Chapter6-Free Electron Fermi Gas

Free electron theory
• What we have discuss all this is just limited to the nature of lattice
vibrations in a harmonic potential.
• In this chapter we will discuss the role of electrons on the physical
properties of metals. We will discuss the theory of free electrons as the
beginning.
• The free electron theory we assume:
• the nucleus is in the sea of electrons. The term ocean may be a
little awkward, but it carries the meaning that is sufficiently
accurate (the number of electrons and free to move)
• Electrons to move freely throughout the volume of metal
• reaction between electrons and between electrons and the nuclei
is negligible
• potential energy is zero
Dr. Suriati Paiman, PHY3201 Solid State Physics

PHY 3201 FIZIK KEADAAN PEPEJAL
•the nucleus is in the sea
of electrons.
• Electrons to move freely
throughout the volume of
metal
• reaction between
electrons and between
electrons and the nuclei
is negligible
• potential energy is zero

Free Electron Fermi Gas
• The properties of materials depends to a large extent on the type of
bonding and the energy distribution of the bonding electrons. The
bonding electrons in the solid find themselves in the potential of their
parent nuclei, other nuclei and other electrons. Because of the intricate
nature of the potential, the theory of solids is quite complex.
•However, it may be simplified by assuming simple models for the
potential appropriate to different types of solids

Many solids conduct electricity.
There are electrons that are not bound to atoms but are able to
move through the whole crystal.
Conducting solids fall into two main classes; metals and

semiconductors.
Metal - Resistivity increases by the addition of small amounts
of impurity. The resistivity normally decreases monotonically
with decreasing temperature.
Semiconductor – Resistivity can be reduced by the addition of

small amounts of impurity. Semiconductors tend to become
insulators at low T.
Why mobile electrons appear in some
solids and not others?
• According to free electron model (FEM), the valance
electrons are responsible for the conduction of electricity,
and for this reason these electrons are termed conduction
electrons.
• Na11 ￫ 1s2 2s2 2p6 3s1 Valance electron (loosely bound)
Core electrons
• This valance electron, which occupies the third atomic shell,

is the electron which is responsible chemical properties of
Na.

A valence electron really belongs to the whole crystal,
since it can move readily from one ion to its neighbour,
and then the neighbour’s neighbour, and so on.
This mobile electron becomes a conduction electron in a
solid.
– The removal of the valance electrons leaves a

positively charged ion.
+ + +
– The charge density associated the positive ion
+ + +
cores is spread uniformly throughout the metal so
that the electrons move in a constant electrostatic
potential. All the details of the crystal structure is
lost when this assumption is made.
According to Free Electron Fermi Gas this potential is

taken as zero and the repulsive force between
conduction electrons are also ignored.
Free Electron Fermi Gas
The main assumptions for metals is as follows:

• The atomic nuclei are fixed on the crystal lattice at regular
positions.
• The electrons in the inner shells of each atom are tightly
bound to the atom; the atomic nucleus “owns” them.
• Electrons in the outer shells are not bound to any particular
atom. They are fairly free to move around in the crystal
lattice, but they are still bound to the solid.
• All atoms together provide a collective potential in which all
the outer electrons are moving. The electrons in turn, by
floating around from one atom to the other, provide bonds
that keep all the atoms together.

free electron theory of metals
A free electron model is the simplest way to represent the
electronic structure of metals. According to this model, the
valence electrons of the constituent atoms of the crystal
become conduction electrons and travel freely throughout the
crystal. The only restriction being that they cannot escape from
the metal. Within this model we also neglect the interaction of
conduction electrons with ions of the lattice and the interaction
between the conduction electrons. Hence the conduction
electrons in a metal are modeled by a free electron gas.
This theory is called the free electron theory of metals

Free electron theory
• We divide the discussion of this chapter into two
main parts:
– the classical theory of free electron,
– free electron theory of quantized

The classical theory of free electron
• Drude, Lorentz, Debye
– Boltzmann distribution
• We should remember that in the general kinetic theory of
gases, particles are considered not highly charged, whereas
in the theory of free electrons are charged particles.
• Because of the properties of this equation the kinetic theory
used to explain the concept: -
– thermal conductivity
– Electrical conductivity (Ohm’s Law)
• but this classical model fails to explain;
– the specific heat of material,
– the average free distance between the electron

• Classical electron model can not explain
some physical properties of metals.
• Which clearly is not actually made up of
metallic electron gas that complies with
Boltzmann distribution.
• In the next chapter we will review the
quantum theory of free electrons.

