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In
semiconductor A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
production, doping is the intentional introduction of impurities into an
intrinsic semiconductor An intrinsic (pure) semiconductor, also called an undoped semiconductor or i-type semiconductor, is a pure semiconductor without any significant dopant species present. The number of charge carriers is therefore determined by the properties of the ...
for the purpose of modulating its electrical, optical and structural properties. The doped material is referred to as an
extrinsic semiconductor An extrinsic semiconductor is one that has been '' doped''; during manufacture of the semiconductor crystal a trace element or chemical called a doping agent has been incorporated chemically into the crystal, for the purpose of giving it different ...
. Small numbers of dopant
atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, and ...
s can change the ability of a semiconductor to conduct electricity. When on the order of one dopant atom is added per 100 million atoms, the doping is said to be ''low'' or ''light''. When many more dopant atoms are added, on the order of one per ten thousand atoms, the doping is referred to as ''high'' or ''heavy''. This is often shown as ''n+'' for n-type doping or ''p+'' for p-type doping. (''See the article on
semiconductors A semiconductor is a material which has an electrical resistivity and conductivity, electrical conductivity value falling between that of a electrical conductor, conductor, such as copper, and an insulator (electricity), insulator, such as glas ...
for a more detailed description of the doping mechanism.'') A semiconductor doped to such high levels that it acts more like a conductor than a semiconductor is referred to as a
degenerate semiconductor A degenerate semiconductor is a semiconductor with such a high level of doping that the material starts to act more like a metal than as a semiconductor. Unlike non-degenerate semiconductors, these kind of semiconductor do not obey law of mass act ...
. A semiconductor can be considered
i-type semiconductor An intrinsic (pure) semiconductor, also called an undoped semiconductor or i-type semiconductor, is a pure semiconductor without any significant dopant species present. The number of charge carriers is therefore determined by the properties of the ...
if it has been doped in equal quantities of p and n. In the context of
phosphor A phosphor is a substance that exhibits the phenomenon of luminescence; it emits light when exposed to some type of radiant energy. The term is used both for fluorescent or phosphorescent substances which glow on exposure to ultraviolet or vi ...
s and
scintillator A scintillator is a material that exhibits scintillation, the property of luminescence, when excited by ionizing radiation. Luminescent materials, when struck by an incoming particle, absorb its energy and scintillate (i.e. re-emit the absorbed ...
s, doping is better known as
activation Activation, in chemistry and biology, is the process whereby something is prepared or excited for a subsequent reaction. Chemistry In chemistry, "activation" refers to the reversible transition of a molecule into a nearly identical chemical or ...
; this is not to be confused with
dopant activation Dopant Activation is the process of obtaining the desired electronic contribution from impurity species in a semiconductor host. The term is often restricted to the application of thermal energy following the ion implantation of dopants. In the mo ...
in semiconductors. Doping is also used to control the color in some pigments.


History

The effects of impurities in semiconductors (doping) were long known empirically in such devices as
crystal radio A crystal radio receiver, also called a crystal set, is a simple radio receiver, popular in the early days of radio. It uses only the power of the received radio signal to produce sound, needing no external power. It is named for its most impo ...
detectors A sensor is a device that produces an output signal for the purpose of sensing a physical phenomenon. In the broadest definition, a sensor is a device, module, machine, or subsystem that detects events or changes in its environment and sends ...
and
selenium rectifiers A selenium rectifier is a type of metal rectifier, invented in 1933. They were used in power supplies for electronic equipment and in high-current battery-charger applications until they were superseded by silicon diode rectifiers in the late 1960 ...
. For instance, in 1885
Shelford Bidwell Shelford Bidwell FRS (6 March 1848 – 18 December 1909) was an English physicist and inventor. He is best known for his work with "telephotography", a precursor to the modern fax machine. Private life He was born in Thetford, Norfolk the elde ...
, and in 1930 the German scientist Bernhard Gudden, each independently reported that the properties of semiconductors were due to the impurities they contained. A doping process was formally developed by John Robert Woodyard working at
Sperry Gyroscope Company Sperry Corporation was a major American equipment and electronics company whose existence spanned more than seven decades of the 20th century. Sperry ceased to exist in 1986 following a prolonged hostile takeover bid engineered by Burroughs ...
during
World War II World War II or the Second World War, often abbreviated as WWII or WW2, was a world war that lasted from 1939 to 1945. It involved the vast majority of the world's countries—including all of the great powers—forming two opposin ...
. Though the word doping is not used in it, his US Patent issued in 1950 describes methods for adding tiny amounts of solid elements from the nitrogen column of the periodic table to germanium to produce rectifying devices. The demands of his work on
radar Radar is a detection system that uses radio waves to determine the distance (''ranging''), angle, and radial velocity of objects relative to the site. It can be used to detect aircraft, ships, spacecraft, guided missiles, motor vehicles, w ...
prevented Woodyard from pursuing further research on semiconductor doping. Similar work was performed 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 mult ...
by Gordon K. Teal and
Morgan Sparks Morgan Sparks (July 6, 1916 – May 3, 2008) was an American scientist and engineer who helped develop the microwatt bipolar junction transistor in 1951, which was a critical step in making transistors usable for every-day electronics. Sparks direc ...
, with a US Patent issued in 1953. Woodyard's prior
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 p ...
proved to be the grounds of extensive litigation by
Sperry Rand Sperry Corporation was a major American equipment and electronics company whose existence spanned more than seven decades of the 20th century. Sperry ceased to exist in 1986 following a prolonged hostile takeover bid engineered by Burroughs ...
.


