Fermi energy and its importance

Fermi level is the maximum energy level up to which the electrons can be filled at 0 K. it is the energy
of a state which the probability of electron occupation is half at any temperature above 0 K. The
important features of Fermi energy level are:

1. Fermi level acts as a reference level that separates the vacant and filled states at 0 K.

2. At absolute zero, all the quantum states below EF are occupied while all the quantum states having
energies greater than E F are unoccupied.

3. When the temperature is increased, few electrons gain the thermal energy and jump to the higher
energy levels.

4. Fermi energy denotes the maximum kinetic energy that electrons can possess at 0 K.

5. Fermi energy levels are used to explain the flow of electrons when two metals are brought into
contact.

Total energy

The total energy ‘Eo’ of all the ‘N’ number of electrons is calculated by adding up the energies of the
individual electrons. For ‘N’ electrons, the number of filled energy levels is ‘N/2’ because each level can
be occupied by two electrons with opposite spins. So, we can write,

𝑛=𝑁/2

𝐸𝑜 = 2 ∑ 𝐸𝑛
𝑛=1

Here, a factor ‘2’ appears because each level contains 2 electrons with equal energy. Therefore using,

ℎ2 𝑛 2
𝐸𝑛 = ( ) , we get,
8𝑚 𝐿

𝑛=𝑁/2
ℎ 1 2
𝐸𝑜 = 2 ( ) ∑ 𝑛2
8𝑚 𝐿
𝑛=1
 1 1 3
Since, ∑n=x 2
n=1 n = x(2 x 2  3 x  1) ≈ 3
x for, x ≫ 1 , therefore,
6

𝑛=𝑁/2
1 𝑁 3
2
∑ 𝑛 ≈ ( )
3 2
𝑛=1

Hence, the expression of total energy becomes,

ℎ2 1 2 1 𝑁 3 1 ℎ2 𝑁 2
𝐸𝑜 = 2 ( ) ( ) = 𝑁
8𝑚 𝐿 3 2 3 32𝑚𝐿2

Therefore,

1
𝐸𝑜 = 𝑁 𝐸𝐹
3

Therefore, the average kinetic energy (𝐸̅ ) of all the electrons at T = 0 K (for 1-D metal lattice), will be

𝐸𝑜 1
𝐸̅ = = 𝐸𝐹
𝑁 3

Fermi – Dirac Distribution Function (or Occupational Probability)

In Fermi Dirac distribution all the particles in the system are indistinguishable and it obeys Pauli’s
exclusive principle (i.e., not more than two electrons can occupy the same energy level) on filling the
particles in the energy levels. This is mainly applicable for fermions (Fermions are the particles with odd
half integral spins (0,1/2,3/2,5/2,…..). It means that the distribution statistics obeyed by quantum
particles like electrons is called the Fermi–Dirac statistics. The Fermi–Dirac distribution function f(E) is
an expression for the distribution of electrons among the energy levels as a function of temperature and
gives the probability of finding an electron in a particular energy state of energy E as

1
f (E) 
 E  EF 
1  exp  
 kT 
Where EF - Fermi energy (highest energy level of an electron)
k - Boltzmann’s constant
T - Absolute temperature
Because Fermi–Dirac distribution function gives, the probability of finding (occupying) an electron in a
particular energy state of energy E, that is why it is also known as occupational probability.

Variation of Fermi function with Temperature

The Fermi function varies with temperatures is discussed below:
(I) At T=0K and E< EF
1 1  1 1 
f (E)   1   e      0 
1  exp    1  0  e  
f(E)=1=100%
It means that there is 100% probability for the electrons to occupy the energy level below the Fermi
energy level.

(II) At T=0 K and E> EF

f (E) 
1

1 1
 0
1  exp   1   

 e    

f(E)=0=0%
It means that there is 0% probability for the electrons to occupy the energy level above the Fermi energy
level.
(III) At T>0 K and E=EF
 f (E) 
1

1

1  exp 0 1  1 2
1
 
 e0  1

f (E)=0.5=50%
It means that 50% probability for the electrons to occupy the Fermi energy level. That is the energy
levels above Fermi level are empty and below Fermi level are filled.

