or half-
filled). The earth alkaline metals are an example for this (second column of the periodic table, Be, Mg, Ca, Sr, Ba),
which are metallic despite having two (n; s)-electrons per unit cell. Systems, where two bands overlap at the Fermi
energy but the overlap is small, are termed semi-metals. The extreme case, where valence and conduction band touch
in isolated points so that there are no electrons at the Fermi energy and still the band gap is zero, as in graphene.
Exercises 2
1. Describe the important concept of the band structures.
2. Describe briefly the important concept and results of the Kronig-Penney model.

3. CONDUCTION IN SEMICONDUCTORS
Semiconductors can be divided into two categories; Intrinsic and extrinsic semiconductors. This
classification is related to the purity of the semiconductors. Intrinsic or pure semiconductors are those
that are ideal, with no defects, and no external impurities. The conductivity i s temperature dependent.
As opposed to intrinsic semiconductors, extrinsic semiconductors h a v e some impurities added to modify
the concentration of charge carriers and hence the conductivity. Extrinsic semiconductors are used
extensively due to the ability to precisely tailor their conductivity by adding the impurities. Intrinsic
semiconductors (especially Si and Ge) are used as optical and x-ray detectors (at low T) where a low
concentration of charge carriers is required.

3.1 Electrons and holes in semiconductors

As pointed out before, semiconductors distinguish themselves from metals and insulators by the fact that
they contain an "almost-empty" conduction band and an "almost-full" valence band. This also means that we
will have to deal with the transport of carriers in both bands. To facilitate the discussion of the transport in
the "almost-full" valence band we will introduce the concept of holes in a semiconductor. It is important to
understand that one could deal with only electrons (since these are the only real particles available in a
semiconductor) if one is willing to keep track of all the electrons in the "almost-full" valence band. The
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concepts of holes is introduced based on the notion that it is a whole lot easier to keep track of the missing
particles in an "almost-full" band, rather than keeping track of the actual electrons in that band.
Now the concept of a hole will be explain and how the hole concept simplifies the analysis will be
point out. Holes are missing electrons. They behave as particles with the same properties as the electrons
would have occupying the same states except that they carry a positive charge. This definition is illustrated
further with the figure below which presents the simplified energy band diagram in the presence of an electric
field.

Fig. 3.1 Energy band diagram in the presence of a uniform electric field. Shown are electrons which move
against the field and holes which move in the direction of the applied field.

A uniform electric field is assumed which causes a constant gradient of the conduction and valence band edges
as well as a constant gradient of the vacuum level. The gradient of the vacuum level requires some further
explanation since the vacuum level is associated with the potential energy of the electrons outside the
semiconductor. However the gradient of the vacuum level represents the electric field within the
semiconductor. The electrons in the conduction band are negatively charged particles which therefore move
in a direction which opposes the direction of the field. Electrons therefore move downhill in the conduction
band. Electrons in the valence band also move in the same direction. The total current due to the electrons in
the valence band can therefore be written as:
1
𝑱𝑣𝑏 = ∑ (−𝑞) 𝑣 − − − 3.1
𝑉
filled states
Where V is the volume of the semiconductor, q is the electronic charge and v is the electron velocity. The sum
is taken over all occupied or filled states in the valence band. This expression can be reformulated by first
taking the sum over all the states in the valence band and subtracting the current due to the electrons which
are actually missing in the valence band. This last term therefore represents the sum taken over all the empty
states in the valence band, i.e.
1
𝑱𝑣𝑏 = ( ∑ (−𝑞) 𝑣 − ∑ (−𝑞) 𝑣) − − − 3.2
𝑉
all states empty states
The sum over all the states in the valence band has to equal zero since electrons in a completely filled band
do not contribute to current, while the remaining term can be written as:
1
𝑱𝑣𝑏 = ∑ (+𝑞) 𝑣 − − − 3.3
𝑉
empty states

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Which indicate that the current is due to positively charged particles associated with the empty states in the
valence band. We call these particles holes. Keep in mind that there is no real particle associated with a hole,
but rather that the combined behavior of all the electrons which occupy states in the valence band is the same
as that of positively charge particles associated with the unoccupied states.
The reason the concept of holes simplifies the analysis is that the density of states function of a whole band
can be rather complex. However it can be dramatically simplified if only states close to the band edge need to
be considered. As illustrated by the above figure, the holes move in the direction of the field (since they are
positively charged particles), they move upward in the energy band diagram.

