metal–semiconductor junction
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solid-state physics Solid-state physics is the study of rigid matter, or solids, through methods such as quantum mechanics, crystallography, electromagnetism, and metallurgy. It is the largest branch of condensed matter physics. Solid-state physics studies how th ...
, a metal–semiconductor (M–S) junction is a type of electrical junction in which a
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
comes in close contact with a
semiconductor A semiconductor is a material which has an electrical conductivity value falling between that of a conductor, such as copper, and an insulator, such as glass. Its resistivity falls as its temperature rises; metals behave in the opposite way ...
material. It is the oldest practical
semiconductor device A semiconductor device is an electronic component that relies on the electronic properties of a semiconductor material (primarily silicon, germanium, and gallium arsenide, as well as organic semiconductors) for its function. Its conductivit ...
. M–S junctions can either be
rectifying A rectifier is an electrical device that converts alternating current (AC), which periodically reverses direction, to direct current (DC), which flows in only one direction. The reverse operation (converting DC to AC) is performed by an inver ...
or non-rectifying. The rectifying metal–semiconductor junction forms a
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...
, making a device known as a
Schottky diode The Schottky diode (named after the German physicist Walter H. Schottky), also known as Schottky barrier diode or hot-carrier diode, is a semiconductor diode formed by the junction of a semiconductor with a metal. It has a low forward voltage ...
, while the non-rectifying junction is called an ohmic contact. (In contrast, a rectifying semiconductor–semiconductor junction, the most common semiconductor device today, is known as a
p–n junction A p–n junction is a boundary or interface between two types of semiconductor materials, p-type and n-type, inside a single crystal of semiconductor. The "p" (positive) side contains an excess of holes, while the "n" (negative) side contai ...
.) Metal–semiconductor junctions are crucial to the operation of all semiconductor devices. Usually an ohmic contact is desired, so that electrical charge can be conducted easily between the active region of a
transistor upright=1.4, gate (G), body (B), source (S) and drain (D) terminals. The gate is separated from the body by an insulating layer (pink). A transistor is a semiconductor device used to Electronic amplifier, amplify or electronic switch, switch ...
and the external circuitry. Occasionally however a
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...
is useful, as in
Schottky diode The Schottky diode (named after the German physicist Walter H. Schottky), also known as Schottky barrier diode or hot-carrier diode, is a semiconductor diode formed by the junction of a semiconductor with a metal. It has a low forward voltage ...
s,
Schottky transistor A Schottky transistor is a combination of a transistor and a Schottky diode that prevents the transistor from saturating by diverting the excessive input current. It is also called a Schottky-clamped transistor. Mechanism Standard transistor ...
s, and metal–semiconductor field effect transistors.


The critical parameter: Schottky barrier height

Whether a given metal-semiconductor junction is an ohmic contact or a Schottky barrier depends on the Schottky barrier height, ΦB, of the junction. For a sufficiently large Schottky barrier height, where ΦB is significantly higher than the thermal energy ''kT'', the semiconductor is depleted near the metal and behaves as a
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...
. For lower Schottky barrier heights, the semiconductor is not depleted and instead forms an ohmic contact to the metal. The Schottky barrier height is defined differently for n-type and p-type semiconductors (being measured from the conduction band edge and valence band edge, respectively). The alignment of the semiconductor's bands near the junction is typically independent of the semiconductor's doping level, so the ''n''-type and ''p''-type Schottky barrier heights are ideally related to each other by: :\Phi_^ + \Phi_^ = E_ where ''E''g is the semiconductor's
band gap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference ( ...
. In practice, the Schottky barrier height is not precisely constant across the interface, and varies over the interfacial surface.


