Work function

In solid-state physics, the work function (sometimes

spelled workfunction) is the minimum thermodynamic
work (i.e. energy) needed to remove an electron from a
solid to a point in the vacuum immediately outside the
solid surface. Here immediately means that the nal
electron position is far from the surface on the atomic
scale, but still too close to the solid to be inuenced by
ambient electric elds in the vacuum. The work function is not a characteristic of a bulk material, but rather
a property of the surface of the material (depending on
crystal face and contamination).

In practice, one directly controls EF by the voltage applied to the material through electrodes, and the work
function is generally a xed characteristic of the surface
material. Consequently, this means that when a voltage
is applied to a material, the electrostatic potential produced in the vacuum will be somewhat lower than the
applied voltage, the dierence depending on the work
function of the material surface. Rearranging the above
equation, one has

=V

W
e

where V = EF/e is the voltage of the material (as measured by a voltmeter, through an attached electrode), relative to an electrical ground that is dened as having zero
Fermi level. The fact that depends on material surface
means that the space between two dissimilar conductors
will have a built-in electric eld, even when those conductors are in total equilibrium with each other (electrically
shorted to each other, and with equal temperatures). An
example of this situation is depicted in the adjacent gure. As described in the next section, these built-in vacuum electric elds can have important consequences in
some cases.

Denition

The work function W for a given surface is dened by the

dierence[1]

W = e EF ,
where e is the charge of an electron, is the electrostatic
potential in the vacuum nearby the surface, and EF is the
Fermi level (electrochemical potential of electrons) inside
the material. The term e is the energy of an electron
at rest in the vacuum nearby the surface, and the meaning
of the term EF is the thermodynamic work required to
remove an electron from the material to a state of zero total energy. In words, the work function is thus dened as
the thermodynamic work required to remove an electron
from the material to a state at rest in the vacuum nearby
the surface.

2 Applications
Thermionic emission: In thermionic electron guns,
the work function and temperature of the hot
cathode are critical parameters in determining the
amount of current that can be emitted. Tungsten,
the common choice for vacuum tube laments, can
survive to high temperatures but its emission is
somewhat limited due to its relatively high work
function (approximately 4.5 eV). By coating the
tungsten with a substance of lower work function
(e.g., thorium or barium oxide), the emission can
be greatly increased. This prolongs the lifetime of
the lament by allowing operation at lower temperatures (for more information, see hot cathode).
Band bending models in solid-state electronics: The
behavior of a solid-state device is strongly dependent on the size of various Schottky barriers and
band osets in the junctions of diering materials, such as metals, semiconductors, and insulators.
Some commonly used heuristic approaches to predict the band alignment between materials, such

Plot of electron energy levels against position, in a gold-vacuumaluminium system. The two metals depicted here are in complete
thermodynamic equilibrium. However, the vacuum electrostatic
potential is not at due to a dierence in work function.

3
as Andersons rule and the Schottky-Mott rule, are
based on the thought experiment of two materials
coming together in vacuum, such that the surfaces
charge up and adjust their work functions to become
equal just before contact. In reality these work function heuristics are inaccurate due to their neglect of
numerous microscopic eects. However. they provide a convenient estimate until the true value can
be determined by experiment.[2][3]
Equilibrium electric elds in vacuum chambers:
Variation in work function between dierent surfaces causes a non-uniform electrostatic potential in
the vacuum. Even on an ostensibly uniform surface,
variations in W known as patch potentials are always present due to microscopic inhomogeneities.
Patch potentials have disrupted sensitive apparatus
that rely on a perfectly uniform vacuum, such as
Casimir force experiments[4] and the Gravity Probe
B experiment.[5] Critical apparatus may have surfaces covered with molybdenum, which shows low
variations in work function between dierent crystal faces.[6]
Contact electrication: If two conducting surfaces
are moved relative to each other, and there is potential dierence in the space between them, then
an electric current will be driven. This is because
the surface charge on a conductor depends on the
magnitude of the electric eld, which in turn depends on the distance between the surfaces. The externally observed electrical eects are largest when
the conductors are separated by the smallest distance without touching (once brought into contact,
the charge will instead ow internally through the
junction between the conductors). Since two conductors in equilibrium can have a built-in potential dierence due to work function dierences, this
means that bringing dissimilar conductors into contact, or pulling them apart, will drive electric currents. These contact currents can damage sensitive
microelectronic circuitry and occur even when the
conductors would be grounded in the absence of
motion.[7]

MEASUREMENT

they average or select dierently among the microscopic

work functions.[8]
Many techniques have been developed based on dierent
physical eects to measure the electronic work function
of a sample. One may distinguish between two groups of
experimental methods for work function measurements:
absolute and relative.
Absolute methods employ electron emission from
the sample induced by photon absorption (photoemission), by high temperature (thermionic emission), due to an electric eld (eld electron emission), or using electron tunnelling.
Relative methods make use of the contact potential
dierence between the sample and a reference electrode. Experimentally, either an anode current of a
diode is used or the displacement current between
the sample and reference, created by an articial
change in the capacitance between the two, is measured (the Kelvin Probe method, Kelvin probe force
microscope).