Carrier concentration

The concentration of the dopant used affects many electrical properties. Most important is the material's
charge carrier 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 ...
concentration. In an intrinsic semiconductor under
thermal equilibrium Two physical systems are in thermal equilibrium if there is no net flow of thermal energy between them when they are connected by a path permeable to heat. Thermal equilibrium obeys the zeroth law of thermodynamics. A system is said to be in ...
, the concentrations of
electron 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 no kn ...
s and
holes A hole is an opening in or through a particular medium, usually a solid body. Holes occur through natural and artificial processes, and may be useful for various purposes, or may represent a problem needing to be addressed in many fields of en ...
are equivalent. That is, :n = p = n_i.\ In a non-intrinsic semiconductor under thermal equilibrium, the relation becomes (for low doping): :n_0 \cdot p_0 = n_i^2\ where ''n''0 is the concentration of conducting electrons, ''p''0 is the conducting hole concentration, and ''ni'' is the material's intrinsic carrier concentration. The intrinsic carrier concentration varies between materials and is dependent on temperature.
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 tab ...
's ''ni'', for example, is roughly 1.08×1010 cm−3 at 300
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and phys ...
s, about
room temperature Colloquially, "room temperature" is a range of air temperatures that most people prefer for indoor settings. It feels comfortable to a person when they are wearing typical indoor clothing. Human comfort can extend beyond this range depending on ...
. In general, increased doping leads to increased conductivity due to the higher concentration of carriers. Degenerate (very highly doped) semiconductors have conductivity levels comparable to
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
s and are often used in
integrated circuit An integrated circuit or monolithic integrated circuit (also referred to as an IC, a chip, or a microchip) is a set of electronic circuits on one small flat piece (or "chip") of semiconductor material, usually silicon. Large numbers of tiny ...
s as a replacement for metal. Often superscript plus and minus symbols are used to denote relative doping concentration in semiconductors. For example, ''n''+ denotes an n-type semiconductor with a high, often degenerate, doping concentration. Similarly, ''p'' would indicate a very lightly doped p-type material. Even degenerate levels of doping imply low concentrations of impurities with respect to the base semiconductor. In intrinsic
crystalline silicon Crystalline silicon or (c-Si) Is the crystalline forms of silicon, either polycrystalline silicon (poly-Si, consisting of small crystals), or monocrystalline silicon (mono-Si, a continuous crystal). Crystalline silicon is the dominant semicondu ...
, there are approximately 5×1022 atoms/cm3. Doping concentration for silicon semiconductors may range anywhere from 1013 cm−3 to 1018 cm−3. Doping concentration above about 1018 cm−3 is considered degenerate at room temperature. Degenerately doped silicon contains a proportion of impurity to silicon on the order of parts per thousand. This proportion may be reduced to parts per billion in very lightly doped silicon. Typical concentration values fall somewhere in this range and are tailored to produce the desired properties in the device that the semiconductor is intended for.


