CHAPTER 2

Free electron theory of conduction in

metal

1
 Crystalline Structure
● Solid materials can be divided into two groups based on the arrangement of the atoms. These
are amorphous and crystalline solids.
● In an Amorphous solid, atoms are not present in an orderly manner. They are haphazardly
arranged. Example: Glass, plastic, rubber, etc.
● In a Crystalline solid, atoms are arranged in an orderly manner. Crystalline solids have
periodically repeating arrangement of atoms which leads to long range order. Example: Iron,
Copper and other metals, Diamond, Gold, Quartz, Solid iodine, NaCl, etc.
● Crystalline solid is a material comprised of one or many crystals. Such solids can be further
sub-classified as Monocrystalline and Polycrystalline.
● Monocrystalline material has a single crystal (there are no grain boundaries).
● Polycrystalline material are comprised of many small crystals or grains. The grains have
different crystallographic orientation. There exist atomic mismatch within the regions where
grains meet. These regions are called grain boundaries.

2
Continued……

3
 Lattice
● Infinite regular arrangement of points in which every point has the same environment as any
other point.

LINEAR
LATTICE

PLANE
LATTICE
LATTICE

SPACE
LATTICE

4
 Space Lattice
● Infinite regular/periodic arrangement of points in three dimension in which every lattice point
has identical surrounding.
● If the periodicity along the line is a, then position of any point along the line can be obtained
by a simple translation, ru = ua .
● Similarly, ruv = ua + vb will repeat the point along a 2D plane, where, u and v are integers
● The position of the lattice points are defined by the lattice vectors.

5
Continued……

6
 Basis
● The way of filling-up of points in a space lattice by the atoms is known as Basis.
● Each point may be occupied by one, two or many atoms in different solids.
● Lattice point do not necessarily lie at the center of the atoms.
● The space lattice when combines with the basis generates a crystal structure.
space lattice + basis = crystal structure

7
 Unit Cell
● Most convenient small cell in a crystal structure that carries the properties of crystal is called
unit cell.
● It is the basic structural unit of a crystal structure.
● A unit cell is the smallest geometrical figure of the crystal lattice which when repeated again
and again in different directions in space forms the crystal lattice.
● A unit cell is characterized by six parameters. These parameters are three edges (axial lengths)
a, b and c and angles between them (interaxial angles) α, β and γ.
● The unit cell will be called monoatomic if only one atom occupies a lattice point. When two
atoms occupy a lattice point, it will make a diatomic unit cell. Similarly the unit cell will be
known as multiatomic when too many atoms occupy a lattice point.
● In diatomic and multiatomic unit cells, the centre of larger atom coincides with the lattice
point.
● A type of unit cell which contain lattice points at corners only and has minimum volume is
called primitive unit cell.

8
 Continued….

Lattice parameters
axial lengths: a , b , c
interaxial angles: α , β , γ

If a crystal has symmetry, the unit cell must have at

least that much symmetry.

9
Types of Unit Cells

10
 Cubic Crystal System
● There are different types of unit cell geometries of crystals of different materials. In cubic type
geometry, there are basically three types, namely Simple Cubic, Face Centered Cubic and
Body Centered Cubic.

Terminologies related to unit cell

● The coordination number is defined as the number of nearest and equidistant atoms with
respect to any other atom in a unit cell.
● The atomic packing fraction is defined as the ratio of total volume of atoms per unit cell, v, to
the total volume of unit cell, V. It is also known as relative density of packing or Atomic
Packing Factor.
● Atomic concentration is defined as the number of atoms in that unit cell to the volume of unit
cell.