3.2 Conductivity in semiconductors

It is well known that the conductivity of a material depends on the concentration of free electrons in it. Good
conductors consist large concentration of free electrons whereas insulators consist small concentration of free
electrons. The concentration level of the free electron in semiconductors is in between the values of density
of free electrons in conductor and insulator. That is why the conductivity of the semiconductor is moderate
not very high and not very low. The typicality of semiconductor is that the valance electrons in the
semiconductor are not free like metal instead they become trapped in the bond between two adjacent atoms.
Germanium and Silicon are two very popularly used semiconductors. The crystal structure of both
semiconductors consists a regular repetition of the three-dimensional unit.

Fig. 3.2 Germanium atom

Taking germanium as an example, where there are 32 orbiting electrons across the nucleus in each
atom as shown in figure 3.2. Each atom in the germanium contributes four valence electrons to make the
covalent bond with four adjacent germanium atoms in the crystal. So the atoms are tetravalent. The inert ionic
core of the germanium acts as a positive charge of +4 electronic charges. The valance electrons in germanium
crystal serve to bind one atom to the next. Hence, it can be said that the valance electrons are tightly bounded
with the atoms in the crystal. Because of that, although a germanium atom has four valence electrons in it
germanium crystal as a whole is not an excellent conductor of electricity (figure 3.3).

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Fig. 3.3 Germanium crystal at absolute zero temperature

At absolute zero temperatures a semiconductor crystal behaves just like an insulator as there are no
free carriers of electricity available. However at room temperature (300oK), some of the covalent bonds in the
crystal are broken due to available energy and this phenomenon makes the availability of free electrons in the
crystal and hence conduction of semiconductor may be some extent possible at room temperature. The energy
required to break the covalent bond is about 0.72 eV in germanium, and that is 1.1 eV in silicon at room
temperature. When one covalent bond breaks, the either of electrons that previously involved in the bond
formation comes out with keeping a vacant place behind it on the bond. This vacancy is referred as a hole.

Fig. 3.4 Germanium crystal at room temperature (300oK) showing holes.

The significance of hole in the semiconductor is that they can also be referred as a carrier of electricity
compared to electrons. The mechanism by which the holes carry electricity is somewhat different from the
mechanism by which electrons carry electricity. When there is an incomplete bond in a semiconductor crystal,
a hole exists in the bond. It is a little bit easier for the electron, to form a bond with neighborhood atoms;
hence, it leaves its previous position for occupying the newly created hole nearby. When an electron moves
to fill a hole from its previous position in the bond, it leaves another new hole behind it. When the second hole
is created, then electron of any other neighborhood bond may come out to fill up the second hole with creating
a new hole behind it. Hence, it can be visualized that as such holes are moving in the direction opposite to the
movement of electrons. In this way semiconductor conducts electricity with help of these two types of
electricity or charge carriers (electrons and holes). Whenever holes move in a respective forward direction,
the negative charge moves in the opposite or backward direction. Negative charge moves in backward
direction imply that the positive charge was moving in forward direction. Hence, it can be concluded that the
movement of a hole involves for carrying a positive charge in a semiconductor crystal. In an ideal
semiconductor crystal number of holes created per unit time is exactly equal to the number of electrons
becomes free during this time. If the temperature increases the rate of creation of electron-hole pair increases
and when the temperature decreases, number electron-hole pairs is reduced due to recombination of electrons
and holes in the crystal.

