Questions to be answered….

1. Write the expression for Fermi-Dirac distribution

function. Sketch schematically the plots of this function
for zero K and for temperature > zero K. [2]
2. Derive the density-of-states function. [5]
3. Assuming the Fermi-Dirac distribution function and the
density-of-states function, obtain (a) an expression for
the density of free-electrons (Mass m) in a metal with
Fermi energy EF, at zero K (b) an expression for Fermi
energy EF in a metal in terms of density (ne) of free
electrons (MASS m), at zero K. [5]

MIT-MANIPAL 1
 FREE ELECTRON THEORY OF METALS
Free-electron = valence electron = conduction electron.

Metal = gas of free-electrons in a lattice of positive ions. The free-

electrons are free to move through the metal but are trapped within a
three-dimensional box formed by the metal surfaces.
 each free-electron is a particle in a box, which is restricted to
quantized energy levels.
 Each energy level can have two states, one for electron with spin
up & the other with spin down.

Pauli exclusion principle allows the occupation of an energy

state by one electron only.
The probability that a particular energy state is occupied by an electron
in a solid is given by the Fermi-Dirac distribution function (quantum
1
statistics): f E  
 E  EF 
exp    1
EF = Fermi energy  kT 
 At zero K, all states with energy < EF f(E)
are occupied and all states with energy AT T = 0K
> EF are vacant. 1.0

AT T > 0K
At T > 0, the probability of electron 0.5
occupation by Fermi level (EF) is half. HIGH TEMP

0 E
EF
DERIVATION OF DENSITY-OF-STATES FUNCTION:
The quantized energy of a particle (mass m) in a one
dimensional box of (length L) are
h2 2  2 2 2 , n = 1, 2, 3, . . .
En  2
n  n
8mL 2 m L2
For a free-electron (mass m) in a metal cube of side L
(three-dimensional box), the quantized energies are
 2 2
En 
2mL 2
n2
x  n2
y  n2
z  nx, ny, nz = quantum numbers.
 Each allowed energy value is characterized by this set of quantum
numbers (nx, ny, nz - one for each degree of freedom) and the spin
quantum number ms (two values).
 Because of the macroscopic size L of the box, the energy levels for
the electrons are very close together. As a result, the quantum
numbers can be treated as continuous variables.

In a three-dimensional quantum
number space with axis representing
nx, ny, nz, the allowed energy states
can be represented as dots located
at positive integral values of the
three quantum numbers.
Energy equation in 3D-box can be written as

2 2 2 E  2 2
n x  n y  nz   n2 where Eo 
Eo 2 m L2
E
This is the equation of a sphere of and n
Eo
radius n.
 Thus, the number of allowed energy
states having energies between E and
E+dE is equal to the number of points in nZ
a spherical shell of radius n and thickness
dn.
 The “volume” of this shell is NUMBER OF dn
STATES FROM E TO E+dE
n
nY
G(E)dE = (⅛)(4n2dn) = (½)n2dn

G(E) is the total number of states. nX

 Since all the nx, ny, nz can have positive values only in an octant
of the three-dimensional space.

g(E) IS THE NUMBER OF STATES PER UNIT VOLUME [V

G(E)
g(E)  IN NORMAL SPACE] PER UNIT ENERGY RANGE
V
E
Replacing n by ,
Eo
 1

 E   E   2
G(E) dE  1
  d  
2
 E o   E o  
 
1 1 3 1
 E  2 1 2 
G(E) dE  1
2
  E o 2 E dE  1
4
 E o E dE
2 2

 Eo 
3
 1
  2 2  2
G(E) dE  1
4
  
2 
E dE
2

 2mL 
 3
2 m 2 L3 1 2
G(E) dE  2 3
E dE , L3  V
2  
3
G(E) 2 m 2 12
g(E) dE  dE  2 3
E dE
V 2  
3
4 2 m 2 1 h
g(E) dE  E 2
dE  
h3 2
To consider the spin states, each particle-in-a-box state
should be multiplied by 2.