11
 Simple Cubic Structure(SC)
● A unit cell having same direction in all direction and containing only corner atoms is called
simple cubic unit cell.
● Each atom touches along the cube edges only and the structure is loosely packed.
● The side of the cube is equal to the distance between the two atoms.
1 𝑡ℎ
● Each corner atom is shared by eight unit cell so only of each corner atoms belong to a
8
1
unit cell. Therefore, number of atoms per unit cell = 8 × = 1.
8
● If 'a' be the side of unit cell and 'r' be the radius of an atom, then we have,
a = 2r
Face diagonal = 2a
Body diagonal = 3a
1
● Atomic Concentration for SC unit cell =
a3

12
 Continued…..
● The coordination number for each corner atom is 6 because in simple cubic unit cell, an atom
can have a close neighbour along positive x-axis and another along negative x-axis which
remains true for y and z axes as well.
volume of atoms in unit cell
● Packing Density APF =
volume of unit cell

4π 3 4π 3
r ×1 r π
= 3 = 3 = = 0.52 = 52%
a3 (2r)3 6
Therefore, 52% space of unit cell is occupied by the corner atoms.

13
 Face Centered Cubic Structure(FCC)
● A cubic unit cell formed by corner atoms along with atom in each face centered position (i.e.
at a point where face diagonal meets) is called face centered cubic unit cell.
● The side of the cube is equal to the distance between the two corner atoms.
1 𝑡ℎ
● Each corner atom is shared by eight unit cell so only of each corner atoms belong to a
8
unit cell.
● Each atom at face centered position is shared by two unit cell so one half of each face centered
atom belongs to a unit cell.
1 1
● Therefore, number of atoms per unit cell = 8 × + 6 × = 4.
8 2
● If 'a' be the side of unit cell and 'r' be the radius of an atom, then we have,
Face diagonal = 2a = 4r ⇒ a = 2 2r
Body diagonal = 3a = 2 6r
4
● Atomic Concentration for SC unit cell =
a3
14
 Continued…..
● The coordination number in this case is 4 × 3 = 12 because in FCC unit cell, each corner
atom can have four close neighbor in each of three xy, yz and zx planes.
volume of atoms in unit cell
● Packing Density APF =
volume of unit cell

4π 3 4π 3
r ×4 r π
= 3 = 3 = = 0.74 = 74%
a3 (2 2r) 3 3 2
Therefore, 74% space of FCC unit cell is occupied by the atoms.

15
 Body Centered Cubic Structure(BCC)
● A cubic unit cell formed by corner atoms along with an atom at body centered position (i.e. at
a point where body diagonal meets) is called body centered cubic unit cell.
● The side of the cube is equal to the distance between the two corner atoms.
1 𝑡ℎ
● Each corner atom is shared by eight unit cell so only of each corner atoms belong to a
8
unit cell.
● The atom at body centered position cannot be shared by any other unit cell.
1
● Therefore, number of atoms per unit cell = 8 × + 1 = 2.
8
● If 'a' be the side of unit cell and 'r' be the radius of an atom, then we have,
2 4
Body diagonal = 2a + a2 = 3a = 4r ⇒ a = r
3
4 2
Face diagonal = 2a = r
3
2
● Atomic Concentration for BCC unit cell =
a3
16
 Continued…..
● The coordination number for interior atom is 8 because in BCC unit cell, the atom inside the
cell has all the corner atom as its close neighbours.
volume of atoms in unit cell
● Packing Density APF =
volume of unit cell

4π 3 8π 3
r ×2 r 3π
= 3 = 3 = = 0.68 = 68%
a3 4 3 8
( r)
3
Therefore, 68% space of BCC unit cell is occupied by the atoms.

17
 Molecular Orbital Bonding Theory
● Molecular orbital (MO) theory was developed by F. Hund and Robert S. Mulliken in 1932.
● The goal of molecular orbital theory is to describe molecules in a similar way like how we
describe atoms, that is, in terms of orbitals, orbital diagrams, and electron configurations.
● It is an approach to bonding in which orbitals encompass the entire molecule rather than being
localized between the atoms.
● This theory help to predict the molecular properties such as shape, magnetism and bond order.
● The salient features of this theory are :
1) The electrons in a molecule are present in the various molecular orbitals as the electrons
of atoms are present in the various atomic orbitals.
2) The atomic orbitals of comparable energies and proper symmetry combine to form
molecular orbitals.
3) While an electron in an atomic orbital is influenced by one nucleus, in a molecular orbital
it is influenced by two or more nuclei depending upon the number of atoms in the
molecule. Thus, an atomic orbital is monocentric while a molecular orbital is polycentric.

