ENGINEERING PHYSICS

Mohana Lakshmi, Ph.D.

Department of Science and Humanities
ENGINEERING PHYSICS - Unit 3
 ENGINEERING PHYSICS
Review of CFET: Assumptions of Classical Free Electron Theory
Proposed by Drude and Lorentz (as early as 1904)
• Valance electrons are treated as conduction electrons
• Valence electrons are considered equivalent to molecules in a gas
• Electrons are moving in a zero potential
• Electrostatic interactions are neglected

Valance electrons in random motion

Image courtesy: www.zweigmedia.com

 Random Thermal Motion

The random motion of the electrons do not contribute to a net drift of electrons across
the metal and hence no current flows through the material
 Under the influence of an applied electric field

In the presence of an Electric field E

the electrons show a net drift across
the metal in a direction opposite to
that of the electric field.
 Drift Velocity
The net average velocity of the conduction electrons in a direction opposite to the
applied electric field is called drift velocity.

Typical value of drift velocity of electrons for an applied electric field of 1 V/m is of the order of 10-3m/S
 Mean Free Path(λ) of a Gas Molecule

According to the kinetic theory of gases, mean free path (λ)

is the average distance travelled by a gas molecule in
between two successive collisions with other molecules.
 Mean Free Path(λ) - CFET

The conduction electrons in the lattice are scattered by

collisions with the ionic cores and other electrons.

Mean Free Path is the average distance travelled by

the conduction electrons between successive
collisions with the positive ion core.
 Mean Collision time
The average time taken by the conduction electrons between two successive collision with
the positive ion core is called mean collision time.
If v is the average velocity of electrons and λ is the mean free path, then the mean time
between collisions is

Relaxation time
When the electric field applied across a conductor is switched off, the drift velocity
decreases exponentially to zero. The time during which the drift velocity reduces to 1/e
times the initial value is called relaxation time.

Taking the mean lattice parameter of 10 nm as the mean free path λ, the relaxation time
can be estimated as
 Expression for Drift Velocity

In the absence of an electric field the free electrons are at random motion. But when
an electric field is applied, some of the electrons acquire a steady velocity, called drift
velocity vd. The resistive force to the motion of the electrons is

If E is the strength of the applied filed, then the force that drives the electrons
opposite to the field is

In the steady state, Fr = F,

The drift velocity vd is given by
 Mobility of Electrons
The mobility of electrons is defined as the magnitude of drift velocity acquired by the
electrons in a unit field.
The electron mobility or the charge carrier mobility is given by

The drift velocity of electrons is extremely low compared to the thermal velocity. To
illustrate, the drift velocity of electrons experiencing an electric field of 1V/m is of
the order of 10-4 ms-1.
 ENGINEERING PHYSICS
Basic Electrical Parameters
𝟑𝒌𝑻
 Thermal velocity, 𝒗𝒕𝒉 =
𝒎

 mean free path, 𝝀 = 𝝉𝒗

𝒎𝒆𝒂𝒏 𝒇𝒓𝒆𝒆 𝒑𝒂𝒕𝒉 (𝝀)
 Relaxation time = mean collision time, 𝝉 =
𝒗𝒕𝒉

 Drift Velocity: Velocity in the presence of an electric field

𝒆𝝉𝑬
𝒗𝒅 =
𝒎

 Electron mobility or Charge carrier mobility: drift velocity

acquired by the electrons in a unit field.
𝒗𝒅 𝒆𝝉
𝝁= =
𝑬 𝒎
 ENGINEERING PHYSICS
Basic Terminologies
𝒒 𝒅𝒒
 Electric Current (I): I = =
𝒕 𝒅𝒕

𝑰
 Current Density (J): J=
𝑨

𝑽
 Electric field (E): E=
𝑳

𝑹𝑨
 Electrical Resistivity (ρ): ρ =
𝑳

𝟏 𝑳
 Electrical Conductivity (σ): σ = =
ρ 𝑹𝑨

 Generalized Ohm’s law: J= σ E

ENGINEERING PHYSICS
Expression for Electrical Conductivity
Expression for current through a conductor
𝑰 = 𝒏𝒆𝒗𝒅 𝑨