Fermi level, Fermi Energy and their importance

Fermi energy level is defined as the highest reference level of a particle at absolute 0 K.
Importance: It is the reference energy level which separates the filled energy levels and vacant energy
levels.
Fermi energy (EF) : The Fermi energy is the maximum energy of the quantum state corresponding to
Fermi energy level at absolute zero
Importance: Fermi energy determines the energy of the particle at any temperature.

Properties of Fermi Function

1. It is applicable for all metals, semiconductors and insulators.
2. In semiconductors the probability of electron occupying an energy level Ei is
1
f e ( Ei ) 
 E  EF 
1  exp  i 
 kT 
3. In semiconductors the probability of hole occupying an energy level Ei is
1
f h ( Ei )  1  f e ( Ei )  1 
 E  EF 
1  exp  i 
 kT 
 E  EF 
1  exp  i  1
i.e. f h ( Ei )   kT 

1
 E  EF   E  Ei 
1  exp  i  exp  F  1
 kT   kT 
4. At T=0 K , if E< EF , f(E)=1=100%
5. At T=0 K , if E> EF , f(E)=0=0%
6. At T>0 K , if E= EF , f(E)=0.5=50% .
Density of States

The Fermi function gives us only the probability of occupation of a quantum energy state by a single
electron. The ability of a metal to conduct electricity depends on how many quantum energy states are
available to for electrons and what are the energies of those states. In physics, a quantum state is
characterized by a set of quantum numbers and represented by an Eigen function. It is not an easy task to
list the energies of so many states individually, instead of this; we find the number of states in a unit
volume of the sample having energies in the range E and E+dE. We write this number as D(E)dE, where
D(E) is called the density of states at energy E. The unit of D(E) is states per cubic meter per electron
volt (m-3eV-1).

We know that the permitted energy levels for electrons in a solid material will be in terms of bands. Let
the energy band be spread in an energy interval between E1 and E2 in the material. Consider an
infinitesimal small increment dE at arbitrary energy value E in the band. Since dE is an infinitesimally
small increment in E, we can assume that D(E) remains constant between E and E+dE.

The density of states is defined as the number of energy states present in a unit energy interval. It is
denoted by D(E) and given by,

𝑑𝑁
𝐷 (𝐸 ) =
𝑑𝐸

Where, dN represents the number of energy states present in the energy interval E and E+dE. Since each
energy level can accommodate 2 electrons, the actual density of states will be twice the above value, i.e.

𝑑𝑁
𝐷 (𝐸 ) = 2
𝑑𝐸

Density of States in 1-D

The density of states is defined as the number of energy states present in a unit energy interval. It is
denoted by D(E) and given by,

𝑑𝑁
𝐷 (𝐸 ) =
𝑑𝐸
Where, dN represents the number of energy states present in the energy interval E and E+dE. Since each
energy level can accommodate 2 electrons, the actual density of states will be twice the above value, i.e.

𝑑𝑁
𝐷 (𝐸 ) = 2
𝑑𝐸

1/2
ℎ2 𝑁 2 1 ℎ2
As we know, 𝐸 = ( ) , therefore, 𝑁 = (8𝑚𝐿2 𝐸 )
8𝑚 𝐿

So,

𝑑𝐸 ℎ2 𝑁
=
𝑑𝑁 4 𝑚 𝐿2

Therefore,

𝑑𝑁 1 8𝑚𝐿
𝐷 (𝐸 ) = 2 = 2 = 2
𝑑𝐸 𝑑𝐸 ℎ 𝑁
𝑑𝑁

Substituting the expression of (1/N) in above equation, we get,

4 𝐿 𝑚 1/2
𝐷 (𝐸 ) = ( )
ℎ 2𝐸

The plot of D(E) versus E is shown in fig (a). All energy levels below EF are completely filled and all
those above is are totally empty at 0 K temperature. Thus, at 0 K, the Fermi energy level divides or
separates the filled energy levels from unfilled energy levels.
Density of States in 2-D

In case of two dimensions, every point in the N-space will have fixed values of (Nx, Ny) and hence,
energy in N-space will be,

ℎ2
𝐸= (𝑁 2 + 𝑁𝑦2 )
8 𝑚 𝐿2 𝑥

Or,

2
8𝑚 𝐿2 𝐸
𝑁𝑥2 + 𝑁𝑦2 = (√ )
ℎ2
 8 𝑚 𝐿2 𝐸
The above equation represents the equation of a circle: x2 +y2 = r2 with radius, 𝑟 = √ in a two
ℎ2

dimensional N-space with axis Nx and Ny as shown in the figure below:

In this case, the total number of states N is the defined as the area of circle with radius ‘r’ in N-space
with axis Nx and Ny. However, number states cannot have negative value. Therefore, the valid states are
represented by the shaded portion (grey) i.e. first quadrant which is one fourth of the area of circle.
Hence, N will be,

1 2
𝑁= 𝜋𝑟
4

1 8 𝑚 𝐿2 𝐸
𝑁= 𝜋
4 ℎ2

Considering the unit area of the solid material, i.e. area = L2 = 1, we get,

𝑚𝐸
𝑁 = 2𝜋
ℎ2

Now,

𝑑𝑁 𝑚
= 2𝜋 2
𝑑𝐸 ℎ
Now, as per definition, density of states is given by,

𝑑𝑁 𝑚
𝐷 (𝐸 ) = 2 = 4𝜋 2
𝑑𝐸 ℎ

The above equation concludes that, the density of states in 2-D, does not depend upon the energy as
shown in fig (b). As the top of the energy gap is reached, there are a significant number of available
states. Taking into account the other energy levels in the quantum well, the density of states becomes the
stair case like function, as shown in figure below:

Density of states in 3-D:

The Fermi function gives us only the probability of occupation of a quantum energy state by a single
electron. The ability of a metal to conduct electricity depends on how many quantum energy states are
available to for electrons and what are the energies of those states. In physics, a quantum state is
characterized by a set of quantum numbers and represented by an Eigen function. It is not an easy task to
list the energies of so many states individually, instead of this; we find the number of states in a unit
volume of the sample having energies in the range E and E+dE. We write this number as D(E)dE, where
D(E) is called the density of states at energy E. The unit of D(E) is states per cubic meter per electron
volt (m-3eV-1).

We know that the permitted energy levels for electrons in a solid material will be in terms of bands. Let
the energy band be spread in an energy interval between E1 and E2 in the material. Consider an
infinitesimal small increment dEat arbitrary energy value E in the band. Since dE is an infinitesimally
small increment in E, we can assume that D(E) remains constant between E and E+dE.

Mathematically, density of states is represented by D(E), where,

dN
D(E) = 2
dE

h2
The equation (2), E = 8 m L2 (Nx2 + Ny2 + Nz2 ), can be re-written as,

2
8 m L2 (3)
(Nx2 + Ny2 + Nz2 ) = (√ E)
h2

8 m L2
The above expression (3) represents the equation of a sphere with radius R = √ E, in 3-D N-space
h2

with perpendicular axis Nx, Ny and Nz. Therefore, the number of states in sphere = numerical value of
the volume expressed in units of cubes of lattice parameters. Note that every point in the N-space will
have a fixed value of (Nx, Ny, Nz)and hence the different points in the N-space will represent different
energy state of the electron inside the metal. Furthermore, as the quantum number N x, Ny and Nz can
only have positive integral values, so the points corresponding to the allowed energy states for the
electron inside the metal can exist only in the positive octant of the sphere in N-space, i.e. the number of
energy states must be equal to the 1/8th of the volume of sphere with radius R or volume of the positive
octant of the sphere with radius R in N-space. i.e.
 1 1 4
N= volume of sphere with radius R = × πR3
8 8 3

3
1 4 8 m L2
N = × π(√ E)
8 3 h2

π 3
8 m 3/2 3/2
N= ×L ( 2 ) E
6 h

For cubical metal lattice with unit volume, Volume of lattice = L3 = V

π 8 m 3/2
N= V ( 2 ) E 3/2
6 h

On differentiating above equation, we get,

8π 3
dN = 3
V(2 m )3/2 E1/2 dE
6h 2

dN 2 π
= 3 V(2 m )3/2 E1/2
dE h
 dN
Now, as per definition, D(E) = 2
dE

2π
D(E) = 2 × V(2 m )3/2 E1/2
h3

Therefore,

4π 3/2 1/2
2 m 3/2 1/2
D(E) = 3 V(2 m ) E = 4 πV ( 2 ) E
h h

In ℏ, form (i.e. ℏ = h/2π)

