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The Fermi level is the total chemical potential for electrons (or electrochemical potentialfor electrons) and is usually denoted byµ or
EF.[1] The Fermi level of a body is a thermodynamic quantity, and its significance is the thermodynamic work required to add one
electron to the body (not counting the work required to remove the electron from wherever it came from). A precise understanding of
the Fermi level—how it relates toelectronic band structurein determining electronic properties, how it relates to the voltage and flow
of charge in an electronic circuit—is essential to an understanding of solid-state physics.
In band structure theory, used in solid state physics to analyze the energy levels in a solid, the Fermi level can be considered to be a
hypothetical energy level of an electron, such that at thermodynamic equilibrium this energy level would have a 50% probability of
being occupied at any given time. The position of the Fermi level with the relation to the band energy levels is a crucial factor in
determining electrical properties. The Fermi level does not necessarily correspond to an actual energy level (in an insulator the Fermi
level lies in the band gap), nor does it require the existence of a band structure. Nonetheless, the Fermi level is a precisely defined
thermodynamic quantity, and differences in Fermi level can be measured simply with avoltmeter.
Contents
The Fermi level and voltage
The Fermi level and band structure
Local conduction band referencing, internal chemical potential and the parameter
ζ
The Fermi level and temperature out of equilibrium
Technicalities
Terminology problems
Fermi level referencing and the location of zero Fermi level
Why it is not advisable to use "the energy in vacuum" as a reference zero
Discrete charging effects in small systems
Footnotes and references
In fact, the quantity called voltage as measured in an electronic circuit has a simple A voltmeter measures differences in
relationship to the chemical potential for electrons (Fermi level). When the leads of a Fermi level divided by electron
charge.
voltmeter are attached to two points in a circuit, the displayed voltage is a measure
of the total work transferred when a unit charge is allowed to move from one point
to the other. If a simple wire is connected between two points of differing voltage (forming a short circuit), current will flow from
positive to negative voltage, converting the available work into heat.
The Fermi level of a body expresses the work required to add an electron to it, or equally the work obtained by removing an electron.
Therefore, VA − VB, the observed difference in voltage between two points, A and B, in an electronic circuit is exactly related to the
corresponding chemical potential difference, µA − µB, in Fermi level by the formula[4]
From the above discussion it can be seen that electrons will move from a body of high µ (low voltage) to low µ (high voltage) if a
simple path is provided. This flow of electrons will cause the lower µ to increase (due to charging or other repulsion effects) and
likewise cause the higher µ to decrease. Eventually, µ will settle down to the same value in both bodies. This leads to an important
fact regarding the equilibrium (off) state of an electronic circuit:
This also means that the voltage (measured with a voltmeter) between any two points will be zero, at equilibrium. Note that
thermodynamic equilibrium here requires that the circuit be internally connected and not contain any batteries or other power
sources, nor any variations in temperature.
The Fermi–Dirac distribution, , gives the probability that (at thermodynamic equilibrium) a state having energy ϵ is occupied by
an electron:[5]
Here, T is the absolute temperature and k is Boltzmann's constant. If there is a state at the Fermi level ϵ
( = µ), then this state will have
a 50% chance of being occupied. The distribution is plotted in the left figure. The closer f is to 1, the higher chance this state is
occupied. The closer f is to 0, the higher chance this state is empty
.
The location of µ within a material's band structure is important in determining the electrical behaviour of the material.
In an insulator, µ lies within a large band gap, far away from any states that are able to carry current.
In a metal, semimetal or degenerate semiconductor, µ lies within a delocalized band. A large number of states
nearby µ are thermally active and readily carry current.
In an intrinsic or lightly doped semiconductor , µ is close enough to a band edge that there are a dilute number of
thermally excited carriers residing near that band edge.
In semiconductors and semimetals the position of µ relative to the band structure can usually be controlled to a significant degree by
doping or gating. These controls do not change µ which is fixed by the electrodes, but rather they cause the entire band structure to
shift up and down (sometimes also changing the band structure's shape). For further information about the Fermi levels of
semiconductors, see (for example) Sze.[6]
Local conduction band referencing, internal chemical potential and the parameterζ
If the symbol ℰ is used to denote an electron energy level measured relative to the energy of the edge of its enclosing band, ϵC, then
in general we have ℰ = ϵ – ϵC. We can define a parameterζ[7] that references the Fermi level with respect to the band edge:
The band theory of metals was initially developed by Sommerfeld, from 1927 onwards, who paid great attention to the underlying
thermodynamics and statistical mechanics. Confusingly, in some contexts the band-referenced quantity ζ may be called the Fermi
level, chemical potential, or electrochemical potential, leading to ambiguity with the globally-referenced Fermi level. In this article,
the terms conduction-band referenced Fermi level or internal chemical potentialare used to refer to ζ.