Quantum model of free electrons in one dimension
• In this model we consider consists of a metal box filled with
electrons. Then the behavior of electrons in this box
reviewed from the point of quantum theory.
• Thus we must solve the Schrodinger problem.
• takes account of the wave-particle nature of the electron
and includes the implications of the Uncertainty Principle
• Solutions to the Schröedinger Equation describe the energy
and probable location for each electron in an atom.
• This theoretical approach is known as Wave Mechanics.

http://chemweb.ucc.ie/courses/FLalor/FJL%20Lecture%205.htm
PHY 3201 FIZIK Dr. Suriati Paiman, PHY3201 Solid State Physics
KEADAAN PEPEJAL
The Time-Independent Schrodinger Equation
The Schrodinger Equation is a mathematical description

of an electron as a wave as suggested by Schrodinger
in 1926. The time independent Schrodinger Equation is
used when the properties of atomic systems have to be
calculated in stationary conditions, i.e. when the property
of the surroundings of the electron does not change with
time. If the potential energy V, depends only on location
(and not, in addition, on time), :
# electron is moving in a wave function

# In this model we consider consists of a metal box filled with electrons. Then
the behavior of electrons in this box reviewed from the point of quantum theory.
The time independent Schrodinger equation has the following

form:
Hψ n = ε nψ
“analogy with classical mechanics, the Hamiltonian is
commonly expressed as the sum of operators
corresponding to the kinetic and potential energies of a
system”
H is the Hamiltonian for electron = total energy of a system =

Kinetic Energy + Potential Energy = T + V(x)
εn is the energy of the electron in orbital n
Ψn is the wavefunction for the orbital n
If we use the assumptions above, the Schrodinger equation for a

metal is simply that of a particle in a box and since the potential is
constant we might as well set it to zero. The Hamiltonian will
then consist of only the kinetic term

# In this model we consider consists of a metal box filled with electrons. Then
the behavior of electrons in this box reviewed from the point of quantum theory.
If we use the assumptions above, the Schrodinger equation for a metal is

simply that of a particle in a box and since the potential is constant we
might as well set it to zero. The Hamiltonian will then consist of only
the kinetic term,
p2 1 d d h2 d 2
H= = (−ih )(−ih ) = −
2m 2 m dx dx 2m dx 2
Where p is the momentum operator, d and m is the mass
of the particle p = −ih
dx
Thus, the Schrodinger eqn. reduces to
h2 d 2
Hψ n = − 2
ψ n = ε nψ n Energy of electron in
orbital (kinetic term)
2m dx
h2 d 2
Hψ n = − 2
ψ n = ε nψ n Energy of electron in
orbital (kinetic term)
2m dx
h2 d 2
− 2
ψ n = ε nψ n
2m dx
d2 2m
2
ψ n = − 2 ε nψ n
dx h
d2 2m
2
ψ n + 2 ε nψ n = 0
dx h
k = wave number

Free electron
For one dimension the Schrodinger equation becomes
∂ 2ψ n 2m
+ 2 ε nψ n = 0 mathematical description of an electron as a
∂ x
2
h wave
2m
Let k 2 = ε ∂ 2ψ 2m
h 2
+ 2 (ε − V )ψ = 0
∂ x h
2
∂ 2ψ n
+ nψ n = 0
2
k
∂ x
2
This is the differential equation for an undamped

vibration and have the following solution
h2 2
ψ ( x ) = A sin kx where ⇒ ε=
2m
k

‘particle in a box’
• The particle in a one-dimensional potential energy box is the most
simple example where restraints lead to the quantization of energy
levels.
• The box is defined as having zero potential energy everywhere inside a
certain region, and infinite potential energy everywhere outside' that
region.
• For the one-dimensional case in the direction, the time-independent
Schrödinger equation can be written as:[48]
1-dimensional potential energy box (or

infinite potential well)

Since no boundary condition had to be considered for
the calculation of the free electrons, all values of the
energy are “allowed” i.e. one obtains an energy
continuum.