Schottky–Mott rule and Fermi level pinning

The SchottkyMott rule of Schottky barrier formation predicts the Schottky barrier height based on the vacuum
work function In solid-state physics, the work function (sometimes spelt 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 ...
of the metal relative to the vacuum electron affinity (or vacuum
ionization energy Ionization, or Ionisation is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule ...
) of the semiconductor: :\Phi_^ \approx \Phi_ - \chi_ This model is derived based on the thought experiment of bringing together the two materials in vacuum, and is closely related in logic to
Anderson's rule Anderson's rule is used for the construction of energy band diagrams of the heterojunction between two semiconductor materials. Anderson's rule states that when constructing an energy band diagram, the vacuum levels of the two semiconductors on e ...
for
semiconductor-semiconductor junction A heterojunction is an interface between two layers or regions of dissimilar semiconductors. These semiconducting materials have unequal band gaps as opposed to a homojunction. It is often advantageous to engineer the electronic energy bands in ma ...
s. Different semiconductors respect the Schottky–Mott rule to varying degrees. Although the Schottky–Mott model correctly predicted the existence of band bending in the semiconductor, it was found experimentally that it would give grossly incorrect predictions for the height of the Schottky barrier. A phenomenon referred to as "Fermi level pinning" caused some point of the band gap, at which finite
DOS DOS is shorthand for the MS-DOS and IBM PC DOS family of operating systems. DOS may also refer to: Computing * Data over signalling (DoS), multiplexing data onto a signalling channel * Denial-of-service attack (DoS), an attack on a communicat ...
exists, to be locked (pinned) to the Fermi level. This made the Schottky barrier height almost completely insensitive to the metal's work function: :\Phi_ \approx \frac E_ where ''E''bandgap is the size of
band gap In solid-state physics, a band gap, also called an energy gap, is an energy range in a solid where no electronic states can exist. In graphs of the electronic band structure of solids, the band gap generally refers to the energy difference ( ...
in the semiconductor. In fact, empirically, it is found that neither of the above extremes is quite correct. The choice of metal does have some effect, and there appears to be a weak correlation between the metal work function and the barrier height, however the influence of the work function is only a fraction of that predicted by the Schottky-Mott rule. It was noted in 1947 by
John Bardeen John Bardeen (; May 23, 1908 – January 30, 1991) was an American physicist and engineer. He is the only person to be awarded the Nobel Prize in Physics twice: first in 1956 with William Shockley and Walter Brattain for the invention of the tra ...
that the Fermi level pinning phenomenon would naturally arise if there were chargeable states in the semiconductor right at the interface, with energies inside the semiconductor's gap. These would either be induced during the direct chemical bonding of the metal and semiconductor ( metal-induced gap states) or be already present in the semiconductor–vacuum surface ( surface states). These highly dense surface states would be able to absorb a large quantity of charge donated from the metal, effectively shielding the semiconductor from the details of the metal. As a result, the semiconductor's bands would necessarily align to a location relative to the surface states which are in turn pinned to the Fermi level (due to their high density), all without influence from the metal. The Fermi level pinning effect is strong in many commercially important semiconductors (Si, Ge, GaAs), and thus can be problematic for the design of semiconductor devices. For example, nearly all metals form a significant Schottky barrier to ''n''-type
germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors ...
and an ohmic contact to ''p''-type germanium, since the valence band edge is strongly pinned to the metal's Fermi level. The solution to this inflexibility requires additional processing steps such as adding an intermediate insulating layer to unpin the bands. (In the case of germanium,
germanium nitride Germanium(IV) nitride is an inorganic compound with the chemical formula Ge3N4. It can be produced through the reaction of germanium and ammonia: :3 Ge + 4 NH3 → Ge3N4 + 6 H2 Structure In its pure state, germanium(IV) nitride is a colorless, ...
has been used)