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 When one electron-hole pair is created, there are two charge carriers produced. One is negative charge
carrier associated with the electron and other is positive charge carrier associated to the hole. The mobility µ
of a carrier in an operational sense is defined as the proportionality constant between the average drift
velocities of a (ensemble of) carriers in the presence of an electrical field E. Let the mobility of the hole in the
crystal be μh and the mobility of electron in the same crystal be μe. These holes and electrons move in opposite
direction. The electrons always tend to move in opposite to the applied electric field, the current density due
to drift of holes is given by,
𝐽ℎ = 𝑒𝑝𝑣ℎ = 𝑒𝑝𝜇ℎ 𝐸 − − − 3.4
And the current density due to drift of electrons is given by,
𝐽ℎ = 𝑒𝑛𝑣𝑒 = 𝑒𝑛𝜇𝑒 𝐸 − − − 3.5
Where vh is holes drift velocity, ve is electrons drift velocity, e is electron charge, n is the magnitude of free
electron concentration and p is the magnitude of hole concentration and E is electric field strength. As the
drifting of holes contributes current in the same direction and drifting of electrons provides current in opposite
direction, in both cases, currents are in the same direction that is in the direction of drifting of holes. Hence,
resultant current due to these both charge carriers will be arithmetic sum of two currents and hence resultant
current density would be,
𝐽 = 𝐽ℎ + 𝐽ℎ = 𝑒𝑝𝜇ℎ 𝐸 + 𝑒𝑛𝜇𝑒 𝐸 = 𝑒𝐸(𝑝𝜇ℎ + 𝑛𝜇𝑒 ) = 𝜎𝐸 − − − 3.6

Where 𝜎 = 𝑒(𝑝𝜇ℎ + 𝑛𝜇𝑒 )the conductivity of the semiconductor, Conductivity in a semiconductor is depends
on two factors
1. Concentration of electrons and holes. Denoted as n and p and is temperature d e p e n d e n t .
2. Ability of the electron and holes to travel in the lattice without s c a t t e r i n g .

3.3 Carrier concentration in semiconductors

The carrier concentration in an energy band is related to the density of available states, g(E), and
the probability of occupation, 𝑓 (𝐸). This is given by
𝑛 = ∫ 𝑔(𝐸)𝑓(𝐸)𝑑𝐸 − − − 3.7
where the integration is over the entire band. 𝑓(𝐸) represents t h e Fermi function and for energy
much greater than 𝑘𝐵 𝑇 it can be approximated by the Boltzmann function

1 𝐸 − 𝐸𝐹
𝑓(𝐸) = ≈ 𝑒𝑥𝑝 (− ) − − − 3.8
𝐸 − 𝐸𝐹 𝑘𝐵 𝑇
1 + 𝐴 𝑒𝑥𝑝 ( )
𝑘𝐵 𝑇

To find the number of electrons in the conduction band (n) then equation 3.7 can be written as
𝐸𝐶 +𝜒
𝑛=∫ 𝑔𝐶𝐵 (𝐸)𝑓(𝐸)𝑑𝐸 − − − 3.9
𝐸𝐶

where the simplified Fermi function is used. The actual density of states function in the CB depends
on the semiconductor material but an approximation of a 3D solid with an uniform potential can be
used. In this case 𝑔𝐶𝐵 (𝐸) turns out to be
8𝜋√2 ∗ 3 1
𝑔𝐶𝐵 (𝐸) = (𝑚 𝑒 ) 2 (𝐸 − 𝐸 )
𝐶 2 − − − 3.10
ℎ3
Since the density of states function is with respect to the bottom of the CB E is replaced by (𝐸 − 𝐸𝐶 ).
To further simplify the integral the limits can be changed from Ec to ∞ instead of Ec +χ. This is because
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most of the electrons in the CB are close to the bottom a n d χ is usually much larger than 𝑘𝐵 𝑇. Hence
making the substitutions in Eqn 3.9 and doing the integration the electron concentration in the
conduction band is given by
(𝐸𝑐 − 𝐸𝐹 )
𝑛 = 𝑁𝑐 𝑒𝑥𝑝 [− ] − − − 3.11
𝑘𝐵 𝑇
3
2𝜋𝑚𝑒∗ 𝑘𝐵 𝑇 2
𝑁𝑐 = 2 ( )
ℎ2
where Nc is a temperature dependent constant called the effective density of states at the conduction
band edge. It gives the total number of available states per unit volume at the bottom of the conduction
band for electrons to occupy. Ec is the bottom of the conduction band and EF is the position of the
Fermi level. A similar equation can be written for holes

(𝐸𝐹 − 𝐸𝑣 )
𝑝 = 𝑁𝑣 𝑒𝑥𝑝 [− ] − − − 3.12
𝑘𝐵 𝑇
3
2𝜋𝑚ℎ∗ 𝑘𝐵 𝑇 2
𝑁𝑣 = 2 ( )
ℎ2

where Nv is the effective density of states at the valence band edge. Equations 3.11 and 3.12 give the
electron and hole concentrations in semiconductors (intrinsic or extrinsic). The concentrations depend
on the position of the Fermi level.