Electron in a potential well (bound electron)
Consider a dimensional potential box in which the
electron can move freely between two infinitely high
potential barriers. The potential barriers do not allow
the electron to escape from the potential well, which
means that ψ = 0 for x ≤0 and x≥L The potential energy
inside the well is zero. Therefore
∞ ∞ ∂ 2ψ n 2m
+ 2 ε nψ n = 0
V ∂ x
2
h
 2π 
ψ n = A sin  x 
 λn 
x 2π
L where k =
λ
The boundary conditions are
ψ=0 at x = 0
ψ=0 at x = L
At x = L,
 2π 
ψ n = A sin  L  = 0
 λn 
2π λn
Which can only be satisfied if L = nπ or L = n
λn 2
Thus,
 nπ 
ψ n = A sin  x
 L 

∞ ∞
V
p 2 h 2 k 2 h 2  2π 
εn = = =  
2 m 2 m 2 m  λn  x
L
h  2π  h  nπ 
2 2 2 2
Energy of electron that is
εn =   =   confined to a 1D box of
2m  2 L / n  2m  L  width L
These solutions correspond to standing waves with a

different number of nodes within the potential well as
is shown in Fig.1.

Now we need to accommodate N valence electrons in
these quantum states. According to the Pauli exclusion
principle no two electrons can have their quantum
number identical.
The electronic state in a 1D solid is characterized by

two quantum numbers that are n and ms, where n
describes the orbital Ψn and ms describes the magnetic
quantum number. Therefore, each orbital labeled by the
quantum number n can accommodate two electrons,
one with spin up and one with spin down orientation.

Let nF denote the highest filled energy level, where we
start filling the levels from the bottom (n = 1) and
continue filling higher levels with electrons until all N
electrons are accommodated. It is convenient to
suppose that N is an even number.
The condition 2nF = N determines nF, the value of n for
the uppermost filled level.
The energy of the highest occupied level is called
the Fermi energy, εF. For the one dimensional system
of N electrons we find
h  nF π  h  Nπ 
2 2 2 2
εF =   =  
2m  L  2m  2 L 

Energy of electron that is confined to a 1D box of
width L
h  2π  h  nπ 
2 2 2 2
εn =   =  
2m  2 L / n  2m  L 
The energy of the highest occupied level
h  nF π  h  Nπ 
2 2 2 2
εF =   =  
2m  L  2m  2 L 

The ground state of the N electron system is illustrated
in Fig.2a: All the electronic levels are filled up to the
Fermi energy. All the levels above are empty.

The distribution of electrons among the levels is usually
described by the distribution function, f(ε), which is
defined as the probability that the level ε is occupied by
an electron. Thus if the level is certainly empty, then, f(ε)
= 0, while if it is certainly full, then f(ε) = 1. In general, f(ε)
has a value between zero and unity.
It follows from the preceding discussion that the
distribution function for electrons at T = 0°K has the form
1 ε < εF
f (ε ) =
0 ε > εF

The distribution function at non-zero temperature is
given by the Fermi distribution function. The Fermi
distribution function determines the probability that an
orbital of energy ε is occupied at thermal equilibrium.
The quantity µ is called the chemical potential.
1
f (ε ) =
exp[(ε − µ ) / k B T ] + 1

Loosely bounded valence electrons are
attracted towards nucleus of other
atoms
Electrons spread out among atoms
forming electron clouds.
The removal of the valance electrons
leaves a positively charged ion.
The charge density associated the
positive ion cores is spread uniformly
throughout the metal so that the
electrons move in a constant
electrostatic potential.
This potential is taken as zero and the
repulsive force between conduction
electrons are also ignored.