3
8 2 m 2 1
 g(E) dE  E 2
dE
h3
g(E) is called the density-of-states function.
For a metal in thermal equilibrium, the number of electrons
per unit volume, N(E) dE, that have energy between E and
E+dE is equal to the product of the number of allowed
states and the probability that a state is occupied:

i.e N(E) dE= g(E) f(E)dE

3 1
8 2 m 2
E 2 dE
N(E) dE 
h3  E  EF 
exp    1
 kT 
EF
The total number of electrons per unit

volume:
ne   N(E) dE
0
3 EF 1
8 2 m 2
E 2 dE
ne 
h3   E  EF 
0
exp    1
 kT  EF
At T = 0, f(E) = 1 for E < EF and f(E) = 0 for E > EF .
3 EF
8 2 m 2 1
 At T = 0, ne 
h3 E
0
2
dE FREE-ELECTRON
DENSITY IN A
METAL AT
3 3
ZERO K
8 2 m 2
16 2  m 2
  EF
3 3
ne  2
3
2
 EF 2
h3 3 h3
2
2
h  3 ne  3
EF 0  
FERMI ENERGY OF A
  METAL AT ZERO K
2m  8
The average energy of a free-electron in a metal at
zero K is 3
E AV  5
EF
At zero K, all levels below EF are filled with electrons and all levels
above EF are empty. At 300 K, a very small fraction of the free
electrons are excited above EF.
SJ-EXAMPLE 43.4: The Fermi Energy of Gold:
Each atom of gold (Au) contributes one free-electron to
the metal. The concentration of free-electron in gold is
5.90 x 1028/m3. Compute the Fermi Energy of gold.
2
Solution: h 2
 3 ne  3
EF 0    
2m  8
2
34 2
 3 (5.90 x10 ) 28 3
EF 0 
(6.626 x10 )
 
2 (9.1x10 31)  8 

Answer: EF=8.85 x 10-19 J=5.53 eV

SJ-PROBLEM 43.29: Sodium is a monovalent metal
having a density of 971 kg/m3 and a molar mass of
0.023 kg/mol. Use this information to calculate (a) the
density of charge carriers and (b) the Fermi energy.

Solution:
Solution:B
2
2
h  3 ne  3
EF 0    
2m  8
2
34 2
 3 (2.54 x10 ) 
28 3
EF 0 
(6.626 x10 )
 
2 (9.1x10 31)  8 

Answer: EF=5.05 x 10-19 J=3.15 eV

 SJ-PROBLEM 43.31: Calculate the energy of a
conduction electron in silver at 800 K, assuming the
probability of finding an electron in that state is 0.950.
The Fermi energy is 5.48 eV at this temperature.
1
Solution: f E  
 E  EF 
exp    1
 kT 
1
  E  EF  
f E   exp    1  0.950
  kT  
 E  EF  1 E  EF
exp    1  0.0526  ln(0.0526)
 kT  0.950 kT
SJ-PROBLEM 43.33: Show that the average kinetic energy of a
conduction electron in a metal at zero K is E  3E AV 5 F

Suggestion: In general, the average kinetic energy is

1
where the density of particles
E AV 
ne  E N(E) dE

ne   N ( E ) dE
0
3 1
8 2 m 2
E dE
2
N(E) dE 
h3  E  EF 
exp    1
 kT 
Solution: We have
1
E AV 
ne  E N(E) dE
 3
2 8 2 m 2 3
But ne  EF 2
3 h3
 SJ-PROBLEM 43.35: (a) Consider a system of electrons confined
to a three-dimensional box. Calculate the ratio of the number of
allowed energy levels at 8.50 eV to the number at 7.00 eV. (b)
Copper has a Fermi energy of 7.0 eV at 300 K. Calculate the ratio
of the number of occupied levels at an energy of 8.50 eV to the
number at Fermi energy. Compare your answer with that obtained
in part (a).
Solution:
(a) The density-of-states at energy E .
3
8 2 m 2 1
g (E)  C E
1
2
g (E)  E 2
h3

Hence the ratio required is.

Solution(b): 3 1
8 2 m 2
E 2
N (E) 
h3  E  EF 
exp    1
 kT 
1
2
CE
N (E) 
 E  EF 
exp    1
 kb T 
 Questions to be answered…
1. Explain briefly the energy band theory of solids. [5]
2. Explain the classification of solids regarding the electrical
properties, based on their energy band diagram. [5]
3. Indicate the position of (a) Fermi-level (b) donor levels
(c) acceptor levels, in the energy band diagram of a
semiconductor. [2]
4. Explain the terms: Conductor, insulator, semiconductor,
intrinsic semiconductor, extrinsic semiconductor, n-type
semiconductor, p-type semiconductor, valence band,
conduction band, donor levels, acceptor levels. [1 Each]

18
 BAND THEORY OF SOLIDS
There are two different wave functions  S (r ) and  S (r ) (for
an atom with single s-electron outside of a closed shell) for
which the probability density is the same.
The wave functions of two atoms combine to form a composite
wave function for the two-atom system when the atoms are
close together. In Figure (a), two atoms with wave functions  S (r)
combine.
In Figure (b), two atoms with wave functions  S (r) and S (r )
combine.
These two possible combinations of wave functions
represent two possible states of the two-atom
system which have slightly different energies.
Thus, each energy level of an atom splits into two
close energy levels when the wave functions of the
two atoms overlap.
Figure (a) shows the splitting of 1s and 2s levels when
two sodium atoms are brought together.