3.1 Methods based on thermionic emission

The work function is important in the theory of
thermionic emission, where thermal uctuations provide
enough energy to evaporate electrons out of a hot material (called the 'emitter') into the vacuum. If these electrons are absorbed by another, cooler material (called the
collector) then a measurable electric current will be observed. Thermionic emission can be used to measure
the work function of both the hot emitter and cold collector. Generally, these measurement involve tting to
Richardsons law, and so they must be carried out in a low
temperature and low current regime where space charge
eects are absent.
3.1.1 Work function of hot electron emitter

Measurement

Certain physical phenomena are highly sensitive to the

value of the work function. The observed data from
these eects can be tted to simplied theoretical models, allowing one to extract a value of the work function.
These phenomenologically extracted work functions may
be slightly dierent from the thermodynamic denition
given above. For inhomogeneous surfaces, the work function varies from place to place, and dierent methods will
yield dierent values of the typical work function as

Energy level diagrams for thermionic diode in forward bias conguration, used to extract all hot electrons coming out from the
emitters surface. The barrier is the vacuum near emitter surface.

In order to move from the hot emitter to the vacuum, an

3.2

Methods based on photoemission

electrons energy must exceed the emitter Fermi level by is the Seebeck voltage in the hot emitter (the inuence
an amount
of VS is often omitted, as it is a small contribution of
order 10 mV). The resulting current density J through
the collector (per unit of collector area) is again given by
Ebarrier = We
Richardsons Law, except now
determined simply by the thermionic work function of
the emitter. If an electric eld is applied towards the surface of the emitter, then all of the escaping electrons will
be accelerated away from the emitter and absorbed into
whichever material is applying the electric eld. According to Richardsons law the emitted current density (per
unit area of emitter), J (A/m2 ), is related to the absolute
temperature T of the emitter by the equation:

Jc = ATe2 eEbarrier /kTe

where A is a Richardson-type constant that depends on
the collector material but may also depend on the emitter
material, and the diode geometry. In this case, the dependence of J on T, or on V , can be tted to yield
W.

This retarding potential method is one of the simplest

and
oldest methods of measuring work functions, and is
Je =
advantageous since the measured material (collector) is
where k is the Boltzmann constant and the proportionality not required to survive high temperatures.
constant A is the Richardsons constant of the emitter. In
this case, the dependence of J on T can be tted to yield
W.
3.2 Methods based on photoemission
Ae Te2 eEbarrier /kTe

3.1.2

Work function of cold electron collector

Photoelectric diode in forward bias conguration, used for measuring the work function We of the illuminated emitter.
Energy level diagrams for thermionic diode in retarding potential
conguration. The barrier is the vacuum near collector surface.

The same setup can be used to instead measure the work

function in the collector, simply by adjusting the applied
voltage. If an electric eld is applied away from the emitter instead, then most of the electrons coming from the
emitter will simply be reected back to the emitter. Only
the highest energy electrons will have enough energy to
reach the collector, and the height of the potential barrier in this case depends on the collectors work function,
rather than the emitters.

The photoelectric work function is the minimum photon

energy required to liberate an electron from a substance,
in the photoelectric eect. If the photons energy is
greater than the substances work function, photoelectric
emission occurs and the electron is liberated from the surface. Similar to the thermionic case described above, the
liberated electrons can be extracted into a collector and
produce a detectable current, if an electric eld is applied
into the surface of the emitter. Excess photon energy results in a liberated electron with non-zero kinetic energy.
It is expected that the minimum photon energy required to liberate an electron (and generate a current) is

The current is still governed by Richardsons law. However, in this case the barrier height is does not depend on
W. The barrier height now depends on the work func- = W
e
tion of the collector, as well as any additional applied
[9]
voltages:
where W is the work function of the emitter.