18
 Continued…..
4) The number of molecular orbital formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One is
known as bonding molecular orbital while the other is called antibonding molecular
orbital.
5) The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
6) Just as the electron probability distribution around a nucleus in an atom is given by an
atomic orbital, the electron probability distribution around a group of nuclei in a molecule
is given by a molecular orbital.
7) The molecular orbitals like atomic orbitals are filled in accordance with the Aufbau
principle (Electrons are placed in molecular orbitals starting with the lowest energy
orbitals first), Pauli’s exclusion principle (A molecular orbital cannot hold more than two
electrons and these two electrons in the same molecular orbital have opposite spins) and
the Hund’s rule (When two or more degenerate molecular orbitals are available, one
electron is placed in each before any one of them gets two electrons)

19
 Condition for combination of orbitals
● When atoms share electrons to form a bond, their atomic orbitals mix to form molecular
bonds. In order for these orbitals to mix they must satisfy following conditions :
1) The combining atomic orbitals must have the same or nearly the same energy.
2) The combining atomic orbitals must have the same symmetry about the molecular axis.
3) The combining atomic orbitals must overlap to the maximum extent.
.

This is an example of orbital mixing. The two atoms share one

electron each from there outer shell. In this case both 1s orbitals
overlap and share their valence electrons.

20
 Formation of Molecular Orbitals
● According to wave mechanics, the atomic orbitals can be expressed by wave functions (ψ's) which
represent the amplitude of the electron waves. These are obtained from the solution of Schrödinger
wave equation.
● However, since it cannot be solved for any system containing more than one electron, molecular
orbitals which are one electron wave functions for molecules are difficult to obtain directly from
the solution of Schrödinger wave equation.
● To overcome this problem, an approximate method known as linear combination of atomic orbitals
(LCAO) has been adopted.
● To explain about this concept, let us consider the hydrogen molecule consisting of two atoms A and
B. Each hydrogen atom in the ground state has one electron in 1s orbital. The atomic orbitals of
these atoms may be represented by the wave functions ψ1s A and ψ1s B .
● When two hydrogen atoms are very far from each other, they cannot influence each other's energy
as each has its own energy levels. When we bring them closer, both electrons interact with each
other and with other nuclei which results in formation of two new wave functions with different
energies and quantum numbers.

21
 Continued…..
● Mathematically, the formation of molecular orbitals may be described by the linear
combination of atomic orbitals that can take place by addition and by subtraction of wave
functions of individual atomic orbitals as shown below :
ψ = ψ1s A ± ψ1s B
Therefore, the two molecular orbitals ψ𝜎 and ψ∗𝜎 are formed as :
ψ𝜎 = ψ1s A + ψ1s B
ψ∗𝜎 = ψ1s A − ψ1s B
● When the wave functions are combined in phase, bonding molecular orbital is created and
when they combine out of phase antibonding molecular orbital is created i.e. the addition of
atomic orbitals results in the bonding molecular orbital, ψ𝜎 while the subtraction of atomic
orbitals results in the antibonding molecular orbital, ψ∗𝜎 .
● The σ molecular orbital has a constructive interference and the σ* molecular orbital exhibits a
destructive interference between the two H-atom wave functions.

22
 Continued…..
● The electron density in a bonding molecular orbital is located between the nuclei of the
bonded atoms because of which the repulsion between the nuclei is very less while in case of
an antibonding molecular orbital, most of the electron density is located away from the space
between the nuclei. In fact, there is a nodal plane (on which the electron density is zero)
between the nuclei and hence the repulsion between the nuclei is high.
● Electrons placed in a bonding molecular orbital tend to hold the nuclei together and stabilize a
molecule. Therefore, a bonding molecular orbital always possesses lower energy than either of
the atomic orbitals that have combined to form it. In contrast, the electrons placed in the
antibonding molecular orbital destabilize the molecule. This is because the mutual repulsion of
the electrons in this orbital is more than the attraction between the electrons and the nuclei,
which causes a net increase in energy. Hence, the energy of an antibonding molecular orbital
is higher than the energy of a bonding molecular orbital.