Intrinsic carrier concentration

Multiplying n and p in Eqns 8 and 9 eliminate 𝐸𝐹 and gives
(𝐸𝑐 − 𝐸𝑣 )
𝑛𝑝 = 𝑁𝑐 𝑁𝑣 𝑒𝑥𝑝 [− ] − − − 3.13
𝑘𝐵 𝑇
But (𝐸𝑐 − 𝐸𝑣 ) is nothing but the band gap (𝐸𝑔 ) so that Eqn 3.13 becomes
(𝐸𝑔 )
𝑛𝑝 = 𝑁𝑐 𝑁𝑣 𝑒𝑥𝑝 [− ] − − − 3.14
𝑘𝐵 𝑇

Thus, the product of electron and hole concentration is independent of the Fermi level position but only
on the band gap and temperature, apart from Nc a n d Nv. In an intrinsic semiconductor 𝑛 = 𝑝
since electron and holes are created in pairs (hole is the absence of electron). 𝑛𝑖 is called intrinsic carrier
concentration or density . Substituting in Eqn 11 the intrinsic carrier concentration can be calculated.
(𝐸𝑔 )
𝑛𝑖 = √𝑁𝑐 𝑁𝑣 𝑒𝑥𝑝 [− ] − − − 3.15
𝑘𝐵 𝑇
Thus, the intrinsic carrier concentration is a semiconductor is dependent only on the band gap (𝐸𝑔 ) . 𝑛𝑖 is
a material property (at a given temperature). Eqn 11 can now be rewritten as

𝑛𝑝 = 𝑛𝑖2 − − − 3.16
This equation is called law of mass action and it valid for any semiconductor at equilibrium. For an
intrinsic semiconductor Eqn 3.16 is trivial since 𝑛 = 𝑝 = 𝑛𝑖 but even when n and p are not equal to
product s houl d still yield 𝑛2 . This has important implications for extrinsic semiconductors.

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 3.4 Donor and Acceptor Impurities in Semiconductor
When we add a small quantity of impurity in a semiconductor than the impurity contributes either free
electrons or holes to the semiconductor. As a result, the conducting property of semiconductor changes. The
process of changing the conductive property of semiconductor by adding impurities is known as doping.
Suppose, we add any pentavalent impurity in any intrinsic semiconductor. The pentavalent impurities are those
which have atoms with five (5) valence electrons. As soon as we add the impurity to the semiconductor, the
impurity atoms will replace some of the semiconductor atoms in the crystal structure. Now four (4) of the five
(5) valance electrons of impurity atom will involve in bonding with four neighbourhood semiconductor atoms,
but the fifth one electron will not find any place to occupy. This fifth electron of the impurity atom can be
available as free electron or negative charge carrier even if a minimal amount of energy is applied. The energy
required to detach the fifth electron from its parent atom is in the range of 0.01 eV to 0.05 eV. Antimony,
Phosphorus, and Arsenic are usually and commercially used pentavalent impurities for a semiconductor. As
pentavalent impurities contribute or donate electrons to the semiconductor, these are called donor impurities
and similarly as these impurities contribute negative charge carriers in the semiconductor this we refer as n-
type impurities. The semiconductor doped with n-type impurities is called n-type semiconductor.
N Type Semiconductor
When we add n-type or donor impurities to the semiconductor, the width of the forbidden energy gap
in the lattice structure is reduced. Due to addition of donor atoms, allowable energy levels are introduced a
small distance below the conduction band as is shown in the figure below. These new allowable levels are
discrete because the added impurity atoms are placed far apart and hence their interaction is small. In the
germanium the discrete allowable energy level or forbidden energy gap is only 0.01 eV (electron volt) and
that for silicon is 0.05 eV (electron volt) at room temperature. So it is predictable at room temperature the fifth
electron of all donor atoms is in the conduction band. On the other hand, the increased number of negative
charge carriers i.e. electrons in the semiconductor causes the decrease in some holes. The number of holes per
unit volume in an n-type semiconductor is even lower than that in the same unit volume of intrinsic
semiconductor at the same temperature. This is because of excess electrons, and there will be the higher rate
of recombination of electron-hole pairs than that in a pure or intrinsic semiconductor. A donor is an atom or
group of atoms whose highest filled atomic orbital or molecular orbital is higher in energy than that of a
reference orbital.