Photoelectric measurements require a great deal of care,

as an incorrectly designed experimental geometry can reEbarrier = Wc e(Vce VS )
sult in an erroneous measurement of work function.[8]
where W is the collectors thermionic work function, This may be responsible for the large variation in work
V is the applied collectoremitter voltage, and VS function values in scientic literature. Moreover, the

5 PHYSICAL FACTORS THAT DETERMINE THE WORK FUNCTION

minimum energy can be misleading in materials where tion maps of a surface with extremely high spatial resoluthere are no actual electron states at the Fermi level that tion, by using a sharp tip for the probe (see Kelvin probe
are available for excitation. For example, in a semi- force microscope).
conductor the minimum photon energy would actually
correspond to the valence band edge rather than work
function.[10]
4 Work functions of elements[11]
Of course, the photoelectric eect may be used in the retarding mode, as with the thermionic apparatus described Below is a table of work function values for various eleabove. In the retarding case, the dark collectors work ments. Note that the work function depends on the confunction is measured instead.
gurations of atoms at the surface of the material. For
example, on polycrystalline silver the work function is
4.26 eV, but on silver crystals it varies for dierent crystal
3.3 Kelvin probe method
faces as (100) face: 4.64 eV, (110) face: 4.52 eV, (111)
face: 4.74 eV.[12] Ranges for typical surfaces are shown
See also: Volta potential and Kelvin probe force micro- in the table below.
scope
The Kelvin probe technique relies on the detection of an

5 Physical factors that determine

the work function

Kelvin probe energy diagram at at vacuum conguration, used

for measuring work function dierence between sample and
probe.

Due to the complications described in the modelling section below, it is dicult to theoretically predict the work
function with accuracy. Various trends have, however,
been identied. The work function tends to be smaller for
metals with an open lattice, and larger for metals in which
the atoms are closely packed. It is somewhat higher on
dense crystal faces than open crystal faces, also depending on surface reconstructions for the given crystal face.

5.1 Surface dipole

electric eld (gradient in ) between a sample material
and probe material. The electric eld can be varied by
the voltage V that is applied to the sample relative to
the probe. If the voltage is chosen such that the electric
eld is eliminated (the at vacuum condition), then

eVsp = Ws Wp ,

when at is.

Since the experimenter controls and knows V , then

nding the at vacuum condition gives directly the work
function dierence between the two materials. The only
question is, how to detect the at vacuum condition?
Typically, the electric eld is detected by varying the distance between the sample and probe. When the distance
is changed but V is held constant, a current will ow
due to the change in capacitance. This current is proportional to the vacuum electric eld, and so when the
electric eld is neutralized no current will ow.
Although the Kelvin probe technique only measures a
work function dierence, it is possible to obtain an absolute work function by rst calibrating the probe against
a reference material (with known work function) and then
using the same probe to measure a desired sample. The
Kelvin probe technique can be used to obtain work func-

The work function is not simply dependent on the internal vacuum level inside the material (i.e., its average
electrostatic potential), because of the formation of an
atomic-scale electric double layer at the surface.[6] This
surface electric dipole gives a jump in the electrostatic
potential between the material and the vacuum.
A variety of factors are responsible for the surface electric
dipole. Even with a completely clean surface, the electrons can spread slightly into the vacuum, leaving behind
a slightly positively charged layer of material. This primarily occurs in metals, where the bound electrons do not
encounter a hard wall potential at the surface but rather a
gradual ramping potential due to image charge attraction.
The amount of surface dipole depends on the detailed layout of the atoms at the surface of the material, leading to
the variation in work function for dierent crystal faces.

5.2 Doping and electric eld eect (semiconductors)

In a semiconductor, the work function is sensitive to the
doping level at the surface of the semiconductor. Since
the doping near the surface can also be controlled by elec-

5
for oscillations in electronic density nearby the abrupt surface (these are similar to Friedel oscillations) as well as
the tail of electron density extending outside the surface.
This model showed why the density of conduction electrons (as represented by the Wigner-Seitz radius rs) is an
important parameter in determining work function.
The jellium model is only a partial explanation, as its predictions still show signicant deviation from real work
functions. More recent models have focussed on including more accurate forms of electron exchange and
correlation eects, as well as including the crystal face
dependence (this requires the inclusion of the actual
atomic lattice, something that is neglected in the jellium
model).[6][18]
The electron behaviour in metals varies with temperature
and is largely reected by the electron work function. A
Band diagram of semiconductor-vacuum interface showing
recent theoretical model explains the underlying mechaelectron anity EEA, dened as the dierence between neartemperature dependence for varisurface vacuum energy Evac, and near-surface conduction band nism and predicts this[19]
ous
crystal
structures.
edge EC. Also shown: Fermi level EF, valence band edge EV,
work function W.

tric elds, the work function of a semiconductor is also

sensitive to the electric eld in the vacuum.
The reason for the dependence is that, typically, the vacuum level and the conduction band edge retain a xed
spacing independent of doping. This spacing is called
the electron anity (note that this has a dierent meaning than the electron anity of chemistry); in silicon
for example the electron anity is 4.05 eV.[14] If the
electron anity EEA and the surfaces band-referenced
Fermi level EF-EC are known, then the work function is
given by

W = EEA + EC EF
where EC is taken at the surface.
From this one might expect that by doping the bulk of
the semiconductor, the work function can be tuned. In
reality, however, the energies of the bands near the surface are often pinned to the Fermi level, due to the inuence of surface states.[15] If there is a large density of surface states, then the work function of the semiconductor
will show a very weak dependence on doping or electric
eld.[16]

5.3

Theoretical models of metal work

functions

Theoretical modelling of the work function is dicult, as

an accurate model requires a careful treatment of both
electronic many body eects and surface chemistry; both
of these topics are already complex in their own right.