𝒆𝝉𝑬
where ,𝒗𝒅 =
𝒎
𝑱 𝑰
From, Ohm’s law, Electrical conductivity, σ= =
𝑬 𝑨𝑬

𝒏𝒆𝒗𝒅 𝑨 𝒏𝒆𝒗𝒅 𝒏𝒆 𝒆𝝉𝑬

σ= = =
𝑨𝑬 𝑬 𝑬 𝒎
𝒏𝒆𝟐 𝝉
∴σ=
𝒎
𝒏𝒆𝟐 𝝉 𝒆𝝉
Electrical conductivity,𝝈 = = 𝒏𝒆 = 𝒏𝒆𝝁
𝒎 𝒎

𝟏 𝒎 𝟏
Electrical resistivity, 𝝆 = = =
𝝈 𝒏𝒆𝟐 𝝉 𝒏𝒆𝝁
 ENGINEERING PHYSICS
Experimental Temperature Dependence of Resistivity

 Matthiessen’s Rule states that 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.
 Net resistivity, 𝛒 = 𝛒𝐫𝐞𝐬 + 𝛒𝐬𝐜

𝐦 𝐦 𝐦
or = +
𝐧𝐞𝟐 𝛕 𝐧𝐞𝟐 𝛕𝐫𝐞𝐬 𝐧𝐞𝟐 𝛕𝐬𝐜
 This gives the effective relaxation time as

𝟏 𝟏 𝟏
= +
𝛕 𝛕𝐫𝐞𝐬 𝛕𝐬𝐜
ENGINEERING PHYSICS
Failures of Classical Free Electron Theory

• Temperature dependence of resistivity

• Specific heat of electrons in a metal

• Conductivity variations with electron concentration

ENGINEERING PHYSICS
Drawbacks of CFET

Failure 1: Temperature dependence of resistivity of metals

𝑚 𝝀
Resistivity, 𝜌 = , 𝒘𝒉𝒆𝒓𝒆, 𝝉 =
𝑛𝑒 2 𝜏 𝒗𝒕𝒉

As per CFET, considering constant mean free path (𝝀) the

relaxation time dependence only on thermal velocity

𝟏
𝟑𝒌𝑩 𝑻 −𝟐
That is, 𝒗𝒕𝒉 = , 𝒗𝒕𝒉 ∝ 𝑻 𝑜𝑟 𝝉 ∝ 𝑻
𝒎

As resistivity 𝝆 ∝ 𝝉−𝟏 , this gives 𝝆 ∝ 𝑻

But experimental observations showed 𝝆 ∝ 𝑻

ENGINEERING PHYSICS
Drawbacks of CFET

Failure 2: Specific heat dependence of electrons in metals

𝒅𝑼
Specific heat, 𝑪𝒆𝒍 =
𝒅𝑻

For 1 mole of a mono valent metal, the energy of the valence

𝟑
electrons is given by U = 𝒌𝑩 𝑻. 𝑵𝒂𝒗𝒈
𝟐

This gives,
𝒅𝑼 𝟑 𝟑
𝑪𝒆𝒍 = = 𝒌𝑩 . 𝑵𝒂𝒗𝒈 = 𝑹 (a constant)
𝒅𝑻 𝟐 𝟐

But experimental estimation of the specific heat of electrons is

only 1% of this value and is temperature dependent
 ENGINEERING PHYSICS
Drawbacks of CFET

Failure 3: Dependence of electron concentration on

conductivity Electrical conductivity values of different metals

𝒏𝒆𝟐 𝝉 Metal Valen conduct

As per CFET, 𝝈 = ,
expected linear dependency on n
𝒎
the free electron concentration cy ivity

But, experimental results show no linear dependence Cu 1

Ag 1
Example:Mono-valent Copper has a higher conductivity
Zn 2
than trivalent Aluminum
Also, Zinc with higher electronic concentration has lesser Cd 2
conductivity than Aluminum Al 3
Ga 3
 ENGINEERING PHYSICS
Assumptions of Quantum Free Electron Theory