P Type Semiconductor
If instead of pentavalent impurity, a trivalent impurity is added to the intrinsic semiconductor, then
instead of excess electrons there will be excess holes created in the crystal. Because when a trivalent impurity
is added to the semiconductor crystal, the trivalent atoms will replace some of the tetravalent semiconductor
atoms. The three (3) valance electrons of trivalent impurity atom will make the bond with three neighborhood
semiconductor atoms. Hence, there will be the lack of an electron in one bond of the fourth neighboring
semiconductor atom which contributes a whole to the crystal. Since trivalent impurities contribute excess
holes to semiconductor crystal, and these holes can accept electrons, these impurities are referred as acceptor
impurities. As the holes virtually carry positive charge, the said impurities are referred as positive - type or p
type impurities and the semiconductor with p type impurities is called p-type semiconductor. When trivalent
impurities are added to a semiconductor, a discrete energy level is created just above the valence band of the
semiconductor. As the gap between valence energy level and the new discrete energy level created by impurity
is quite less, the electron can easily migrate to the new higher energy level with the help of tiny amount of
external energy. When an electron migrates to new energy level, it creates a vacancy in the valence band
behind it, and this contributes hold to the semiconductor. An acceptor is an atom or group of atoms whose
lowest unfilled atomic or molecular orbital is lower in energy than that of a reference orbital.
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 When we add an n-type impurity to the semiconductor, there will be excess electron is a crystal but it
does not mean that there would not be any hole. Due to intrinsic nature of semiconductor at room temperature,
there are always be some electron-holes pairs in the semiconductor. Due to an addition of n-type impurities,
the electrons will be added to that electron-hole pairs and also the number of holes reduced excess
recombination for excess electrons. Hence, the total number of negative charge carriers or free electrons will
be more than that of holes in the n-type semiconductor. That is why in n-type semiconductor, the electrons are
called majority charge carriers whereas poles are called minority charge carriers. Similarly in p-type
semiconductor, holes are called the majority charge carriers and electrons are called minority charge carriers.

3.5 charge densities

The charge density in a semiconductor depends on the free electron and hole density and on the ionized
impurity densities. Ionized donors have given off an electron and are then positively charged, while ionized
acceptors have accepted an electron and are negatively charged. The total charge density ρ is therefore given
by:
𝜌 = 𝑞(𝑝 − 𝑛 + 𝑁𝑑+ − 𝑁𝑎− ) − − − 3.17

3.6 Fermi Level in Intrinsic Semiconductors

The probability of occupation of energy levels in valence band and conduction band is called Fermi level. At
absolute zero temperature intrinsic semiconductor acts as perfect insulator. However as the temperature
increases free electrons and holes gets generated. In intrinsic or pure semiconductor, the number of holes in
valence band is equal to the number of electrons in the conduction band. Hence, the probability of occupation
of energy levels in conduction band and valence band are equal. Therefore, the Fermi level for the intrinsic
semiconductor lies in the middle of forbidden band as shown in figure 3.5.

Fig. 3.5
Fermi level in the middle of forbidden band indicates equal concentration of free electrons and holes.
The hole-concentration in the valence band is given as (Eqn 3.12)
(𝐸𝐹 − 𝐸𝑣 )
𝑝 = 𝑁𝑣 𝑒𝑥𝑝 [− ]
𝑘𝐵 𝑇

The electron-concentration in the conduction band is given as (Eqn 3.11)

(𝐸𝑐 − 𝐸𝐹 )
𝑛 = 𝑁𝑐 𝑒𝑥𝑝 [− ]
𝑘𝐵 𝑇

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Where 𝐸𝐹 is the Fermi level, 𝐸𝑐 is the conduction band, 𝐸𝑣 is the valence band 𝑘𝐵 is the Boltzmann
constant, 𝑇 is the absolute temperature of the intrinsic semiconductor, 𝑁𝑐 is the effective density of states in
the conduction band and 𝑁𝑣 is the effective density of states in the valence band.