History

The rectification property of metal–semiconductor contacts was discovered by
Ferdinand Braun Karl Ferdinand Braun (; 6 June 1850 – 20 April 1918) was a German electrical engineer, inventor, physicist and Nobel laureate in physics. Braun contributed significantly to the development of radio and television technology: he shared the ...
in 1874 using mercury metal contacted with
copper sulfide Copper sulfides describe a family of chemical compounds and minerals with the formula CuxSy. Both minerals and synthetic materials comprise these compounds. Some copper sulfides are economically important ores. Prominent copper sulfide mineral ...
and
iron sulfide Iron sulfide or Iron sulphide can refer to range of chemical compounds composed of iron and sulfur. Minerals By increasing order of stability: * Iron(II) sulfide, FeS * Greigite, Fe3S4 (cubic) * Pyrrhotite, Fe1−xS (where x = 0 to 0.2) (mono ...
semiconductors.
Sir Jagadish Chandra Bose Sir Jagadish Chandra Bose (;, ; 30 November 1858 – 23 November 1937) was a biologist, physicist, botanist and an early writer of science fiction. He was a pioneer in the investigation of radio microwave optics, made significant contributions ...
applied for a US patent for a metal-semiconductor diode in 1901. This patent was awarded in 1904. G.W. Pickard received a
patent A patent is a type of intellectual property that gives its owner the legal right to exclude others from making, using, or selling an invention for a limited period of time in exchange for publishing an enabling disclosure of the invention."A ...
in 1906 on a point-contact rectifier using
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
. In 1907, George W. Pierce published a paper in
Physical Review ''Physical Review'' is a peer-reviewed scientific journal established in 1893 by Edward Nichols. It publishes original research as well as scientific and literature reviews on all aspects of physics. It is published by the American Physical ...
showing rectification properties of
diode A diode is a two-terminal electronic component that conducts current primarily in one direction (asymmetric conductance); it has low (ideally zero) resistance in one direction, and high (ideally infinite) resistance in the other. A diod ...
s made by sputtering many metals on many semiconductors. The use of the metal–semiconductor diode rectifier was proposed by
Lilienfeld Lilienfeld () is a city in Lower Austria (Niederösterreich), Austria, south of St. Pölten, noted as the site of Lilienfeld Abbey. It is also the site of a regional hospital Landesklinikum Voralpen Lilienfeld. The city is located in the valley ...
in 1926 in the first of his three transistor patents as the gate of the metal–semiconductor field effect transistors. The theory of the
field-effect transistor The field-effect transistor (FET) is a type of transistor that uses an electric field to control the flow of current in a semiconductor. FETs (JFETs or MOSFETs) are devices with three terminals: ''source'', ''gate'', and ''drain''. FETs co ...
using a metal/semiconductor gate was advanced by
William Shockley William Bradford Shockley Jr. (February 13, 1910 – August 12, 1989) was an American physicist and inventor. He was the manager of a research group at Bell Labs that included John Bardeen and Walter Brattain. The three scientists were jointl ...
in 1939. The earliest metal–semiconductor diodes in
electronics The field of electronics is a branch of physics and electrical engineering that deals with the emission, behaviour and effects of electrons using electronic devices. Electronics uses active devices to control electron flow by amplification ...
application occurred around 1900, when the cat's whisker rectifiers were used in receivers. They consisted of pointed tungsten wire (in the shape of a cat's whisker) whose tip or point was pressed against the surface of a
galena Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver. Galena is one of the most abundant and widely distributed sulfide minerals. It cr ...
(lead sulfide) crystal. The first large area rectifier appeared around 1926 which consisted of a
copper(I) oxide Copper(I) oxide or cuprous oxide is the inorganic compound with the formula Cu2O. It is one of the principal oxides of copper, the other being or copper(II) oxide or cupric oxide (CuO). This red-coloured solid is a component of some antifoulin ...
semiconductor thermally grown on a copper substrate. Subsequently,
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
films were
evaporated Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. High concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humi ...
onto large metal substrates to form the rectifying diodes. These selenium rectifiers were used (and are still used) to convert alternating current to direct current in electrical power applications. During 1925–1940, diodes consisting of a pointed