Sommerfeld proposed the Quantum free electron model in 1928

 Applies quantum mechanical principles to the CFET
• Valence electrons occupy discrete energy states following Pauli’s
exclusion principle.
 Statistical distribution is described by the Fermi Dirac distribution
function
• The free electrons travel in a constant potential inside the metal
and stay confined within its boundaries
• The electrostatic interactions, the electron – electron and the
electron – ion are negligible
 ENGINEERING PHYSICS
Variation of Density of States with Energy
𝟑
𝟏
𝝅 𝟖𝒎 𝟐
• Density of states, 𝒈 𝑬 𝒅𝑬 = 𝑬 𝒅𝑬
𝟐
𝟐 𝒉𝟐

• The distribution of electrons in energy states vary non-

linearly with increasing energy E

Density of states filled in the order of increasing energy

Image courtesy: slideshare
 ENGINEERING PHYSICS
Density of Occupied States

• Represents possible number of states of electrons and occupancy

is determined by Fermi factor, Fd

• Product of density of states (g(E)) and occupancy probability (Fd)

𝐍 𝐄 = 𝐠 𝐄 ∗ 𝐅𝐝

• Probability that an energy state is occupied

𝟏
𝐅𝐝 = 𝐄−𝐄𝐟
𝟏 + 𝐞 𝐤𝐁𝐓

• Same as multiplying g(E) by a number between 0 and 1

depending on the energy relative to the Fermi energy
 ENGINEERING PHYSICS
Variation of Density of Occupied States with Energy
Three distinct results
• States below Ef – kBT
completely occupied (Fd = 1)
• States in the range of kBT below Ef :
Emptied (Fd between 1 and 0.5)
• States above Ef in the range kBT
Occupied (Fd between 0.50 and 0.00)

Image courtesy: slideshare Variation of N(E) with E

ENGINEERING PHYSICS
Merits of Quantum Free Electron Theory

Merit 1: Heat capacity due to free electrons

• Correct evaluation of electronic specific heat considering
valence electrons close to the Fermi level
• Heat absorption happens due to this small fraction of
electrons
• This effective number in one mole of monovalent metal
will be
𝑵𝒂
𝒏 𝒆𝒇𝒇 = . 𝒌𝑩 𝑻
𝑬𝒇
𝟑
Considering average thermal energy as 𝒌𝑩 𝐓
𝟐
Total energy of effective electrons
𝟑 𝟑 𝑵𝒂 𝟑 𝑵𝒂
𝐔 = 𝒏𝒆𝒇𝒇 . 𝒌𝑩 𝐓 = 𝒌𝑩 𝐓 . 𝒌𝑩 𝐓 = . . 𝒌𝑩 𝟐 𝑻𝟐
𝟐 𝟐 𝑬𝒇 𝟐 𝑬𝒇
ENGINEERING PHYSICS
Correct Evaluation of Specific Heat
𝟑 𝑵𝒂
• Using total energy, 𝐔 = . . 𝒌𝑩 𝟐 𝑻𝟐
𝟐 𝑬𝒇
• Specific heat
𝒅𝑼 𝑵𝒂 𝒌𝑻
𝑪𝒆𝒍 = = 𝟑. . 𝒌𝑩 𝟐 𝐓 = 𝟑𝐑.
𝒅𝑻 𝑬𝒇 𝑬𝒇

• Thus electronic specific heat is a fraction of the value as

predicted by CFET
𝒌𝑻
• is a fraction less than 1% and temperature dependent
𝑬𝒇
• Quantum free electron model gives correct correlation
with the experimental results
• A more accurate evaluation using ideas of number of
electrons in the levels above Ef gives
𝝅𝟐 𝒌𝑩 𝟐 𝑻
𝑪𝒆𝒍 = 𝑵∗
𝟐 𝑬𝒇
ENGINEERING PHYSICS
Merits of Quantum Free Electron Theory
Merit 2: Temperature dependence of the resistivity
• As per CFET resistivity arises due to scattering mechanism
with stationary ionic centers
• For resistance effect, quantum free electron model considers
scattering mechanism with thermally vibrating ionic array
• Amplitude of vibrations increase with temperature followed
by increase in electron scattering
• Effective cross sectional area for scattering 𝒓𝟐 , (r is the
amplitude of vibration) is inversely proportional to mean
free path
• Thus, mean free path reduces as 𝝀 ∝ 𝟏/𝑻
ENGINEERING PHYSICS
Correct Temperature Dependence of Resistivity