23
Continued…..

24
 Continued…..

As interatomic separation, R decreases and the two atom get closer, the energy of ψ𝜎 orbital
becomes minimum at R = a, where, a is the closest interatomic distance.

25
 Continued…..
● If the two electrons enter the ψ𝜎 orbital and pair their spins, the new configuration is
energetically more favorable than two isolated H-atoms and ψ∗𝜎 orbital which is responsible
for formation of H2 molecule. The energy difference between that of two isolated H-atoms and
the Eσ minimum energy at R = a is called bonding energy.
● The bond order of H2 molecule can be calculated as given below:
1
Bond order = (Nb −Na ) = 1
2
Where, Nb is the number of electrons occupying bonding orbitals and Na is the number
of electrons occupying antibonding orbitals.
● This means that the two hydrogen atoms are bonded together by a single covalent bond Since
no unpaired electron is present in hydrogen molecule, therefore, it is diamagnetic.

26
 Band Theory of Solids
● In between the time period of 1928 and 1931, three scientist namely Bloch, Willson, and
Peierls extended their concept from the lattice to the whole three dimensional solid and invent
the so called band theory.
● They gave convincing explanations of metallic insulating and semi conducting behavior of
solids. That means the physical origin of the band gap was successfully explained based on
this model.
● A solid is made of enormous number of closely packed atoms. When these atoms are isolated,
they have discrete set of energy levels as 1s, 2s, 3s, 3p and so on. Like we know if we consider
silicon, it has 14 electrons and we know we can put these electrons in different atomic levels.
● To form a solid many isolated atoms are brought together then a continuously increasing
interactions occurs between them, so that the split energy levels form essentially continuous
band of energies.

27
 Continued….
● Energy band gaps looks like a continuous although there are different discrete energy levels
lies inside them.

28
 Continued…..
● Now the energy bands in solids corresponds to the energy levels in atoms. Generally lower
levels are splitted less than the higher levels or almost unsplitted because these levels contain
mostly inner electrons, which are not affected by the neighboring atoms.
● An electron can have only energies that can fall within these energy bands. The energy bands
in a solid may be overlapping or not depending on the structure of solid. If they do not
overlap, then the interval between them represents energies, which the electrons in the solid
cannot have.
● These intervals are called forbidden energy gap or the band gap.

29
Continued…..

In the figure, we are considering two closely

packed states. We are considering 2s orbitals and
2p orbitals where these two orbitals has been
splitted and we can see that both of them form
an energy band having separation between them.
Later on at T = 0 K, one of them is completely
filled whereas other one is completely empty
called as valence band and conduction band
respectively.

30
 Band formation in Silicon
● Let us try to understand this phenomena for a real practical example - Silicon, a semiconductor
which is very commonly used for making solar cells. Let us understand it by imaginary
formation of a silicon crystal from isolated silicon atoms.
● Each isolated silicon atoms have 14 electrons and where does these 14 electrons stay? They lie
in different energy orbitals and their electronic configuration can be written as
1s 2 , 2s 2 , 2p6 , 3s 2 , 3p2
● So each atom has available two 1s states, two 2s states, six 2p states, three 2s states and two 3p
states. Now if we consider N atoms, there will be 2N 1s states, 2N 2s states, 6N 2p states, 2N
3s states and 6N 3p states respectively. As the interatomic spacing decrease 3s-3p level merges
to form a energy band and this band contains 8N available states. So this band further splits
into two bands separated by an energy gap Eg .
● The upper conduction band contain the 4N states as does the lower valence band. So the
silicon crystal has two bands of available energy separated by a distance Eg which contains no
allowed energy levels for electrons to occupy. This gap is called forbidden energy gap.
31
 Continued…..
● As shown in the figure, let us suppose interatomic
separation between the silicon atoms is a.
● Let the atoms are brought from locations r>>a to
their actual location
● When r = d1 ; energy levels are well defined
● When r = d2 ; splitting of energy level takes place.
● When r = d3 ; energy gap between 3s and 3p level
completely disappears and all 8N levels are
continuously distributed in an energy band. There
are 8N energy levels with 4N levels filled and 4N
levels empty.
● When r = a (actual interatomic separation), the 8N levels splits into 2 bands, the 4N filled energy
level forming valance band and the 4N empty energy levels forming conduction band. The
energy difference between valance and conduction band is called forbidden energy gap.
32
 Classification of materials
● Based on the concept of energy band gap, materials are classified into three distinct classes,
namely, conductor, insulator, and semi-conductor.
● In conductors, valence band and conduction band overlap each other so, there is virtually no
gap between these bands.
● In semiconductor, there is a very narrow energy gap of order one electron volt between the
valence band and conduction band.
● Insulators are solid having a wide energy gap of the order 10 eV between a filled valence band
and an empty conduction band and they are called insulators because electrons on valence
band cannot jump or cannot acquire the required energy from the applied field that they could
cross the band gap and reach to the conduction band, hence conduction is impossible in them.