The number of electrons in the conduction band is depends on effective density of states in the conduction
band and the distance of Fermi level from the conduction band. The number of holes in the valence band is
depends on effective density of states in the valence band and the distance of Fermi level from the valence
band.
Recall for an intrinsic semiconductor, the electron-carrier concentration is equal to the hole-carrier
concentration.
It can be written as 𝑛 = 𝑝
(𝐸𝐹 − 𝐸𝑣 ) (𝐸𝑐 − 𝐸𝐹 )
∴ 𝑁𝑣 𝑒𝑥𝑝 [− ] = 𝑁𝑐 𝑒𝑥𝑝 [− ]
𝑘𝐵 𝑇 𝑘𝐵 𝑇
Rearranging this equation yields,
2𝐸𝐹 − 𝐸𝑐 − 𝐸𝑣 𝑁𝑣
𝑒𝑥𝑝 ( )=
𝑘𝐵 𝑇 𝑁𝑐
Take the logarithm,
2𝐸𝐹 − 𝐸𝑐 − 𝐸𝑣 𝑁𝑣
( ) = 𝑙𝑛 ( )
𝑘𝐵 𝑇 𝑁𝑐
Solving for 𝐸𝐹 ,
𝐸𝑐 + 𝐸𝑣 𝑘𝐵 𝑇 𝑁𝑣
𝐸𝐹 = + 𝑙𝑛 ( ) − − − 3.18
2 2 𝑁𝑐
𝐸𝑐 +𝐸𝑣
The Fermi energy is in the middle of the band gap plus a small correction that depends linearly on the
2
temperature. The correction term is small at room temperature since 𝐸𝑔 ~ 1 𝑒𝑉 while 𝑘𝐵 𝑇~ 0.025 eV. For Si
and Ge, 𝑁𝑐 > 𝑁𝑣 and the correction term is negative while for GaAs 𝑁𝑐 < 𝑁𝑣 and the correction term is
positive.

3.7 Hall Effect

When a magnetic field is applied to a current carrying conductor in a direction perpendicular to that of the
flow of current, a potential difference or transverse electric field is created across a conductor. This
phenomenon is known as Hall Effect. Hall Effect was discovered by Edwin Hall in 1879.

Fig. 3.6 Hall Effect

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The voltage or electric field produced due to the application of magnetic field is also referred to as Hall voltage
or Hall field. In the n-type semiconductor, free electrons are the majority carriers and holes are the minority
carriers. That means most of the current in the n-type semiconductor is conducted by free electrons while in
the p-type semiconductor, holes are the majority carriers and free electrons are the minority carriers. That
means most of the current in the p-type semiconductor is conducted by holes.
Free electrons and holes are the very small particles, they can’t see them directly with the eyes. But by
using Hall Effect it can be easily identify whether the semiconductor is a p-type or n-type. When a voltage is
applied to a conductor or semiconductor, electric current starts flowing through it. In conductors, the electric
current is conducted by free electrons whereas in semiconductors, electric current is conducted by both free
electrons and holes. The free electrons in a semiconductor or conductor always try to flow in a straight path.
However, because of the continuous collisions with the atoms, free electrons slightly change their direction.
But if the applied voltage is strong enough, the free electrons forcefully follow the straight path. This happens
only if no other forces are applied to it in other direction. If a force is applied in other direction by using the
magnetic field, the free electrons in the conductor or semiconductor change their direction.
Consider a material, either a semiconductor or conductor as shown in figure 3.7. When a voltage is applied,
electric current starts flowing in the positive x-direction (from left to right).

Fig. 3.7
If a magnetic field is applied to this current carrying conductor or semiconductor in a direction perpendicular
to that of the flow of current (that is z-direction), an electric field is produced in it that exerts force in the
negative y direction (downwards). This phenomenon is known as Hall Effect. Hall Effect was named after
American Physicist Edwin Hall, who discovered the phenomenon in 1879.
3.7.1 Hall Effect in conductor
The electric field produced in the material pushes the charge carriers downwards. If the material is a conductor,
the electric field pushes the free electrons downwards (that is in negative y-direction). As a result, a large
number of charge carriers (free electrons) are accumulated at the bottom surface of the conductor.