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isol ...
metal wire in contact with a
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
crystal base, were fabricated in laboratories to detect microwaves in the
UHF Ultra high frequency (UHF) is the ITU designation for radio frequencies in the range between 300 megahertz (MHz) and 3 gigahertz (GHz), also known as the decimetre band as the wavelengths range from one meter to one tenth of a meter (on ...
range. A World War II program to manufacture high-purity silicon as the crystal base for the point-contact rectifier was suggested by
Frederick Seitz Frederick Seitz (July 4, 1911 – March 2, 2008) was an American physicist and a pioneer of solid state physics and lobbyist. Seitz was the 4th president of Rockefeller University from 1968–1978, and the 17th president of the United States Nat ...
in 1942 and successfully undertaken by the Experimental Station of the E. I du Pont de Nemours Company. The first theory that predicted the correct direction of rectification of the metal–semiconductor junction was given by Nevill Mott in 1939. He found the solution for both the
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical ...
and
drift Drift or Drifts may refer to: Geography * Drift or ford (crossing) of a river * Drift, Kentucky, unincorporated community in the United States * In Cornwall, England: ** Drift, Cornwall, village ** Drift Reservoir, associated with the village ...
currents of the
majority carriers In physics, a charge carrier is a particle or quasiparticle that is free to move, carrying an electric charge, especially the particles that carry electric charges in electrical conductors. Examples are electrons, ions and holes. The term is used ...
through the semiconductor surface space charge layer which has been known since about 1948 as the Mott barrier.
Walter H. Schottky Walter Hans Schottky (23 July 1886 – 4 March 1976) was a German physicist who played a major early role in developing the theory of electron and ion emission phenomena, invented the screen-grid vacuum tube in 1915 while working at Siemen ...
and Spenke extended Mott's theory by including a donor ion whose
density Density (volumetric mass density or specific mass) is the substance's mass per unit of volume. The symbol most often used for density is ''ρ'' (the lower case Greek letter rho), although the Latin letter ''D'' can also be used. Mathematicall ...
is spatially constant through the semiconductor surface layer. This changed the constant
electric field An electric field (sometimes E-field) is the physical field that surrounds electrically charged particles and exerts force on all other charged particles in the field, either attracting or repelling them. It also refers to the physical field ...
assumed by Mott to a linearly decaying electric field. This semiconductor space-charge layer under the metal is known as the
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...
. A similar theory was also proposed by
Davydov Davydov (russian: Давыдов), or Davydova (feminine; ), is a surname common in Russia and Ukraine. * Alexander Davydov, Soviet and Ukrainian physicist * Alexander Davydov, Soviet Red Army major and an illegitimate child of Joseph Stalin * Al ...
in 1939. Although it gives the correct direction of rectification, it has also been proven that the Mott theory and its Schottky-Davydov extension gives the wrong current limiting mechanism and wrong current-voltage formulae in silicon metal/semiconductor diode rectifiers. The correct theory was developed by
Hans Bethe Hans Albrecht Bethe (; July 2, 1906 – March 6, 2005) was a German-American theoretical physicist who made major contributions to nuclear physics, astrophysics, quantum electrodynamics, and solid-state physics, and who won the 1967 Nobel ...
and reported by him in a M.I.T. Radiation Laboratory Report dated November 23, 1942. In Bethe's theory, the current is limited by
thermionic emission Thermionic emission is the liberation of electrons from an electrode by virtue of its temperature (releasing of energy supplied by heat). This occurs because the thermal energy given to the charge carrier overcomes the work function of the mater ...
of
electrons The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have n ...
over the metal–semiconductor potential barrier. Thus, the appropriate name for the metal–semiconductor diode should be the Bethe diode, instead of the
Schottky diode The Schottky diode (named after the German physicist Walter H. Schottky), also known as Schottky barrier diode or hot-carrier diode, is a semiconductor diode formed by the junction of a semiconductor with a metal. It has a low forward voltage ...
