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The Concepts of Fermi Energy
The Concepts of Fermi Energy
| Krishna Ray|
1
1. History
The difficulty encountered by the electronic theory of metals at that time was due to considering
that electrons were (according to classical statistics theory) all equivalent. In other words it was
believed that each electron contributed to the specific heat an amount of the order of the
Boltzmann constant k. This statistical problem remained unsolved until the discovery of F-D
statistics.
F-D statistics was first published in 1926 by Enrico Fermi and Paul Dirac. F-D statistics was
applied in 1926 by Fowler to describe the collapse of a star to a white dwarf. In 1927
Sommerfeld applied it to electrons in metals and in 1928 Fowler and Nordheim applied it to
field electron emission from metals. Fermi-Dirac statistics continues to be an important part of
physics.
The concepts of Fermi energy and Fermi level are of paramount importance in theories of
electrical conductivity, thermal conductivity, and a wide array of thermodynamical and chemical
phenomena. The Fermi level was named after the famous physicist Enrico Fermi, who had a
significant hand in developing the atom bomb. In thermodynamics and solid-state physics, the
Fermi level is the most energetic state occupied by an electron when the system is in the lowest
energy configuration (i.e. at absolute zero). It is a measure of the energy of the least tightly held
electrons within a solid. It is important in determining the electrical and thermal properties of
solids. The value of the Fermi level at absolute zero (−273.15 °C) is called the Fermi energy
and is a constant for each solid.
Fermi level is the term used to describe the top of the collection of electron energy levels at
absolute zero temperature. It is the energy level at which an average of 50% of available
quantum states are filled by an electron. The Fermi Level relates the probable location of
electrons in a band diagram. In a band diagram of a substance (usually a semiconductor) the
Fermi Level for Intrinsic, p-type and n-type materials
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Fermi Level tells the average location of electron. For metals the Fermi Level lies in the
conduction band and in insulators, the Fermi level lies between, and far from the bands and for
semiconductors the Fermi Level lies in the band gap.
Figure 1: The energy arrangement in atoms. Figure 2: Fermi Energy Level for Different Materials
The Fermi level changes as the solid is warmed and as electrons are added to or withdrawn from
the solid. In doped semiconductors, p-type and n-type, the Fermi level is shifted by the
impurities, illustrated by their band gaps. Each of the many distinct energies with which an
electron can be held within a solid is called an energy level. According to the laws of quantum
mechanics, each energy level can accommodate only a limited number of electrons. The Fermi
level is any energy level having the probability that it is exactly half filled with electrons. Levels
of lower energy than the Fermi level tend to be entirely filled with electrons, whereas energy
levels higher than the Fermi tend to be empty.
In quantum mechanics, a group of particles known as fermions (for example, electrons, protons
and neutrons are fermions) obey the Pauli exclusion principle, which states that no two fermions
can occupy the same quantum state. The states are labeled by a set of quantum numbers. In a
system containing many fermions (like electrons in a metal) each fermion will have a different
set of quantum numbers. Considering electrons as fermions, at absolute zero they pack into the
lowest available energy states and build up a "Fermi sea" of electron energy states. The Fermi
level is the surface of that sea at absolute zero where no electrons will have enough energy to rise
above the surface. The concept of the Fermi energy is a crucially important concept for the
understanding of the electrical and thermal properties of solids. Both ordinary electrical and
thermal processes involve energies of a small fraction of an electron volt. But the Fermi energies
of metals are on the order of electron volts. This implies that the vast majority of the electrons
cannot receive energy from those processes because there are no available energy states for them
to go to within a fraction of an electron volt of their present energy. Limited to a tiny depth of
energy, these interactions are limited to "ripples on the Fermi sea".
Fig: The carrier distribution of an intrinsic material. Here, E i = E F , is the Fermi level of the intrinsic material.
Acceptor Donor
state state
Fig: The carrier distribution of a n-type material. Here, E F , is closed to the conduction band.