∂ 2ψ n 2m
+ 2 ε nψ n = 0
∞ ∞ ∂ x
2
h
V The boundary conditions are
ψ=0 at x = 0
ψ=0 at x = L
At x = L,
x
L
h 2  2π  h 2  nπ 
2 2
εn =   =  
2m  2 L / n  2m  L 

The distribution of electrons among the levels is usually described by the
distribution function, f(ε), which is defined as the probability that the level ε
is occupied by an electron.
1 • fFD=? At 0°K
f FD =
1 + e ( E − EF ) / kBT
fFD(E,T) i. E<EF
1
f FD = ( E − EF ) / k B T
=1
1+ e
0.5 ii. E>EF

1
f FD = ( E − EF ) / k BT
=0
1+ e
E
E<EF EF E>EF
FREE ELECTRON GAS IN THREE
DIMENSION
The free particle Schrodinger equation in three
dimension is
rrrr
h2  ∂2 ∂2 ∂2 
−  2 + 2 + 2 ψ k ( r ) = ε ψ ( )
kkkk
kkkk
2m  ∂x ∂y ∂z 
If the electrons are confined to a cube of edge L, the
solution is the standing wave
ψ n (r ) = A sin k x x sin k y y sin k z z
where n xπ n yπ nzπ
kx = , ky = , kz =
L L L
Periodic Boundary Conditions
To apply the boundary conditions to the free electrons
wave function in a solid, it is more convenient to write the
solution to the Schrodinger equation as:
For a cubic solid of dimension L, the wave function must

satisfy the relation

If we impose the above conditon in the x direction
To satisfy the boundary condition
2π 4π
k x = 0,± ,± ,..
L L
and similarly for ky and kz.

The energy of the orbital with wavevector k
εk =
h2 2 h2 2
2m
k =
2m
(
k x + k y2 + k z2 )
In the ground state of a system of N free electrons, the
occupied orbitals may be represented as points inside a
sphere in k space. Therefore all the occupied states lie
inside the sphere of radius kF. The energy at the surface
of this sphere is the Fermi energy. The magnitude of the
wavevector kF and the Fermi energy are related by the
following equation: 2
h 2
εF = kF
2m
The Fermi energy and the Fermi wavevector
(momentum) are determined by the number of valence
electrons in the system. In order to find the relationship
between N and kF, we need to count the total number of
orbitals in a sphere of radius kF which should be equal to
N. There are two available spin states for a given set of
kx, ky, and kz. The volume in the k space which is
occupies by this state is equal to (2π/ L)3. Thus in the
sphere of 4πkF3/3 the total number of states is
4πk / 33
V 3
2. F
= kF = N
(2π / L ) 3
3π 2

Then
1/ 3
 3π N  2
k F =  
 V 
which depends only on the particle concentration.
Therefore, the Fermi energy is
2/3
h  3π N 
2 2
εF =  
vvvv
kkkk
2m  V 
The particle velocity in the orbital k is given by =h /m
The electron velocity vF at the Fermi surface is
1/ 3
 hk F   h  3π N  2
vF =   =   
 m   m  V 
Meaning of the Fermi Temperature
The Fermi temperature is not the temperature of the
electron gas!
It is a measure of where the Fermi energy is at

(typically on the order of ~ 10000 K)
So, for most metals say at room temperature, not

many electrons are excited above the Fermi energy.

Density of States
In phase space a surface of
constant energy is a sphere, is
as schematically shown in the
picture.
Any "state", i.e. solution of the
Schroedinger equation with a
specific k, occupies the
volume given by one of the
little cubes in phase space.
The number of cubes fitting
inside the sphere at energy E
thus is the number of all
energy levels up to E

The density of states, D(ε) is defined as the number of
dN
orbitals per unit energy range, D(ε ) ≡
dε
V  2mε 
3/ 2
With N = 2  2  to obtain the total number of

3π  h 
orbitals of energy ≤ ε
3/ 2
V  2m  3N
D(ε ) =  2  ε 1/ 2
=
2π  h 
2
2ε

Example
• What are the assumptions of the free electrons theory of metal?
[4]
• What does the Schrodinger Equation represent? Write down the
equation for one-dimensional, time-independent Schrodinger equation.
[4]
• Find the energy of an electron that is confined to a one-dimensional box
of width L. [8]
• Define Fermi energy and using the results above find the Fermi energy
for a one dimensional system of N electrons. [4]