Figure (b) shows the splitting of 1s and 2s levels into five

levels each when five sodium atoms are brought together.

Figure (c) shows formation of energy bands (bunches of

closely spaced energy levels) when a large number of
sodium atoms are assembled to form a solid.

ENERGY BANDS OF
SODIUM CRYSTAL
3p
3s
E
2p
2s
1s
• Thus, in a crystalline solid there are a large number of
allowed energy bands that arise from the various atomic
energy levels.

• Forbidden energy gaps occur between the allowed bands.

Some bands may be wide enough in energy so that there is
an overlap between the adjacent bands.
• The 1s, 2s, and 2p bands of solid sodium are filled
completely with electrons. Since there are 2(2l+1) energy
states in a subshell each energy band has 2(2l+1)N energy
states ENERGY BANDS OF
SODIUM CRYSTAL
where N = number of atoms in the crystal. 3p
3s
E
2p
2s
1s
 ELECTRICAL CONDUCTION IN METALS,
INSULATORS AND SEMICONDUCTORS
Good electrical conductors contain high density of free
charge carriers, and the density of free charge carriers in
insulators is nearly zero. In semiconductors free-charge-
carrier densities are intermediate between those of
insulators and those of conductors.
Metals: Metal (an electrical conductor) has a partially
filled energy band. Highest electron-occupied energy level
is the Fermi-level, at zero K. If a potential difference is
applied to the metal, electrons having energies near the
Fermi energy require only a

Eg = 0
small amount of additional energy from
PARTIALLY FILLED the applied field to reach nearby empty
VB & CB E=EF
energy states above the Fermi-level.
E=0 Hence metal is a good electrical
CONDUCTOR
conductor.
Insulators: In these the outermost energy bands are filled
(valence band) and empty conduction band with a large
energy gap (Eg>>kT, kT = thermal energy). The Fermi-
level lies in the energy gap. Thermal energy at room
temperature is not sufficient to excite the electrons from
valence-band to conduction band. Since the free-electron
density is nearly zero, these materials are bad conductors
of electricity.
Semiconductors: These have the same type of band
structure as an insulator but the energy gap is much
smaller ( 1 eV). At room temperature a small fraction of
valence electrons are thermally excited to conduction band

CONDUCTION
EMPTY CB BAND
Eg EF
Eg EF
FILLED VB VALENCE BAND

INSULATOR SEMICONDUCTOR
At zero K, all electrons in semiconductors are in the
valence band, and no energy is available to excite them
across the energy gap.
Thus, semiconductors are poor conductors at very low
temperatures. Because the thermal excitation of electrons
across the narrow gap is more probable at higher
temperatures, the conductivity of semiconductors increases
rapidly with temperature.
[The conductivity of a metal decreases slowly with
increasing temperature.]

The charge carriers in a semiconductors are

electrons and holes. When an electron moves from the
valence band into the conduction band, it leaves behind
a vacant site, called a hole (particle with a positive
charge +e).
 When a conduction electron from a nearby site transfers into
the hole, the hole is said to drift to the position of the
conduction electron. Thus, the hole migrates opposite to the
direction of electron movement.
In an intrinsic semiconductor (pure semiconductor) there are
equal number of conduction electrons and holes.

ELECTRONS In the presence of an external

CONDUCTION HOLES electric field, the holes move in
ELECTRONS CONDUCTION
the direction of field and the
BAND
conduction electrons move
ENERGY GAP opposite to the direction of the
field. Both these motions
VALENCE BAND
correspond to the current in the
APPLIED E-FIELD
same direction.
Doped Semiconductors: Doping is the process of adding
impurities to a semiconductor. By doping both the band
structure of the semiconductor and its resistivity are modified.
If a tetravalent semiconductor (Si or Ge) is doped with a
pentavalent impurity atom (donor atom), four of the electrons
form covalent bonds with atoms of the semiconductor and one
is left over. At zero K, this extra electron resides in the donor-
levels, that lie in the energy gap, just below the conduction
band.
Since the energy Ed between the donor levels and the bottom
of the conduction band is small, at room temperature, the
extra electron is thermally excited to the conduction band.

This type of semiconductors are called n-type semiconductors

because the majority of charge carriers are electrons (negatively
charged).