, since the Schottky theory does not predict the modern metal–semiconductor diode characteristics correctly. If a metal-semiconductor junction is formed by placing a
droplet A drop or droplet is a small column of liquid, bounded completely or almost completely by free surfaces. A drop may form when liquid accumulates at the lower end of a tube or other surface boundary, producing a hanging drop called a pendant ...
of mercury, as
Braun Braun is a common surname, originating from the German word for the color brown. The name is the 22nd most common family name in Germany. Many German emigrants to the United States also changed their name to ''Brown'' (''see Brown (surname)''). ...
did, onto a semiconductor, e.g.
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
, to form a
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...
in a
Schottky diode The Schottky diode (named after the German physicist Walter H. Schottky), also known as Schottky barrier diode or hot-carrier diode, is a semiconductor diode formed by the junction of a semiconductor with a metal. It has a low forward voltage ...
electrical setup – electrowetting can be observed, where the droplet spreads out with increasing voltage. Depending on the doping type and density in the semiconductor, the droplet spreading depends on the magnitude and sign of the voltage applied to the mercury droplet. This effect has been termed ‘Schottky electrowetting’, effectively linking electrowetting and semiconductor effects. The
MOSFET The metal–oxide–semiconductor field-effect transistor (MOSFET, MOS-FET, or MOS FET) is a type of field-effect transistor (FET), most commonly fabricated by the controlled oxidation of silicon. It has an insulated gate, the voltage of which d ...
(metal-oxide-semiconductor field-effect transistor) was invented by
Mohamed Atalla Mohamed M. Atalla ( ar, محمد عطاالله; August 4, 1924 – December 30, 2009) was an Egyptian-American engineer, physicist, cryptographer, inventor and entrepreneur. He was a semiconductor pioneer who made important contributions t ...
and
Dawon Kahng Dawon Kahng ( ko, 강대원; May 4, 1931 – May 13, 1992) was a Korean-American electrical engineer and inventor, known for his work in solid-state electronics. He is best known for inventing the MOSFET (metal–oxide–semiconductor field-effe ...
at
Bell Labs Nokia Bell Labs, originally named Bell Telephone Laboratories (1925–1984), then AT&T Bell Laboratories (1984–1996) and Bell Labs Innovations (1996–2007), is an American industrial research and scientific development company owned by mul ...
in 1959, and presented in 1960. They extended their work on MOS technology to do pioneering work on hot carrier devices, which used what would later be called a Schottky barrier. The Schottky diode, also known as the Schottky-barrier diode, was theorized for years, but was first practically realized as a result of the work of Atalla and Kahng during 19601961. They published their results in 1962 and called their device the "hot electron" triode structure with semiconductor-metal emitter. It was one of the first metal-base transistors. Atalla continued research on Schottky diodes with Robert J. Archer at HP Associates. They developed high
vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or " void". An approximation to such vacuum is a region with a gaseous pressure much less than atmospheric pressure. Physicists often ...
metal film
deposition Deposition may refer to: * Deposition (law), taking testimony outside of court * Deposition (politics), the removal of a person of authority from political power * Deposition (university), a widespread initiation ritual for new students practiced f ...
technology, and fabricated stable
evaporated Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. High concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humi ...
/ sputtered contacts, publishing their results in January 1963. Their work was a breakthrough in metal–semiconductor junction and Schottky barrier research, as it overcame most of the
fabrication Fabrication may refer to: * Manufacturing, specifically the crafting of individual parts as a solo product or as part of a larger combined product. Processes in arts, crafts and manufacturing * Semiconductor device fabrication, the process used ...
problems inherent in point-contact diodes and made it possible to build practical Schottky diodes.


See also

*
Schottky barrier A Schottky barrier, named after Walter H. Schottky, is a potential energy barrier for electrons formed at a metal–semiconductor junction. Schottky barriers have rectifying characteristics, suitable for use as a diode. One of the primary ch ...


References


Further reading

* {{DEFAULTSORT:Metal-semiconductor junction Semiconductor structures