Fig: The carrier distribution of a n-type material. Here, E F , is closed to the valance band.
by an electron. The Fermi energy level, E F , is the energy at which the probability of occupancy
is exactly 𝟏𝟏�𝟐𝟐for temperatures greater than zero. The Fermi function is given by,
Here, E F is the Fermi energy of the electrons in the solid, k (=1.38062´10-23 J K-1) is the
Boltzmann’s constant and T is the temperature (kT is the thermal energy, 25 meV at room
temperature).
In a band diagram, the position of the Fermi level determines which carrier dominates. If the
semiconductor contains more electrons than holes then it’s an n-type material and the Fermi level
is positioned above mid gap. If holes are more abundant than electrons then it’s a p-type
material and E F is positioned below mid gap. When the electron and hole concentrations are
approximately equal or in an intrinsic material, E F is positioned at mid gap. The Fermi function,
or level, also varies with temperature and carrier concentration.
1
• The probability an energy state is occupied: 𝑓𝑓(𝐸𝐸 ) = (𝐸𝐸−𝐸𝐸 𝐹𝐹 )
�
1+𝑒𝑒 𝑘𝑘𝑘𝑘
• The probability an energy state is empty: [1- f (E)]
• The Fermi function at E = EF : f (E) = 1�2
• The Fermi function is simply a mathematical 0 < f (E) < 1
function and has no units
An energy level may contain several sublevels, all with the same energy. Each sublevel is called
a "state," and can be occupied by exactly one electron. Suppose there are N allowed states at
energy E. Then the probability of finding an occupied state at energy E is N×F(E). In
continuous-band theory we represent N as a density of states. The density of states reveals how
the allowed sublevels are spread out across energy bands in a specific material.
In a semiconductor, not every energy level is allowed. For example, there are no allowed states
within the forbidden gap. To make use of the Fermi function, we need another function that has
units of states per energy level per volume. In a solid with numerous atoms, a large number of
states appear at energy levels very close to each other. We approximate these states as a
continuous "band" and imagine that an "energy level" is a vanishingly small energy interval of
width dE. The density of states, N(E) is the fraction of all allowed states that lie within E and
E+dE. The Fermi function tells us the probability that a state is occupied. The density of states
complements the Fermi function by telling us how many states actually exist in a particular
material.
To begin to understand the meaning of the distribution function and the Fcrmi energy, we can
plot the distribution function versus energy.
• E < EF [At T = 0 K]
Semiconductor energy level (E) is lower than Fermi energy level E F
1 1
𝑓𝑓(𝐸𝐸 ) = =
1 + 𝑒𝑒
(𝐸𝐸−𝐸𝐸𝐹𝐹 )�
𝑘𝑘𝑘𝑘
1 + 𝑒𝑒 −∝
1
𝑓𝑓(𝐸𝐸 ) = =1
1+0
∴ At T = 0 K, the lower states of E F are always filled.
• E > EF [At T = 0 K]
Semiconductor energy level (E) is higher than Fermi energy level E F
1 1
𝑓𝑓(𝐸𝐸 ) = =
1 + 𝑒𝑒
(𝐸𝐸−𝐸𝐸𝐹𝐹 )�
𝑘𝑘𝑘𝑘
1 + 𝑒𝑒 +∝
1
𝑓𝑓(𝐸𝐸 ) = =0
1+∝
Field
states
Empty
States
Fig: Fermi Level, Fermi Function and Electron Occupancy of Localized Energy States at T=0K
1 1
𝑓𝑓(𝐸𝐸 ) = =
1+1 2
∴ At any temperature, at Fermi Level the probability of finding electron is 50%.
Fig: Fermi Level, Fermi Function and Electron Occupancy of Localized Energy States at any Temperature
Throughout nature, particles seek to occupy the lowest energy state possible. Therefore electrons
in a solid will tend to fill the lowest energy states first. Electrons fill up the available states like
water filling a bucket, from the bottom up. At T=0, every low-energy state is occupied, right up
to the Fermi level, but no states are filled at energies greater than E F .
