Module - 2 Outline

Electrical Properties of Metals and Semiconductors:

Failures of classical free electron theory, Mechanisms of electron scattering in solids,

Matheissen’s rule, Assumptions of Quantum Free Electron Theory, Density of States,
Fermi Dirac statistics, Fermi Energy, Variation of Fermi Factor With Temperature and
Energy, Fermi Dirac Distribution, Expression for Carrier Concentration in
conductors, Success of QFET, Derivation of electron concentration in an intrinsic
semiconductor, Expression for electron and hole concentration in extrinsic
semiconductor, Fermi level for intrinsic(with derivation) and extrinsic semiconductor
(no derivation), Hall effect, Numerical Problems.
2.1. Introduction:

The electrical behavior of a material is determined by the arrangement of electrons in its energy
bands. Depending on this band structure, solids are broadly classified as metals,
semiconductors, and insulators.

 Metals possess either a partially filled conduction band or an overlap between the
valence band and conduction band. This provides a high density of free electrons,
making them excellent conductors of electricity. Their conductivity is high, resistivity
is low, and it decreases with lowering temperature.
 Semiconductors have a small but finite band gap (typically < 3 eV). At absolute zero,
they behave like insulators since the conduction band is empty. However, at higher
temperatures or through doping, electrons can cross the band gap, leaving behind
mobile holes in the valence band. This results in moderate conductivity, which
increases with temperature—opposite to metals.
 Insulators have a large band gap (greater than ~3 eV). Electrons in the valence band
cannot easily move to the conduction band, so almost no free charge carriers are
available under normal conditions. As a result, insulators exhibit extremely low
conductivity and very high resistivity.

Thus, the key distinction among these classes of materials lies in the band gap energy and the
availability of mobile charge carriers. Understanding these properties is fundamental to solid-
state physics and the operation of modern electronic devices.
Band gap energy
Basic Definitions:
Resistivity (ρ):
Electrical resistivity is a measure of how strongly it opposes the flow of current. The ohm meter (m) is the SI unit of
electrical resistivity.
“The electrical resistivity of a material of a conductor is defined as the resistance offered by the unit length and
unit cross-sectional area of a wire of the given material”.

MOBILITY:
“It is defined as the magnitude of the drift velocity vd acquired by the electrons in an electric field E”.
𝒗𝒅
𝝁=
𝑬

Where 𝜇 is called the mobility of the charge carrier.

CONDUCTIVITY (σ): It characterizes the conducting capability of the material. It is denoted by σ and it is inversely proportional to the
resistivity.

1
𝜎=
𝜌

Electrical Conductivity:
It is defined as the rate of charge flow across unit area in a conductor. Electrical conductivity ( ) per unit potential (voltage) gradient.
J
𝜎= Its unit is -1 m -1
𝐸

(a) CURRENT DENSITY (J): If ‘I’ is the current flowing in a conductor of cross sectional area “A” then the current density ‘J’ is the current
flowing per unit area of cross- section of an imaginary plane held normal to the direction of current in a current carrying conductor.

𝐼
𝐽=
𝐴
(a) ELECTRIC FIELD(E): If ‘L’ is the length of the conductor of uniform cross sectional area “A” and of uniform material composition, and
‘V’ is the potential difference between the two ends then the electric field ‘E’ at any point inside is given by

𝑉
𝐸=
𝐿
Note: Some important Definitions:
1. Thermal Velocity (vth): The velocity with which the free electrons keep moving due to
thermal agitation is called Thermal velocity.

2. Drift velocity (vd): The average velocity acquired by a free electron in a conductor under
the influence of an electric field is called the drift velocity.
3. Mean free path (λ): The average distance travelled by the conduction electrons between
successive collisions with lattice ions.

4. Mean collision time (τ): The average time that elapses between two consecutive collisions
of an electron with the lattice points is called mean collision time.
τ = λ/v
where ‘λ’ is the mean free path, v ≈ vth is velocity same as combined effect of thermal & drift
velocities.
5. Relaxation time (τ r): From the instant of sudden disappearance of an electric field across
a metal, the average velocity of the conduction electrons decays exponentially to zero, and
the time required in this process for the average velocity to reduce to (1/e) times its value is
known as Relaxation time.
𝑛𝑒 2𝜆
6. Electrical conductivity σ = (according to classical free electron theory)
3𝑘𝑇𝑚
𝑛𝑒 2
Electrical Conductivity σ = (in terms of mean collision)
𝑚
Mechanisms of Electron Scattering in Solids
In solids, the motion of electrons is not perfectly free. As electrons move through the crystal lattice, they
undergo scattering events that limit their mobility and hence affect the electrical conductivity.
The main scattering mechanisms are:
(i) Lattice (Phonon) Scattering
 Caused by vibrations of atoms in the crystal lattice.
 At higher temperatures, lattice vibrations (phonons) increase, disturbing the periodic potential seen by
electrons.
 This leads to frequent collisions between electrons and vibrating ions.
 Effect: Electrical resistivity increases with temperature in metals due to phonon scattering.
(ii) Impurity or Defect Scattering
 Caused by the presence of foreign atoms, vacancies, dislocations, or crystal imperfections.
 Impurities disturb the periodic potential, deflecting electrons.
 Dominant at low temperatures, where phonon vibrations are small, but impurity effects remain.
 Effect: Residual resistivity even as temperature → 0 K.
(iii) Electron–Electron Scattering
 Electrons can collide with each other, exchanging energy and momentum.
 Usually less significant compared to phonon and impurity scattering but becomes important at very high
electron densities (e.g., in metals).
iv) Electron–Boundary Scattering
 Important in nanomaterials and thin films.
 When the electron mean free path is comparable to the sample size, electrons scatter at grain
boundaries or surfaces.
 Effect: Reduces conductivity in polycrystalline or nanostructured materials.
(v) Electron–Phonon Interaction in Semiconductors
 In semiconductors, scattering is more complex:
o Acoustic phonon scattering: due to lattice vibrations (dominant at moderate temperatures).
o Optical phonon scattering: due to higher-energy lattice vibrations (important at high T).
o Ionized impurity scattering: scattering by charged dopant atoms (dominant at low T).
 At low temperature → impurity scattering dominates.
 At room temperature → phonon scattering dominates.
 In nanostructures → boundary scattering becomes significant.
Concept of phonon:
“Phonons are quantized sounds that are created due to the oscillation of atoms within a crystal. It is a form of
vibrational energy”
All metals and their alloys are crystalline materials. Hence the atoms or ions are situated at a particular position in a
crystal lattice. Because of the thermal energy these ions are vibrating in all directions from the mean position in space.
These vibrated ions in crystal lattice are quantized. The quantized lattice vibrations are called phonons. The amplitude
of lattice vibrations directly proportional to temperature.
Variation of resistivity with temperature and Impurity: (Mathiessen’s Rule)
• The resistivity of metals to the flow of current is due to scattering of the conduction electrons by lattice
vibrations or phonon. Hence the electron moves under the action of electric field in the phonon field. The
amplitude of lattice vibrations or phonons proportional to temperature.
• If the temperature of the material increases amplitude of the lattice vibration also increases, then more and
more electrons scattered which leads to increases the resistivity of metals directly proportional to
temperature. The dependence of resistivity of metals under normal conducting state is shown in fig. below
Matheissen’s rule