The value of ζ at zero temperature is widely known as the Fermi energy, sometimes written ζ0. Confusingly (again), the name Fermi
energy sometimes is used to refer toζ at non-zero temperature.
The quasi-equilibrium approach allows one to build a simple picture of some non-equilibrium effects as the electrical conductivityof
a piece of metal (as resulting from a gradient of μ) or its thermal conductivity (as resulting from a gradient in T). The quasi-μ and
quasi-T can vary (or not exist at all) in any non-equilibrium situation, such as:
Technicalities
Terminology problems
The term, Fermi level, is mainly used in discussing the solid state physics of electrons in semiconductors, and a precise usage of this
term is necessary to describe band diagrams in devices comprising different materials with different levels of doping. In these
contexts, however, one may also see Fermi level used imprecisely to refer to the band-referenced Fermi level, µ − ϵC, called ζ above.
It is common to see scientists and engineers refer to "controlling", "pinning", or "tuning" the Fermi level inside a conductor, when
they are in fact describing changes in ϵC due to doping or the field effect. In fact, thermodynamic equilibrium guarantees that the
Fermi level in a conductor is always fixed to be exactly equal to the Fermi level of the electrodes; only the band structure (not the
Fermi level) can be changed by doping or the field effect (see also band diagram). A similar ambiguity exists between the terms,
chemical potential and electrochemical potential.
It is also important to note that Fermi level is not necessarily the same thing as Fermi energy. In the wider context of quantum
mechanics, the term Fermi energy usually refers to the maximum kinetic energy of a fermion in an idealized non-interacting, disorder
free, zero temperature Fermi gas. This concept is very theoretical (there is no such thing as a non-interacting Fermi gas, and zero
temperature is impossible to achieve). However, it finds some use in approximately describing white dwarfs, neutron stars, atomic
nuclei, and electrons in a metal. On the other hand, in the fields of semiconductor physics and engineering, Fermi energy often is
[9]
used to refer to the Fermi level described in this article.
Fermi level referencing and the location of zero Fermi level
Much like the choice of origin in a coordinate system, the zero point of ener
gy can be defined arbitrarily. Observable phenomena only
depend on energy differences. When comparing distinct bodies, however, it is important that they all be consistent in their choice of
the location of zero energy, or else nonsensical results will be obtained. It can therefore be helpful to explicitly name a common point
to ensure that different components are in agreement. On the other hand, if a reference point is inherently ambiguous (such as "the
vacuum", see below) it will instead cause more problems.
A practical and well-justified choice of common point is a bulky, physical conductor, such as the electrical ground or earth. Such a
conductor can be considered to be in a good thermodynamic equilibrium and so its
µ is well defined. It provides a reservoir of charge,
so that large numbers of electrons may be added or removed without incurring charging effects. It also has the advantage of being
accessible, so that the Fermi level of any other object can be measured simply with a voltmeter
.
In this case one must be precise about the thermodynamic definition of the chemical potential as well as the state of the device: is it
electrically isolated, or is it connected to an electrode?
When the body is able to exchange electrons and energy with an electrode (reservoir), it is described by the grand
canonical ensemble. The value of chemical potentialµ can be said to be fixed by the electrode, and the number of
electrons N on the body may fluctuate. In this case, the chemical potential of a body is the infinitesimal amount of
work needed to increase theaverage number of electrons by an infinitesimal amount (even though the number of
electrons at any time is an integer, the average number varies continuously.):
where F(N, T) is the free energy function of the grand canonical ensemble.
If the number of electrons in the body is fixed (but the body is still thermally connected to a heat bath), then it is in
the canonical ensemble. We can define a "chemical potential" in thiscase literally as the work required to add one
electron to a body that already has exactlyN electrons,[11]
where F(N, T) is the free energy function of the canonical ensemble, or alternatively as the work obtained by
removing an electron from that body,
These chemical potentials are not equivalent, µ ≠ µ' ≠ µ'', except in the thermodynamic limit. The distinction is important in small
systems such as those showingCoulomb blockade.[12] The parameter, µ, (i.e., in the case where the number of electrons is allowed to
fluctuate) remains exactly related to the voltmeter voltage, even in small systems. To be precise, then, the Fermi level is defined not
by a deterministic charging event by one electron charge, but rather a statistical charging event by an infinitesimal fraction of an
electron.
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