Heat Capacity of the Electron Gas
Heat Capacity, C
The heat capacity, C is the amount of heat dQ, which is
needs to be transferred to a substance on order to raise
its temperature by a certain temperature interval.
The heat capacity at constant volume is defined as
 ∂U 
CV =  
 ∂T V
The specific heat capacity is the heat capacity per unit

mass C
c=
m
Source: Chris Wiebe

Source: Chris Wiebe

Electronic Heat Capacity
The increase ∆U≡U(T)-U(0) in the total energy of a

system of N electrons when heated from 0 to T is
∞ εF
At 0 K, the upper limit is εF
∆U = ∫ dεεD(ε ) f (ε ) − ∫ dεεD(ε ) and the FD function is 1
0 0
where f(ε,T) is the Fermi distribution function and D(ε) is
the density of states.
The Fermi-Dirac Distribution Function is given as
1
f (ε , T ) =
exp[(ε − µ ) / k BT ] + 1
The function f(ε, T) gives the probability that the energy
level ε, is occupied by an electron at Temperature T
We multiply the identity
∞ εF
N = ∫ dεD(ε ) f (ε ) = ∫ dεD(ε )
0 0
By εF to obtain
εF ∞ εF
( ∫ + ∫ )dεε F D(ε ) f (ε ) = ∫ dεε F D(ε )
0 εF 0
εF ∞ εF
∫ dεε
0
F D(ε ) f (ε ) + ∫ dεε F D(ε ) f (ε ) − ∫ dεε F D(ε ) = 0
εF 0

∞ εF
∆U = ∫ dεεD(ε ) f (ε ) − ∫ dεεD(ε )
0 0
εF ∞ εF
∆U = ∫ dεεD(ε ) f (ε ) + ∫ dεεD(ε ) f (ε ) − ∫ dεεD(ε )
0 εF 0
εF ∞ εF
∆U = ∫ dεεD(ε ) f (ε ) + ∫ dεεD(ε ) f (ε ) − ∫ dεεD(ε ) −
0 εF 0
εF ∞ εF
( ∫ dεε F D(ε ) f (ε ) + ∫ dεε F D(ε ) f (ε ) − ∫ dεε F D(ε ))
0 εF 0
∞ εF
∆U = ∫ dε (ε − ε F ) D(ε ) f (ε ) + ∫ dε (ε F − ε )[1 − f (ε )]D(ε )
εF 0

∞ εF
∆U = ∫ dε (ε − ε F ) D(ε ) f (ε ) + ∫ dε (ε F − ε )[1 − f (ε )]D(ε )
εF 0
The energy needed to take electrons from εF to

the orbital of energy ε > εF
Energy needed to bring the electrons
to εF from orbital below εF
εF
∞ 
d  ∫ dε (ε − ε F )D(ε ) f (ε ) + ∫ dε (ε F − ε )[1− f (ε )]D(ε ) 
ε 
Cel =
dU
=  F 0 
dT dT

∞ εF
dU df (ε ) df (ε )
Cel = = ∫ dε (ε − ε F )D(ε ) − ∫ dε (ε F − ε ) D(ε )
dT ε F dT 0
dT
∞
df (ε , T )
Cel = ∫ dε (ε − ε F ) D(ε )
0
dT
Since the electrons at εF are of importance, we make
D(ε) = D(εF)
∞
df (ε , T )
Cel ≅ D(ε F ) ∫ dε (ε − ε F )
0
dT

If we ignore the variation of the chemical potential with
temperature and assume that µ = εF, which is good
approximation at room temperature and below. Then
df (ε , T ) ε − ε F exp(ε − ε F ) / k B T
=
dT k B T 2 [exp(ε − ε F ) / k B T + 1]2
Therefore,
( ε −ε F )
∞
(ε − ε F ) ∞
x 2 (k B T )
k BT 3
e ex
C el = D(ε F )∫ dε = D(ε F ) ∫
[ ]
2 2 2 2
dx
0 k BT  (εk−εTF )  −ε F / k B T k BT e +1
x
e B
+ 1
 

Taking into account that εF >>kBT, we can put the low
integration limit to minus infinity and obtain
∞
x 2e x π2
C el = D(ε F )k B2T ∫ [e dx = D(ε F )k B2T
−∞
x
+1 ]
2
3
Using the density of states for a free electron gas
3N
D(ε F ) =
2ε F
we finally obtain
π 2
T
C el = Nk B where we defined the Fermi
2 TF temperature TF = EF/kB