Fig. 3.8 Hall Effect in conductor

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Because of this large accumulation of negative charges (free electrons) at the bottom surface and deficiency
of negative charges (free electrons) at the upper surface, the bottom surface is negatively charged and the
upper surface is positively charged.
As a result, an electrical difference or potential difference develops between the upper surface and bottom
surface of the conductor. This potential difference is known as Hall voltage. In a conductor, the electric field
is produced due to the negatively charged free electrons. So the hall voltage produced in the conductor is
negative.
3.7.2 Hall Effect in n-type semiconductor
If the magnetic field is applied to an n-type semiconductor, both free electrons and holes are pushed
down towards the bottom surface of the n-type semiconductor. Since the holes are negligible in n-type
semiconductor, so free electrons are mostly accumulated at the bottom surface of the n-type semiconductor.

Fig. 3.9 Hall Effect in n-type semiconductor

This produces a negative charge on the bottom surface with an equal amount of positive charge on the upper
surface. So in n-type semiconductor, the bottom surface is negatively charged and the upper surface is
positively charged.
As a result, the potential difference is developed between the upper and bottom surface of the n-type
semiconductor. In the n-type semiconductor, the electric field is primarily produced due to the negatively
charged free electrons. So the hall voltage produced in the n-type semiconductor is negative.

3.7.3 Hall Effect in p-type semiconductor

If the magnetic field is applied to a p-type semiconductor, the majority carriers (holes) and the minority carriers
(free electrons) are pushed down towards the bottom surface of the p-type semiconductor. In the p-type
semiconductor, free electrons are negligible. So holes are mostly accumulated at the bottom surface of the p-
type semiconductor.

Fig. 3.10 Hall Effect in p-type semiconductor

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So in the p-type semiconductor, the bottom surface is positively charged and the upper surface is negatively
charged. As a result, the potential difference is developed between the upper and bottom surface of the p-type
semiconductor. In the p-type semiconductor, the electric field is primarily produced due to the positively
charged holes. So the hall voltage produced in the p-type semiconductor is positive. This leads to the fact that
the produced electric field is having a direction in the positive y-direction.

The Hall voltage is directly proportional to the current flowing through the material, and the magnetic
field strength, and it is inversely proportional to the number of mobile charges in the material, and the thickness
of the material. So in order to produce a large Hall voltage we need to use a thin material with few mobile
charges per unit volume. Mathematical expression for the Hall voltage is given by
𝐼𝐵
𝑉𝐻 = − − − 3.19
𝑞𝑛𝑑

Where,
VH = Hall voltage
I = current flowing through the material
B = magnetic field strength
q = charge
n = number of mobile charge carriers per unit volume
d = thickness of the material
3.7.4 Applications of Hall Effect
i. Hall Effect is used to find whether a semiconductor is N-type or P-type.
ii. Hall Effect is used to find carrier concentration.
iii. Hall Effect is used to calculate the mobility of charge carriers (free electrons and holes).
iv. Hall Effect is used to measure conductivity.
v. Hall Effect is used to measure a.c. power and the strength of magnetic field.
vi. Hall Effect is used in an instrument called Hall Effect multiplier which gives the output proportional
to the product of two input signals.
Exercises 3
1. Calculate the effective densities of states in the conduction and valence bands of germanium, silicon and
gallium arsenide at 300 K.
2. Where is 𝐸F located in the energy band of silicon, at 300K with 𝑛 = 1017 𝑐𝑚−3? And for 𝑝 =
1014 𝑐𝑚−3 ?
3. Calculate the conductivity and resistivity of intrinsic silicon. Use 𝑛𝑖 = 1010 𝑐𝑚−3, 𝑛𝑒 =
1400 𝑐𝑚2 𝑉 𝑠𝑒𝑐 −1 and 𝑛ℎ = 450 𝑐𝑚2 𝑉 𝑠𝑒𝑐 −1
4. What are holes? Carefully justify your definition.
5. What is the difference between a doped semiconductor and an extrinsic semiconductor?

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