6 References
[1] Kittel, Charles. Introduction to Solid State Physics (7th
ed.). Wiley.
[2] Herbert Kroemer, "Quasi-Electric Fields and Band Osets: Teaching Electrons New Tricks" Nobel lecture
[3] http://academic.brooklyn.cuny.edu/physics/tung/
Schottky/systematics.htm
[4] Behunin, R. O.; Intravaia, F.; Dalvit, D. A. R.; Neto, P.
A. M.; Reynaud, S. (2012). Modeling electrostatic patch
eects in Casimir force measurements. Physical Review
A 85. doi:10.1103/PhysRevA.85.012504.
[5] Will, C. M. (2011). Finally, results from Gravity Probe
B. Physics 4. doi:10.1103/Physics.4.43.
[6] http://venables.asu.edu/qmms/PROJ/metal1a.html
[7] Thomas Iii, S. W.; Vella, S. J.; Dickey, M. D.; Kaufman, G. K.; Whitesides, G. M. (2009). Controlling
the Kinetics of Contact Electrication with Patterned
Surfaces. Journal of the American Chemical Society
131 (25): 87468747. doi:10.1021/ja902862b. PMID
19499916.
[8] Helander, M. G.; Greiner, M. T.; Wang, Z. B.; Lu, Z. H.
(2010). Pitfalls in measuring work function using photoelectron spectroscopy. Applied Surface Science 256 (8):
2602. doi:10.1016/j.apsusc.2009.11.002.
[9] G.L. Kulcinski, Thermionic Energy Conversion
[10] http://www.virginia.edu/ep/SurfaceScience/PEE.html

One of the earliest successful models for metal work [11] CRC Handbook of Chemistry and Physics version 2008,
function trends was the jellium model,[17] which allowed
p. 12114.

[12] Dweydari, A. W.; Mee, C. H. B. (1975). Work

function measurements on (100) and (110) surfaces
of silver.
Physica Status Solidi (a) 27: 223.
doi:10.1002/pssa.2210270126.
[13] Nikolic, M. V.; Radic, S. M.; Minic, V.; Ristic, M. M.
(February 1996). The dependence of the work function of rare earth metals on their electron structure. Microelectronics Journal 27 (1): 9396. doi:10.1016/00262692(95)00097-6. ISSN 0026-2692. Retrieved 2009-0922.
[14] http://www.virginiasemi.com/pdf/
generalpropertiessi62002.pdf
[15] http://academic.brooklyn.cuny.edu/physics/tung/
Schottky/surface.htm
[16] Bardeen, J. (1947). Surface States and Rectication at a Metal Semi-Conductor Contact. Physical
Review 71 (10): 717. Bibcode:1947PhRv...71..717B.
doi:10.1103/PhysRev.71.717.
[17] Lang, N.; Kohn, W. (1971).
Theory of Metal
Surfaces: Work Function.
Physical Review B
3 (4):
1215.
Bibcode:1971PhRvB...3.1215L.
doi:10.1103/PhysRevB.3.1215.
[18] Kiejna, A.; Wojciechowski, K.F. (1996). Metal Surface
Electron Physics. Elsevier. ISBN 9780080536347.
[19] Rahemi, Reza; Li, Dongyang (April 2015). Variation in
electron work function with temperature and its eect on
the Youngs modulus of metals. Scripta Materialia 99:
4144. doi:10.1016/j.scriptamat.2014.11.022.

Further reading
Ashcroft; Mermin (1976).
Thomson Learning, Inc.

Solid State Physics.

Goldstein, Newbury; et al. (2003). Scanning Electron Microscopy and X-Ray Microanalysis. New
York: Springer.
For a quick reference to values of work function of the
elements:
Michaelson, Herbert B. (1977). The work function of the elements and its periodicity. J. Appl.
Phys. 48: 4729. Bibcode:1977JAP....48.4729M.
doi:10.1063/1.323539.

External links
Work function of polymeric insulators (Table 2.1)
Work function of diamond and doped carbon
Work functions of common metals

EXTERNAL LINKS

Work functions of various metals for the photoelectric eect

Physics of free surfaces of semiconductors
*Some of the work functions listed on these sites do not
agree!*

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