Figure 1: Illustration of the Fermi function for zero temperature. All electrons are stacked neatly below the Fermi level.
For T > 0, some electrons can be excited into higher-energy states. This is similar to a bucket of
hot water. Most of the water molecules stick around the bottom of the bucket. The Fermi level is
like the water line. A fraction of water molecules are excited and drift above the water line as
vapor, just as electrons can sometimes drift above the Fermi level.
Figure: Illustration of the Fermi function for temperatures above zero. Some electrons drift above the Fermi level. Their density
at higher energies is proportional to the Fermi function.
The plot of the distribution function versus energy shows a rectangular shaped distribution at
T=0K. Therefore, at T = 0 K, every available energy state up to E F is filled and with electrons
and all states above EF is empty.
f(E)
EF
E
Figure: Fermi-Dirac Distribution Function
At temperature higher than 0 K, some probability exists for status above the Fermi Level to be
filled. Thus, at T = 300 K, there is some probability f(E) that status above E F are filled and there
is a corresponding probability [1- f (E)] that states below E F are empty.
One feature that is very important about the Fermi-Dirac distribution is that it is symmetric about
the chemical potential. F(E) is the probability of occupancy of an available state at E. Thus if
there is no available state at E, there is no possibility of finding an electron there. We can best
visualize the relation between f(E) and band structure by turning the f(E) vs. E diagram on its
side so that the E-scale corresponds to the energies of the band diagram. For intrinsic material,
the concentration of holes in the valance band is equal to the concentration of electrons in the
conduction band. Therefore, the Fermi level E F must lie at the middle of the band gap in the
intrinsic material. Since f(E) is symmetrical above E F , the electron probability “tail” of f(E)
extending into the conduction band is symmetrical with the hole probability tail [1- f (E)] in the
valence band. The distribution has values within the band gap between E V and E C but there is no
energy status available, and electrons occupancy results from f(E) in this range.
In n-type material there is a high concentration of electron in the conduction band compared
with the hole concentration in the valence band. Thus in n-type material the distribution function
f(E) must be above its intrinsic position on the energy scale. Since, f(E) retains in its shape for a
particular temperature, the larger concentration of electrons at E C in n-type material implies a
correspondingly smaller hole concentration at E V . We obtain that the value of f(E) for each
energy level in conduction band increases as E F moves closer to E C . Thus energy difference
(E C - E F ) gives a measure of n i .
For p-type semiconductors the behavior is similar, but the other way around. For p-type material
the Fermi level lies near the valence band such that the [1- f (E)] tail below EV is larger than the
f(E) tail above EC. The value of (EF - EC) indicates how strongly p-type the material is.
In a solid semiconductor at thermal equilibrium, every mobile electron leaves behind a hole in
the valence band. Since holes are also mobile, we need to account for the density of "hole states"
that remain in the valence band. Because a hole is an unoccupied state, the probability of a
mobile hole existing at energy E is 1-F(E).
Figure 4:
Figure: The density of mobile electrons is shown in the conduction band. The corresponding density of mobile holes is shown in
the valence band.
Now,
1
𝑁𝑁(𝐸𝐸) ∝ 𝐸𝐸 �2
∴ 𝑁𝑁(𝐸𝐸) ↑ → 𝐸𝐸 ↑
∴ 𝑓𝑓(𝐸𝐸) ↓ → 𝐸𝐸 ↑
f(E)N(E) decreases rapidly above E C , and very few electrons occupy energy states far above the
conduction band edge.
Figure: Tthe density of states. For an intrinsic semiconductor the Fermi energy is in the middle of the band gap and n=p.