The total heat capacity, taking into account the electron
and the lattice contribution, equals to:
C = γT + AT 3 For temperatures below both the Debye temperature θ

and Fermi Temperature, TF

Results for simple metals (in units mJ/mol K)
show that the FEFG values are in reasonable
agreement with experiment, but are always
γexpt/ γFEFG = too high:
Metal γexpt γFEG
m*/m
Li 1.63 0.749 2.18

The departure from unity involves three
separate effects:
Na 1.38 1.094 1.26 1. Interaction of conduction electrons with
the periodic potential of the lattice
K 2.08 1.668 1.25
2. Interaction of conduction electrons with
Cu 0.695 0.505 1.38 phonons (phonons can distort the
lattice that the electrons see .electron-
Ag 0.646 0.645 1.00 phonon scattering is common in most
materials)
Au 0.729 0.642 1.14
3. Interaction of the conduction electrons
Al 1.35 0.912 1.48 with themselves (these are negative
charges, which should repel one
another!)

Conductivity – Classical
Electron Theory
Drude model
The simplest treatment of the electrical conductivity was
given by Drude. There are four major assumptions within
the Drude model.
1. Electrons are treated as classical particles within a
free-electron approximation.
2. Electrons move free only between collisions with
scattering centers.

3. An electron experiences a collision, resulting in an
abrupt change in its velocity, with a probability per unit
time 1/t. The time t is therefore an average time between
the two consecutive scattering events. It known as, the
collision time (relaxation time).
4. Electrons are assumed to achieve thermal equilibrium
with their surroundings only through collisions. These
collisions are assumed to maintain local thermo-dynamic
equilibrium in a particularly simple way: immediately after
each collision an electron is taken to emerge with a
velocity that is not related to its velocity just before the
collision, but randomly directed and with a speed
appropriate to the temperature prevailing at the place
where the collision occurred.
According to Ohm's law, the current I flowing in a wire is
proportional to the potential drop V=V2-V1 along the wire:
V = IR.
It is much more convenient to express the Ohm's law in a
form which is independent of the dimensions of the wire
because these factors are irrelevant to the basic physics of
the conduction.
j=σE [1]
The current density j is a vector, parallel to the flow of
charge, whose magnitude is j = I/A.
The current density is frequently express by
j = -nev [2]
n is electrons per unit volume all move with velocity v,

At any point in a metal, electrons are always moving in a
variety of directions with a variety of thermal energies. The
net current density is thus given by Eq.(2), where v is the
average electronic velocity or drift velocity. In the absence
of an electric field, electrons are as likely to be moving in
any one direction as in any other, v averages to zero, and,
as expected, there is no net electric current density. In the
presence of a field E, however, there will be a drift velocity
directed opposite to the field (the electronic charge being
negative), which we can express in the form of Newton’s
Law
dv
m = eE [3]
dt

An electron accelerated by an electric field, will increase
its drift velocity until it encounters a collision. Thus eqn
[3] is modified as follows;
dv
m + γv = eE [4]
dt
The second term in eqn [4] is a damping or friction force.
The electrons are thought to be accelerated until a final
drift velocity vmax is reached. For the steady state case
(v= vmax), dv/dt = 0 and [4] reduces to
γvmax=eE [5]
which yielded eE
γ = [6]
vmax
Substitute [6] back into [4]
dv eE
m + v = eE [7]
dt vmax
The solution to this equation is
   eE  
v = vmax 1 − exp −  t   [8]
   mvmax  
We define the quantity
mvmax
τ= [9]
eE
as the relaxation time (average time between two
consecutive collision).
Rearranging [9] yields
τeE
vmax = [10]
m
Using [10] in [2] resulted in
ne 2τ
j = nevmax = E = σE [11]
m
The conductivity is, therefore, given by
ne 2τ
σ= [12]
m

Conductivity – Quantum
Mechanical Consideration
The situation changes when a field is applied. If the field is in the positive x-
direction, each electron acquires a drift velocity, as given by Eq.(10). Thus the
whole Fermi sphere is displaced to the left, as shown in Fig.3(b). Although the
displacement is very small, and although the great majority of the electrons still
cancel each other pairwise, some electrons - in the shaded crescent in the
figure - remain uncompensated. It is these electrons which produce the
observed current.