33
Continued…..

34
 Velocity of an electron
According to quantum theory, an electron moving with velocity v is equal to a wave packet or
group of waves moving with velocity 𝑣𝑔 (group velocity).
dw
𝑣 = 𝑣𝑔 = (1)
dk
As we know that,
h
E = hf = × 2πf = ħw (2)
2π
Differentiating equation (2) w.r.t. 'k', we get
dE dw dw 1 dE
=ħ ⇒ = (3)
dk dk dk ħ dk
Comparing equations (1) and (3), we have
1 dE
𝑣= (4)
ħ dk
35
 Continued…..
We also know that,
p2
E= (5)
2m
By de-Broglie hypothesis, we have,
h h h 2π
λ= ⇒p= = × = ħk 6
p λ 2π λ
Substituting this value of 'p' in equation (5) and differentiating equation (5) w.r.t. 'k', we get
dE d (ħk)2 ħ2 k
= = 7
dk dk 2m m
Using equations (4) and (7), we get
ħk 𝑝
𝑣= = (8)
m 𝑚
This equation (8) shows that the velocity of electron is directly proportional to propagation
constant, k 36
 Effective mass of an electron
In Kronig-Penny model, the electrons in a crystal are not completely free but they experience a
periodic potential. When an electron in a periodic potential is accelerated by electric field then
mass of electron varies with velocity. This means that mass of an electron is function of velocity
and is known as effective mass of electron denoted by m*.
Due to applied electric field, the electron gets accelerated, so force acting on an electron is given
by
∗
F
F=m a⇒a= ∗ 1
m
We also have,
1 dE
𝑣= (2)
ħ dk
Velocity and acceleration are related to each other by,
d𝑣 d 1 dE 1 dk d2 E
a= = = (3)
dt dt ħ dk ħ dt dk 2
37
 Continued…..
We also know that,
dp dk
p = ħk ⇒ =ħ
dt dt
dp
Since, F = , so we can write
dt
dk
F=ħ 4
dt
Substituting this value of 'F' in equation (1), we get
F 1 dk
a= ∗ = ∗×ħ 5
m 𝑚 dt
Using equations (3) and (5), we get
1 dk 1 dk d2 E
∗
×ħ =
m dt ħ dt dk 2
1 1 d2 E
=
m∗ ħ2 dk 2 38
 Continued…..
2
ħ
∴ m∗ = 2 (6)
d E
dk 2
Equation (6) shows that effective mass of an electron is associated with curvature of energy in k-
d2 E
space. For free particle, this curvature remains constant, so E-k diagram is parabolic. But in
dk2
d2 E
crystal solids, the curvature does not remain constant for bands representing E-k diagram
dk2
because the electron is not completely free within the solids. The E-K diagram for an electron
motion in the conduction band is shown in the figure.

Note:
Differential of increasing function is positive and decreasing function is negative.