V 2 m 3/2 1/2
D(E) = ( ) E
2π2 ℏ2

The above express can be written as,

V 2 m 3/2 1/2
D(E) dE = ( ) E dE
2π2 ℏ2

The above equation shows that the density of states D(E) is a parabolic function of energy E as shown in
the figure below,
It is obvious that D(E) increases with increase in crystal’s volume. The number of energy states present
in unit volume having energy values lying between E and E+dE (called energy density of energy states)
can be obtained by putting V = L3 = 1 in equation (7),

1 2 m 3/2 1/2 2 m 3/2 1/2

D(E) dE = ( ) E dE = 4 π ( 2 ) E dE
2π2 ℏ2 h

Fermi energy in 3-D and Density of electrons:

Let us consider, the occupancy probability of allowed energy states at absolute zero temeperature i.e.
T=0 K. To add one electron to the allowed energy states, first, ground state is to be filled then the higher
energy states (i.e. excited states). Similarily, until the last electron in the metal is added at a level above
which all the other states are unoccupied. This level is defined as the Fermi level and is denoted by E F(0)
at T = 0 K i.e. Fermi level is the top most energy level filled with electrons at 0 K temeperature. In other
words, the Fermi level EF(0) divides or seperates the filled and empty energy states at zero kelvin. The
energy of the Fermi level is called Fermi energy. To find out the expression of Fermi energy in 3-D, the
expression for the total number of electrons inside the metal is to be formulated.

The total number of energy states in the metal wih energy ≤ E, is given by

π 8 m 3/2
N= V ( 2 ) E 3/2
6 h

Since, every energy level can occupy two electrons, so total number of electrons in the energy states
lying between E = 0 to E = EF(0) at 0 K, will be,

π 8 m 3/2
Ne = 2N = 2 × V ( 2 ) EF(0) 3/2
6 h

π 8 m 3/2
Ne = V ( 2 ) EF(0) 3/2
3 h

Therefore, the numberdensity of electron per unit volume is,

 Ne π 8 m 3/2
n= = ( 2 ) EF(0) 3/2
V 3 h

Hence, Fermi energy can be expressed as,

3/2
3/2 3n h2
EF(0) = ( )
π 8m

3/2
3/2 3n h2
EF(0) = ( )
π 8m

3n 2/3 h2 ℏ2
EF(0) = ( ) ( ) = (3 n π2 )2/3 ( )
π 8m 2m

So, the Fermi energy may be calculated simply by knowing the electron concentration ‘n’. The
calculated value of EF(0) is the order of 5 eV. This is a special feature of quantum mechanics. According
to classical theory, the elctrons have zero energy at absolute zero.

Variation of Fermi energy with temperature:

Fermi energy decreases with increase in temperature. An approximate relationship between Fermi
energy at a temperature ‘T’ and Fermi energy at T = 0, represented by E F(T) and EF(0) respectively is
given by.

2
π2 k T
EF(T) = EF(0) [1 − ( ) ]
12 EF(0)

At room temerature, i.e. T = 300 K, for E F(0) = 1.7 eV (i.e. metals) the value of the ratio:

kT
= 0.015
EF(0)

Therefore, it follows that the temperature dependency of Fermi energy is very slight and for all practical
puposes (at room temeperature), we can assume at T> 0 K, Fermi level no longer represents the top-
most filled energy.
Average Kinetic energy at zero kelvin:

The average kinetic energy of an electron at a temeprature T, is given by,

∞
1
̅
E= ∫ E. D(E). F(E)dE
Ne
0

However, at T = 0 K, the maximum energy of electron is E F(0) and F(E) = 1, therefore,

EF(0)
1
̅=
E ∫ E. D(E) dE
Ne
0

Substituting the expression of D(E), we get,

EF(0)
1 V 2 m 3/2 1/2
̅
E= ∫ E ( ) E dE
Ne 2π2 ℏ2
0

EF(0)
1 V 2 m 3/2 1 V 2 m 3/2 2 5/2
̅=
E ( ) ∫ E 3/2
dE = ( ) E
Ne 2π2 ℏ2 Ne 2π2 ℏ2 5 F(0)
0

V 2 m 3/2
Now,substituting,Ne = ( ) EF(0) 3/2 in above equation, we get,
3 π2 ℏ2

V 2 m 3/2 2 5/2
2( 2 ) EF(0) 3
E = 2π ℏ 3/2 5
̅ = EF(0)
V 2m 5
( ) EF(0) 3/2
3 π2 ℏ2

3
̅
E = EF(0)
5