“The total resistivity of a metal is the sum of the resistivity due to phonon scattering which is
temperature dependent and the resistivity due to scattering by impurities which is temperature
independent”
𝝆 = 𝝆𝒑𝒉 + 𝝆𝒊

Where 𝜌𝑝ℎ 𝑖𝑠 the resistivity due to lattice vibration is increases with temperature and 𝜌𝑖 is the resistivity due
to scattering of conduction electrons by impurities and imperfections.
Classical free electron theory: (Qualitative)
The properties of metals such as electrical conduction, thermal conduction, specific heat etc are due to the free
electrons or conduction electrons in metals. The first theory to explain the electrical conductivity of metals is
‘Free electron theory’ and it was proposed by Drude in the year 1900 and later developed and refined by Lorentz.
Hence the classical free electron theory is known as Drude- Lorentz’s theory. It failed to account the facts such as
temperature dependence of conductivity and dependence of electrical conductivity on electron concentration.

2.5.1. Failures of Classical Free Electron Theory:

Electrical and thermal conductivities can be explained from classical free electron theory. It fails to account the
facts such as specific heat, temperature dependence of conductivity and dependence of electrical conductivity on
electron concentration.
i. Temperature dependence of electrical conductivity:

We know, the conductivity of a metal is proportional to inverse of temperature, i.e.,

1
σ =
𝑇
1
But following Drude-Lorentz theory one arrives at the condition σ = which is not
𝑇
valid according to quantum mechanics.

ii. Dependence of electrical conductivity on electron concentration:

According to classical free electron theory, electrical conductivity is give n by,

𝑛 𝑒 2𝜆
σ =
3𝑘𝑇𝑚

therefore, σ α n Experimentally determined values of some metals are given below

Metal Electron Concentration (n) Electrical Conductivity (σ)

1028/ m3 107 /Ωm
Copper 8.45 5.88
Aluminum 18.46 3.66

From the table it is clear that, though electron concentration in copper is 2.13 times less than
that of Aluminum, its electrical conductivity is much greater than that of Al. Hence, the
classical free electron theory fails to explain the dependence of σ on electron concentration.
iii. Specific heat of conduction electrons:
The specific heat of conduction electrons as per classical free electron theory is given by
Cv = 3/2 R
Where R is gas constant and Cv is the specific heat of conduction electrons. But experimental evidence showed that the
Cv of conduction electron is
Cv = 10-4 RT
Where Cv is the specific heat, R is a gas constant, T is absolute temperature of metal
From the above discussions, it is clear that classical free electron theory fails to explain many of the experimentally
observed facts.
Assumptions of Quantum Free Electron Theory

In order to rectify the drawbacks of the classical free electron theory, Sommerfeld proposed the quantum free
electron theory in 1928. This theory is based on quantum concepts.

Assumptions of QFE Theory:

1. The energy values of the conduction electrons are quantized.
2. The distribution of energy among the free electrons is according to Fermi-Dirac statistics.
3. The distribution of electrons in the various allowed energy levels occur as per Pauli’s exclusion principle.
4. The electrons travel with a constant potential inside the metal but confined within its boundaries.
Density of States

• There are large numbers of allowed energy levels for electrons in solid materials. A group of energy levels close to each
other is called as energy band. Each energy band is spread over a few electron-volt energy ranges.
• In 1mm3 volume of the material, there will be large number of permitted energy levels in an energy range of few electron-
volts. Because of this, the energy values appear to be virtually continuous over a band spread.
• To represent it technically it is stated as density of energy levels. The dependence of density of energy levels on the energy
is denoted by g(E). It is called density of states function. The graph shows variation of g(E) versus E.

The density of states in range E and (E+dE) is denoted by g(E)dE.

It is clear g(E) is proportional to √𝐸 in the interval dE.

Fermi Dirac statistics
2.8.1. Fermi Energy
Definition: The Fermi energy (EF) is the highest energy level occupied by electrons in a
solid at absolute zero temperature (0 K).