If a tetravalent semiconductor is doped with a trivalent

impurity atom (acceptor atom), the three electrons form
covalent bonds with neighbouring semiconductor atoms,
leaving an electron deficiency (a hole) at the site of fourth
bond.
At zero K, this hole resides in the acceptor levels that lie in
the energy gap just above the valence band.
Since the energy Ea between the acceptor levels and the top of
the valence band is small, at room temperature, an electron
from the valence band is thermally excited to the acceptor
levels leaving behind a hole in the valence band.
This type of semiconductors are called p-type semiconductors
because the majority of charge carriers are holes (positively
charged).

The doped semiconductors are called extrinsic

semiconductors.
SJ-PROBLEM 43.37: Light from a hydrogen
discharge tube is incident on a CdS crystal (Eg= 2.42
eV). Which spectral line from the Balmer series are
absorbed and which are transmitted ?

Solution: Photons of energy greater than 2.42 eV will be

absorbed. This means wavelength shorter than

All Balmer lines absorbed except the red line (656 nm)
which is transmitted.

Note: Balmer lines are 656nm, 486nm, 434nm, 410nm, …

SJ-PROBLEM 43.39: Most solar radiation has a
wavelength of 1 μm or less. What energy gap should
the material in solar cell have in order to absorb this
radiation ? Is silicon (Eg= 1.14 eV) appropriate ?

Thus, the energy gap for the collector material should be

Eg ≤ 1.24 eV. Since Si has an energy gap Eg ≈ 1.14 eV, it will absorb
radiation of this energy and greater. Therefore, Si is acceptable as a
material for a solar collector.
 Questions to be Answered today…

1. Sketch schematically the plot of resistance of a

superconducting material vs temperature, near the critical
temperature. [1]
2. Explain Meissner effect. [2]
3. Give a brief account of superconductivity. [5]
4. Explain briefly the BCS theory of superconductivity in
metals. [4]

31
R SUPERCONDUCTIVITY
Superconductors are the materials whose electrical
resistance (R) decreases to zero below a certain
temperature TC called the critical temperature (4.2
K for Hg).
0 T
TC
Meissner effect is the exclusion
of magnetic flux from the interior
SUPERCONDUCTING ROD
IN MAGBETIC FIELD B

of superconductors when their

temperature is decreased below
the critical temperature.
V
Re sis tan ce, R 
I

∆V  E
E = electric field in the material
MIT- MANIPAL 32
Since R = 0 in the superconductor below TC , ∆V = 0
or E=0
Faraday,s law dB
of induction: 
E  ds  
dt
i.e., the line integral of the electric field around any
closed loop is equal to the negative rate of change in the
magnetic flux B through the loop.
Since E = 0 in the super conductor (below TC)
dB
 E  ds  0   dt
i.e., the magnetic flux in the superconductor cannot change.
 magnetic field, B = B/A = constant inside the superconductor.
From Meissner effect, one can write, B = 0 or B = 0 inside a
superconductor, below TC.  the superconductor is a perfect
diamagnet. 33
If a magnetic field B is applied on the superconductor and
its Tc is increased, the superconductivity disappears when B
> BC = critical magnetic field.
A diamagnet has a negative magnetic susceptibility. It is
repelled by a magnetic field. Because of this a small
permanent magnet can be made to float (levitate) in air,
above a superconductor (below TC).
A superconductor expels magnetic flux (Meissner effect) by
forming surface currents. These surface currents induced in
the superconductor produce a magnetic field that
exactly cancels the externally applied magnetic field inside
the superconductor.
MAGNETIC LEVITATION 34
 BCS theory of superconductivity in metals:
BCS theory — proposed by Bardeen, Cooper, and Schrieffer in
1957 — is the first microscopic theory of superconductivity since
its discovery in 1911
According to this theory, two electrons can interact via
distortions in the array of lattice ions so that there is a
net attractive force between the electrons.
As a result, the two electrons, are bound into an entity
called a Cooper pair. The Cooper pair behaves like a
boson (= particle with integral spin that do not obey the
Pauli exclusion principle).
At very low temperature, it is possible for all bosons in a
collection of such particles to be in the lowest quantum
state.
As a result, the entire collection of Cooper pairs in the
metal is described by a single wave function. Above the
energy level associated with this wave function is an energy
gap equal to the binding energy of a Cooper pair.
Under the action of an applied electric field, the
Cooper pairs experience an electric force and move
through the metal.
A random scattering event of a Cooper pair from a
lattice ion would represent resistance to the electric
current. Such a collision would change the energy of
the Cooper pair because some energy would be
transferred to the lattice ion.
But there are no available energy levels below that
of the Cooper pair (it is already in the lowest state)
and none available above, because of the energy
gap.
As a result, collisions do not occur and there is no
resistance to the movement of Cooper pairs.
Note: Preparation meets the opportunity is luck!
So, prepare well….Surely luck will follow
you…!!