The actual picture of electrical conduction is thus quite
different from the classical one. In the classical picture, we
assumed that the current is carried equally by all electrons,
each moving with a very small drift velocity v. In the
quantum-mechanical picture the current is carried only by
very small fraction of electrons, all moving with the Fermi
velocity. The relaxation time is determined only by electrons
at the Fermi surface, because only these electrons can
contribute to the transport properties. Both approaches
lead to the same result, but the latter is conceptually the
more accurate.

Since only electrons at the Fermi surface contribute to the
conductance, we can define the mean free path of
electrons as l=tvF. We can make an estimate of the mean
free path for metal at room temperature. This estimate
gives a value of 100Å. So it is of the order of a few tens
interatomic distances. At low temperatures for very pure
metals the mean free path can be made as high as a few
cm.
We see that between two collisions, the electron travels a
distance of more than 20 times the interatomic distance.
This is much larger than one would expect if the electron
really did collide with the ions whenever it passed them.
This paradox can be explained only using quantum
concepts according to which an electron has a wave
character.
The origin of collision time.
It is well known from the theory of wave propagation in
periodic structures that, when a wave passes through a
periodic lattice, it continues propagating indefinitely without
scattering. Therefore we see that, if the ions form a perfect
lattice, there is no collision at all.
The finiteness of σ must thus be due to the deviation of the

lattice from perfect periodicity; this happens either because
of (1) thermal vibration of the ions, or because of (2) the
presence of imperfections or foreign impurities.

Figure 4 shows the observed curve for Na. At T ~ 0°K,
resistivity, ρ has a small constant value; above that, ρ
increases with T, slowly at first, but afterward ρ increases
linearly with T. The linear behavior continues essentially
until the melting point is reached. This pattern is followed
by most metals, and usually room temperature falls into
the linear range.
Since resistivity is the reciprocal of conductivity, we have
1 m
ρ= = 2 [13]
σ ne τ
We group the deviations from a perfect lattice into two
classes.
a) Lattice vibrations (phonons) of the ions around their
equilibrium position due to thermal excitation of the ions.
b) All static imperfections, such as impurities or crystal
defects. Of this latter group we shall take impurities as an
example.
The total probability for an electron to be scattered in a unit
time is the sum of the probabilities of scattering by phonons
and by impurities. This is because these two mechanisms
are assumed to act independently. Therefore we may write
1 1 1
= + [14]
τ τi τ ph
Substitute [14] into [13] leads to
m m
ρ = ρ i + ρ ph = + [15]
ne 2τ i ne 2τ ph
We see that ρ has split into two terms. A term ρi due to

scattering by impurities, which is independent of T, is called
the residual resistivity. Another term, ρph(T), is due to
scattering by phonons; hence it is temperature dependent.
Sometimes it is called the lattice resistivity. The statement
that ρ can be split into two parts, is known as the
Matthiessen rule.

Hall Effect
• When a current carrying conductor or
semiconductor is placed in a magnetic field
such that the direction of the field is
perpendicular to the direction of the current,
an electric field will be generated in the third
mutually perpendicular direction. This effect
is known as the Hall effect.

Suppose that an electric current Jx is flowing in a wire in
the x-direction, and a magnetic field Bz is applied normal
to the wire in the z-direction.

Ex y
jx
x
z
The drift velocity of the negatively charged electrons

immediately after the electric field is applied. The deflection
in –y direction is caused by the magnetic field. Electrons
accumulated on face of the rod and a positive ion excess is
established on the opposite face.