39
Continued…..

40
 Continued…..
𝜋
● Velocity changes from negative to zero as value of k goes from − to 0. Similarly, when k
𝑎
𝜋
changes from 0 to , velocity changes from zero to positive values.
𝑎
d2 E
● The effective mass of an electron is positive for the curvature of > 0 i.e. the curvature is
dk2
concave upward.
d2 E
● The effective mass of an electron is negative for the curvature of < 0 i.e. the curvature is
dk2
concave downward.
● For certain value of k, the curvature is zero which implies that the mass is infinite.
● Positive effective mass implies that the electron is accelerated in the direction of applied
external force
● Negative effective mass implies that the electron is decelerated in the direction of applied
external force. This can happen if the external applied force is overmatched by internal forces
due to crystal lattice i.e. when the external force tries to impel into a region dominated by a
repulsive potential whose magnitude increases as the particle penetrates farther into the region.
41
 Thermal Velocity of an electron
● Metals have large number of free electrons approximately 1028 electrons per m3 .
● In the absence of electric field, electrons of conductor absorb thermal energy at room
temperature and gets converted into kinetic energy.
● Due to this, these electrons are in the state of continuous random motion and they move with
velocities in the order of 105 m/s. But these velocities are distributed randomly in all
directions known as thermal velocities.
● In any portion of the conductor, the flow of electrons is so directed that the average thermal
velocity of free electrons in a conductor is zero.
uavg = u1 + u2 + u3 +………. un = 0

42
 Continued…..
Consider an electron of mass 'm' is free to move inside a box of length 'a'. The electron has
momentum +m𝑣𝑥 while moving in positive x-direction and −m𝑣𝑥 in negative x-direction after its
reflection from walls of the box.
Therefore, change in momentum ∆p = 2m𝑣𝑥
2a
The time interval between the collision, ∆t =
𝑣𝑥
∆p m𝑣𝑥2 𝑣2
Force exerted on the wall F = =
∆t a
𝐹 m𝑣𝑥2 m𝑣𝑥2
Pressure on the wall, p = = = 3
𝐴 a×a2 a
Since, the molecules are in random motion and collide randomly with each other, mean square
velocity in x-direction will be equal to that in y and z directions. So,
𝑣𝑥2 = 𝑣𝑦2 = 𝑣𝑧2 ⇒ 𝑣 2 = 𝑣𝑥2 + 𝑣𝑦2 + 𝑣𝑧2 = 3𝑣𝑥2

𝑣2
∴ 𝑣𝑥2 =
3
43
 Continued…..
Nm𝑣 2
Total pressure on the wall by all ,P=
3V
Nm𝑣 2
⇒ PV = (1)
3
Where, V = a3 is the volume of box
From ideal gas equation, we have
PV = nRT (2)
Where,
P = pressure of gas inside the box
V = volume of box
R = Universal gas constant = 8.31 J/mol-K
T = temperature in Kelvin
Number of electron, N
n= is the number of moles of gas
Number of electrons in one mole, NA
NA = 6.023 × 1023 mol−1 is also called Avogadro's number

44
 Continued…..
Comparing equation (1) and (2), we get
Nm𝑣 2 3nRT
= nRT ⇒ 𝑣 2 =
3 Nm
n 1 3RT 3RT
Since, = So, we get 𝑣 2 = ⇒𝑣=
N NA NA m NA m

3KT
∴𝑣= (3)
m
R
Where, K = = 1.38 × 10−23 J/K is Boltzmann constant
NA
KT
The average kinetic energy per degree of freedom is . So , for three degrees of freedom, it is
2
3KT
. Therefore,
2
m𝑣 2 3KT
=
2 2
3KT
∴𝑣= (4)
m
45
 Continued…..
Equation (3) or (4) gives the thermal velocity of electron at equilibrium. This equilibrium is
maintained by the electron interaction with the lattice called lattice vibration. This results in
production of waves called phonons. The energy exchange between electron and lattice crystal is
called lattice scattering.