As per QFET,
𝒎 𝒎𝒗𝒇
Resistivity 𝝆= =
𝒏𝒆𝟐 𝝉 𝒏𝒆𝟐 𝝀
or
𝒏𝒆𝟐 𝝉 𝒏𝒆𝟐 𝝀
Conductivity 𝝈= =
𝒎 𝒎𝒗𝒇
Resistivity is inversely proportional to mean free path
Thus, conductivity will be inversely proportional to temperature
or resistivity 𝝆 ∝ 𝑻 as is found experimentally
ENGINEERING PHYSICS
Correct Dependence of Conductivity on Free electron concentration

As per QFET,
𝒏𝒆𝟐 𝝉 𝒏𝒆𝟐 𝝀
Conductivity 𝝈= =
𝒎 𝒎𝒗𝒇

λ
𝝈 = 𝒏 and 𝝈 =
𝒗𝒇
ENGINEERING PHYSICS
Wiedemann-Franz law
(Relation between electrical conductivity and thermal conductivity )

• As per the quantum model, electrons close to the Fermi energy are
responsible for the electrical or thermal conduction
• So it is possible to find a relation between these two different physical
phenomena
𝟏 𝐂𝐞𝐥
Thermal conductivity of the metal 𝐊 = . . 𝒗. 𝐋
𝟑 𝐕

V is the volume, 𝒗 is the velocity of electrons and L is the mean free path(𝛌)

𝝅𝟐 𝒌𝑩 𝟐 𝑻
Where the electronic specific heat, 𝑪𝒆𝒍 = 𝐍. ,
𝟐 𝑬𝒇
 ENGINEERING PHYSICS
Relation between electrical and thermal conductivities
• The mean free path of electrons is L = v 𝛕 and as conduction
electrons are located about Fermi energy, taking velocity v = vF
Expression for thermal conductivity can be re-written
𝟏 𝟏 𝝅𝟐 𝒌𝑩 𝟐 𝑻 𝝅𝟐 𝒌𝑩 𝟐 𝑻 𝟐
𝐊 = . . 𝐍. . 𝒗𝑭 . (𝒗𝑭 𝛕) = . 𝐧. . 𝒗𝑭 . 𝛕
𝟑 𝑽 𝟐 𝑬𝒇 𝟔 𝑬𝒇
𝐍 𝟏
• (𝐧 = is the concentration of free electrons and 𝑬𝒇 = 𝐦𝒗𝟐𝑭 )
𝐕 𝟐

𝛑𝟐 𝐤𝐁𝟐𝐓 𝟐 𝛑𝟐 𝐤𝐁𝟐𝐓
𝐊= . 𝐧. . 𝒗𝑭 . 𝛕 = . 𝐧. .𝛕
𝟔 𝟏 𝟑 𝐦
𝐦𝒗𝟐𝑭
𝟐
𝐧𝒆𝟐 𝝉
• Expression for electrical conductivity, 𝛔 =
𝒎
𝑲 𝝅𝟐
• The ratio, = 𝒌𝑩 𝟐 𝐓
𝝈 𝟑𝒆𝟐
This relation is called the Wiedemann-Franz law
ENGINEERING PHYSICS
Lorenz Number

• From the Wiedemann-Franz law,

• Lorenz’s observation!
𝐊 𝛑𝟐
Ratio = 𝐤 𝐁 𝟐 is a constant irrespective of the metal
𝛔𝐓 𝟑𝐞𝟐

• The Lorenz number has a value = 2.4 x10-8 WΩK-2

ENGINEERING PHYSICS
Sommerfeld Model (QFET) -1928

 Systematically recast Drude-Lorentz theory in

terms of Fermi Dirac Statistics rather than
Maxwell-Boltzmann statistics
 Wiedemann_Franz law (still) came out right
 Difficulties remained: Demerits of QFET
 ENGINEERING PHYSICS
Drawbacks of Quantum Free Electron Theory

 Doesn’t differentiate electrical conduction in metals, semiconductors and insulators.

 fails to explain origin of band gap in semiconductors and insulators.
 QFET fails to explain the experimentally observed positive Hall co-efficient observed in
some metals like Zinc.