Here,
Fermi Level for Intrinsic, p-type and n-type materials
13
3�
2𝜋𝜋𝑚𝑚𝑛𝑛∗ 𝑘𝑘𝑘𝑘 2
𝑁𝑁𝑐𝑐 = 2 � �
ℎ2
And,
3�
2𝜋𝜋𝑚𝑚𝑝𝑝∗ 𝑘𝑘𝑘𝑘 2
𝑁𝑁𝑣𝑣 = 2 � �
ℎ2
Here,
𝑚𝑚𝑛𝑛∗ = effective mass of electron
and, 𝑚𝑚𝑝𝑝∗ = effective mass of hole
n-type
Intrinsic
p-type
Figure: Density of states, occupancy factors and carrier contributions for different positions of the Fermi energy.
where E i is called intrinsic (Fermi) level. This level is in the middle of the bandgap,
displaced from it by a term which can usually by neglected.
The distribution (with respect to energy) of electrons in the conduction band is given by the
density of allowed quantum states times the probability that a state is occupied by an electron.
This statement is written in equation form as,
𝒏𝒏(𝑬𝑬) = 𝒈𝒈𝒄𝒄 (𝑬𝑬)𝒇𝒇𝑭𝑭 (𝑬𝑬)
where 𝑓𝑓𝐹𝐹 (𝐸𝐸)is the Fermi-Dirac probability function and 𝑔𝑔𝑐𝑐 (𝐸𝐸) is the density of quantum states in
the conduction band.
Fermi Level for Intrinsic, p-type and n-type materials
15
Similarly, the distribution (with respect to energy) of holes in the valence bend is the density of
allowed quantum states in the valence band multiplied by the probability that a state is not
occupied by an electron. We may express this as,
Figure : (a) Density of states functions, Fermi-Dirac probability function, and areas representing electron and hole
concentrations for the case when E F is near the midgap energy; (b) expanded view near the cunduction band energy;
and (c) expanded view near the valence band energy.
Figure(a) shows a plot of the density of states function in the conduction band 𝒈𝒈𝒄𝒄 (𝑬𝑬), the density
of states function in the valence band 𝒈𝒈𝒗𝒗 (𝑬𝑬), and the Fermi-Dirdc probability function for
T >0K when E f is approximately halfway between E c and E v ,. If we assume, for the moment,
that the electron and hole effective masses are equal, then 𝒈𝒈𝒄𝒄 (𝑬𝑬)and 𝒈𝒈𝒗𝒗 (𝑬𝑬) are symmetrical
functions about the midgap energy. The function, f F (E) for E > E F is symmetrical to the
function 1 - f F (E) for E < E F about the energy E = E F . This also means that the function f F (E)
for E = E F + dE is equal to the function 1 -f F (E)fo r E = E F - d E .
The Fermi energy level changes as dopant atoms are added. In general, both donors and
acceptors are present in a piece of a semiconductor although one outnumbers the other one.
When E F > E Fi , the electron concentration is larger than the hole concentration, and
when E F < E Fi . the hole concentration is larger than the electron concentration..
Figure: Density of states functions, Fermi-Dirac probability function and areas representing electron and hole concentrations
for the case when E F is (a) above and (b) below the intrinsic Fermi energy.
References
Books-
• Fundamentals of classical and statistical thermodynamics By Bimalendu Narayan Roy
• System Integration By Kurt Hoffmann
• On the Theory of Quantum Mechanics By Dirac, P. A. M. (1926)
• Solid State Electronics Devices (Sixth edition) By Ben G. Streetman , SanjayKumar Banerjee
• Semiconductor Physics And Devices (3rd edition) By J. Neamen
• Physics and Technology of Semiconductor Devices By A.S. Grove (1967)
• Mobility of holes and electrons in high electric fields By E.J. Ryder (1953)
• Introduction to Solid State Physics By C. Kittel (1986)
Websites-
Digitally signed by
Krishna Ray
DN: cn=Krishna
Ray, o=Sync, ou=1,
Fermi Level for Intrinsic, p-type and n-type materials
email=krishna_ray
@live.com, c=BD
Date: 2010.08.28
19:06:37 +06'00'