46
 Electron mobility, Conductivity and
Resistivity

● When an electric field is applied across the conductor, the free electrons accelerate in a
direction opposite to the direction of applied field.
● Due to this acceleration, the electrons get extra velocity but for a short time because the
accelerated electrons collide with other free electrons and ions in the conductor and during the
collision the extra velocity gained is destroyed.
47
 Continued……
● Again the electrons get accelerated and comes to rest after collision with other electrons and
ions.
● Therefore, the motion of electrons in a conductor is like a pause(stop) and go motion.
● As a net result the electrons acquire a small velocity called drift velocity in the direction of
applied electric field.
● Hence, drift velocity is defined as the average velocity with which free electron in a conductor
gets drifted in a direction opposite of applied external field.
● The mean path of electrons between two successive collision is known as mean free path(λ).
● The average time (small interval) between two successive collisions is known as relaxation
time(𝜏).
● Consider a conductor where the potential difference between the ends is V and L is the length
of the conductor. So, the electric field will be given by
V
E = (1)
L
48
 Continued……
● Under the influence of an external electric field, each electron will experience a force. The
force experienced by each electron is given by
F = −eE (2)
● With this force, electron is accelerated in opposite direction to field, so
F = ma (3)
Where, m is the effective mass and a is the acceleration.
So, from equations (2) and (3), we get
ma = − e E
eE
∴a= − (4)
m
● The average drift velocity of an electron is given by
eEτ eτ
𝑣𝑑 = aτ = − =− E
𝑚 𝑚
∴ 𝑣𝑑 = −μd E
eτ
Where, μd = is the drift mobility of an electron.
𝑚

49
 Continued……
● If Ne is the concentration of electron in solid metal then number of electrons crossing unit
area per second is given by
Electron flow = Ne 𝑣𝑑
● The current density is defined as the flow of charge per unit time per unit area and is given by
eτ e2 τNe
J = Ne 𝑣𝑑 e = −Ne Ee = − E
m m
∴ J = −σE
e2 τNe
Where, σ = is the electrical conductivity of an electron
m
● Thus, drift mobility and electrical conductivity of an electron can be related as
e2 τNe
σ= = 𝑣𝑑 eNe
m
● So, it is clear that conductivity of any metal is the product of charge density(electron density)
and drift mobility of electron.
● The reciprocal of conductivity is termed as resistivity
1
𝜌=
σ

50
 Diffusion of Electrons
● When there is a local concentration of charged particles in a small portion of a volume, the
particle tend to spread out until they are uniformly distributed through out the available
space. The process by which charge carriers in a material moves from a region of higher
concentration to a region of lower concentration is called diffusion. During diffusion , there is
motion of charged particle which give rise to a current called diffusion current

51
 Fick’s Law
● It states that carrier flux i.e. the number of particles crossing per unit area per unit time is
proportional to concentration gradient.
dn
∅ = −D
dx
● The negative sign in above equation signifies that diffusion occurs in a direction opposite to
that of increasing concentration. That is, diffusion occurs in the direction of decreasing
concentration of diffusant; thus, the flux is always a positive quantity.
● The diffusion coefficient, D does not ordinarily remain constant but it is affected by
concentration, temperature, pressure, solvent properties and the chemical nature of the
diffusant. Therefore, D is referred to more correctly as a diffusion coefficient rather than as a
constant.
For electron, the diffusion current density is given by
dn
J = (−e)∅ = eD
dx
52
 Fick’s Law
Therefore, the total current density becomes
dn
J = Jdrift + Jdiffusion = neμE + eD
dx
For holes, the diffusion current density is given by
dn
J = e∅ = −eD
dx
Therefore, the total current density becomes
dn
J = Jdrift + Jdiffusion = peμE − eD
dx

53
 Einstein’s relation between mobility and
diffusion coefficient
● In the presence of electric field, the total current density in a conductor is given by
J = Jdrift + Jdiffusion
dn
= neμE + eD
dx
● Under equilibrium conditions, the total current must be zero.
dn dn
neμE + eD = 0 ⇒ eD = −neμE
dx dx
dn μE
∴ = − dx
n D
On Integrating, we get
dn μE
න = න − dx
n D
μEx
ln n = − +C
D 54
 Continued…..
μEx
ln n = − + ln(A)
D
n μEx
ln =−
A D
μEx
− D
∴n= Ae … … … (1)
From Boltzmann’s statistics, for an electric field we have,
eEx
−
n = Ae KT … … . (2)

Comparing equations (1) and (2), we get

μEx eEx μ e
= ⇒ =
D KT D KT
D KT
∴ = (3)
μ e
Equation (3) gives the relation between electron mobility and diffusion coefficient called
Einstein’s relation. 55