• These demerits reflects that real potentials of ionic centers in metal was ignored in the
development of quantum free electron gas model
ENGINEERING PHYSICS
Classification of Solids-Energy Band Diagram
 ENGINEERING PHYSICS
Motion of electron in 1D periodic potential

The free electron in a metal are not free from electrostatic

potentials and move in a a periodic potential due to the regular
arrangements of the ionic centres
 ENGINEERING PHYSICS
One Dimensional Periodic Potential distribution for a crystal
Because of the symmetry of the potentials (same surroundings), the
Potential is periodic 𝑽 𝒙 = 𝑽 𝒙 + 𝒂 = 𝑽 𝒙 + 𝟐𝒂
 ENGINEERING PHYSICS
Bloch’s Theorem or Bloch’s Function
 Bloch postulated that since the potential varies periodically, the
probability of finding a electron also should vary periodically.
 Therefore, in such a periodic medium, the wave function should be of
the form 𝝍 𝒙 = 𝒆𝒊𝒌𝒙 . 𝑽(𝒙)

where k is the wave number of the electron waves

• This wave function is solution of the Schrödinger equation when the

potential is periodic
 ENGINEERING PHYSICS
Motion of electron in 1D periodic potential
• The columbic potential in the real crystal can be approximated by
rectangular potentials. In K-P model, the periodic potential seen by the
electrons is assumed to be a simple potential consisting of series of
potential barriers plus potential wells.

The Kronig-Penney model treats the potential in a crystal as a periodic potential consisting of
a chain of finite square wells, of barrier height V0 and barrier thickness c, and regions of zero
potentials of width b, such that the period of repetition is a =b+c.
 ENGINEERING PHYSICS
K-P Solution: Allowed Energies
The motion of the electron through the crystal is then explained
as the tunneling of the electrons through the potential barrier
with a high transmission probability since c is very small
compared to a.
The continuity of the wave functions at the boundaries of the
three regions, results in a transcendental equation

𝒎𝒂 𝑺𝒊𝒏(𝑲𝒂)
𝑪𝒐𝒔 𝒌𝒂 = 𝑽 . 𝒄. + 𝐜𝐨𝐬(𝑲𝒂)
ℏ𝟐 𝒐 𝑲𝒂

𝟐𝒎(𝑽𝒐 −𝑬)
where 𝑲 =
ℏ𝟐

The solutions of the problem exist when 𝒌𝒂 = ±𝒏𝝅

ENGINEERING PHYSICS
ℏ 𝟐 𝑲𝟐
The equation gets satisfied when, 𝒌 = 𝑲 and hence we get the energy 𝑬 =
𝟐𝒎
which is the solution for a free particle
 ENGINEERING PHYSICS
Kronig-Penney Model: E-k diagram

• Since the functions are symmetric (and periodic with period

𝝅
of 𝟐 ), it is possible to represent the energy band diagram in a
𝒂
𝝅 𝝅
single zone of + 𝒕𝒐 −
𝒂 𝒂
Reduced Zone
ENGINEERING PHYSICS
K-P Model: Classification of Solids
ENGINEERING PHYSICS
Effective mass of charge carriers in a periodic potential

The expression for energy in terms of momentum is given by

ENGINEERING PHYSICS
Effective mass of charge carriers in a periodic potential

Differentiating the expression twice with respect to k

or

Curvature of E-K graph gives effective mass m*

ENGINEERING PHYSICS
Effective mass of charge carriers in a periodic potential

 Higher the curvature of E-K , (large

d2E/dK2 ) effective mass will be small.
 Smaller the curvature (small d2E/dK2)
effective mass will be higher
 At the band edges, effective mass of
the charge carriers is highest.
THANK YOU

Mohana Lakshmi, Ph.D.

Assistant Professor, Department of Science and Humanities

[email protected]
+91 998623409