Ex
+ + + +
+ + + y
jx
x
z
Ey
- - - -
The transverse electric field (Hall Field) just cancels the

Lorentz force due to the magnetic field

Source:Chris Wiebe

Source:Chris Wiebe

Source:Chris Wiebe

Let us now evaluate the Hall field. We start from the
Lorentz force acting on each electron F = -e[E+(v x B)].
We find the equation of motion is written as
vvvv
EEEE
vvvv
BBBB
 d 1  1 
m +  = −e + × 
 dt τ   c 
Let a static magnetic field B lie along the z axis. Thus,

v=(vx, vy, vz), E=(Ex, 0, 0), B=(0, 0, B), Then the component
equations of motion are

 d 1  B  Net force in the –x
m + v x = −e E x + v y  direction
 dt τ   c 
 d 1  B 
m + v y = −e E y + v z  Net force in the –y
 dt τ   c  direction
 d 1
m + v z = −eE z
 dt τ 

In the steady state in static electric field the time derivatives
are zero, so that the drift velocity is
eτ eτ eτ
v x = − E x − ωcτv y ; v y = − E y + ωcτv x ; v z = − E z
m m m
where ωc = eB / mc is the cyclotron frequency

If the current can’t flow out of the metal in the y-direction,
then in the steady state, the velocity of the electrons in the
y-direction must be zero (vy= 0).
eτ mω c v x
v y = − E y + ωcτv x = 0 Ey =
m e
eτ
vx = − Ex
m
therefore
eBτ
E y = −ω cτE x = − Ex
mc

The Hall coefficient is defined by
Ey ne 2τ
RH = using jx = Ex
jx B m
eBτE x / mc 1
RH = − 2 =−
ne τE x B / m nec
Measuring RH is an important way of measuring the
carrier concentration.

Applications of Hall Effect
• The measurement of magnetic field.
Since the Hall voltage is directly proportional to the
strength of the magnetic field, a semiconducting
specimen can be used as a sensor for measuring
the magnetic field. The specimen is placed in a
known magnetic fields and the Hall voltage is
measured for variuos magnetic field strengths. This
calibration can be used to directly measure
unknown magnetic field strength.

• Determination of the sign of the majority
carriers in an extrinsic semiconductor.
We can determine whether a material is n-
type or p-type semiconductor
• The determination of the mobility of the
charge carriers


Chapter6-Free Electron Fermi Gas

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Chapter6-Free Electron Fermi Gas

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Free electron theory

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Conducting solids fall into two main classes; metals and

Semiconductor – Resistivity can be reduced by the addition of

• Na11 ￫ 1s2 2s2 2p6 3s1 Valance electron (loosely bound)

• This valance electron, which occupies the third atomic shell,

Dr. Suriati Paiman, PHY3201 Solid State Physics

– The removal of the valance electrons leaves a

According to Free Electron Fermi Gas this potential is

The main assumptions for metals is as follows:

Dr. Suriati Paiman, PHY3201 Solid State Physics

This theory is called the free electron theory of metals

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

The Schrodinger Equation is a mathematical description

# electron is moving in a wave function

Dr. Suriati Paiman, PHY3201 Solid State Physics

The time independent Schrodinger equation has the following

H is the Hamiltonian for electron = total energy of a system =

If we use the assumptions above, the Schrodinger equation for a

Dr. Suriati Paiman, PHY3201 Solid State Physics

If we use the assumptions above, the Schrodinger equation for a metal is

Dr. Suriati Paiman, PHY3201 Solid State Physics

This is the differential equation for an undamped

Dr. Suriati Paiman, PHY3201 Solid State Physics

1-dimensional potential energy box (or

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

These solutions correspond to standing waves with a

Dr. Suriati Paiman, PHY3201 Solid State Physics

The electronic state in a 1D solid is characterized by

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

The energy of the highest occupied level

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

0.5 ii. E>EF

For a cubic solid of dimension L, the wave function must

Dr. Suriati Paiman, PHY3201 Solid State Physics

To satisfy the boundary condition

and similarly for ky and kz.

Dr. Suriati Paiman, PHY3201 Solid State Physics

It is a measure of where the Fermi energy is at

So, for most metals say at room temperature, not

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

With N = 2  2  to obtain the total number of

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

The specific heat capacity is the heat capacity per unit

Dr. Suriati Paiman, PHY3201 Solid State Physics

Dr. Suriati Paiman, PHY3201 Solid State Physics

The increase ∆U≡U(T)-U(0) in the total energy of a

Dr. Suriati Paiman, PHY3201 Solid State Physics