Effect on band structure

Doping a semiconductor in a good crystal introduces allowed energy states within the
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 ...
, but very close to the energy band that corresponds to the dopant type. In other words,
electron donor In chemistry, an electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. Typical reducing agents undergo permanent chem ...
impurities create states near the
conduction band In solid-state physics, the valence band and conduction band are the bands closest to the Fermi level, and thus determine the electrical conductivity of the solid. In nonmetals, the valence band is the highest range of electron energies in w ...
while
electron acceptor An electron acceptor is a chemical entity that accepts electrons transferred to it from another compound. It is an oxidizing agent that, by virtue of its accepting electrons, is itself reduced in the process. Electron acceptors are sometimes mista ...
impurities create states near the valence band. The gap between these energy states and the nearest energy band is usually referred to as dopant-site
bonding energy In chemistry, bond energy (''BE''), also called the mean bond enthalpy or average bond enthalpy is the measure of bond strength in a chemical bond. IUPAC defines bond energy as the average value of the gas-phase bond-dissociation energy (usually a ...
or ''EB'' and is relatively small. For example, the ''EB'' for
boron Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
in silicon bulk is 0.045 eV, compared with silicon's band gap of about 1.12 eV. Because ''EB'' is so small, room temperature is hot enough to thermally ionize practically all of the dopant atoms and create free
charge carrier 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 ...
s in the conduction or valence bands. Dopants also have the important effect of shifting the energy bands relative to the
Fermi level The Fermi level of a solid-state body is the thermodynamic work required to add one electron to the body. It is a thermodynamic quantity usually denoted by ''µ'' or ''E''F for brevity. The Fermi level does not include the work required to remove ...
. The energy band that corresponds with the dopant with the greatest concentration ends up closer to the Fermi level. Since the Fermi level must remain constant in a system in
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In thermod ...
, stacking layers of materials with different properties leads to many useful electrical properties induced by
band bending In solid-state physics, band bending refers to the process in which the electronic band structure in a material curves up or down near a junction or interface. It does not involve any physical (spatial) bending. When the electrochemical potential ...
, if the interfaces can be made cleanly enough. For example, the p-n junction's properties are due to the band bending that happens as a result of the necessity to line up the bands in contacting regions of p-type and n-type material. This effect is shown in a
band diagram In solid-state physics of semiconductors, a band diagram is a diagram plotting various key electron energy levels (Fermi level and nearby energy band edges) as a function of some spatial dimension, which is often denoted ''x''. These diagrams ...
. The band diagram typically indicates the variation in the valence band and conduction band edges versus some spatial dimension, often denoted ''x''. The Fermi level is also usually indicated in the diagram. Sometimes the ''intrinsic Fermi level'', ''Ei'', which is the Fermi level in the absence of doping, is shown. These diagrams are useful in explaining the operation of many kinds of
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 conductivity li ...
s.


Relationship to carrier concentration (low doping)

For low levels of doping, the relevant energy states are populated sparsely by electrons (conduction band) or holes (valence band). It is possible to write simple expressions for the electron and hole carrier concentrations, by ignoring Pauli exclusion (via
Maxwell–Boltzmann statistics In statistical mechanics, Maxwell–Boltzmann statistics describes the distribution of Classical physics, classical material particles over various energy states in thermal equilibrium. It is applicable when the temperature is high enough or the ...
): :n_e = N_(T) \exp((E_ - E_)/kT), \quad n_h = N_(T) \exp((E_ - E_)/kT), where is the
Fermi level The Fermi level of a solid-state body is the thermodynamic work required to add one electron to the body. It is a thermodynamic quantity usually denoted by ''µ'' or ''E''F for brevity. The Fermi level does not include the work required to remove ...
, is the minimum energy of the conduction band, and is the maximum energy of the valence band. These are related to the value of the intrinsic concentration via :n_i^2 = n_h n_e = N_(T) N_(T) \exp((E_-E_)/kT), an expression which is independent of the doping level, since (the
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 ...
) does not change with doping. The concentration factors and are given by :N_(T) = 2(2\pi m_e^* kT/h^2)^ \quad N_(T) = 2(2\pi m_h^* kT/h^2)^. where and are the density of states effective masses of electrons and holes, respectively, quantities that are roughly constant over temperature.


Techniques of doping and synthesis


Doping during crystal growth

Some
dopant A dopant, also called a doping agent, is a trace of impurity element that is introduced into a chemical material to alter its original electrical or optical properties. The amount of dopant necessary to cause changes is typically very low. When ...
s are added as the (usually
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 tab ...
) boule is grown by
Czochralski method The Czochralski method, also Czochralski technique or Czochralski process, is a method of crystal growth used to obtain single crystals of semiconductors (e.g. silicon, germanium and gallium arsenide), metals (e.g. palladium, platinum, silver, ...
, giving each
wafer A wafer is a crisp, often sweet, very thin, flat, light and dry biscuit, often used to decorate ice cream, and also used as a garnish on some sweet dishes. Wafers can also be made into cookies with cream flavoring sandwiched between them. They ...
an almost uniform initial doping. Alternately, synthesis of semiconductor devices may involve the use of vapor-phase epitaxy. In vapor-phase epitaxy, a gas containing the dopant precursor can be introduced into the reactor. For example, in the case of n-type gas doping of
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
,
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
is added, and sulfur is incorporated into the structure. This process is characterized by a constant concentration of sulfur on the surface. In the case of semiconductors in general, only a very thin layer of the wafer needs to be doped in order to obtain the desired electronic properties.


Post-growth doping

To define circuit elements, selected areas — typically controlled by
photolithography In integrated circuit manufacturing, photolithography or optical lithography is a general term used for techniques that use light to produce minutely patterned thin films of suitable materials over a substrate, such as a silicon wafer, to protect ...
— are further doped by such processes as
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 p ...
and
ion implantation Ion implantation is a low-temperature process by which ions of one element are accelerated into a solid target, thereby changing the physical, chemical, or electrical properties of the target. Ion implantation is used in semiconductor device fab ...
, the latter method being more popular in large production runs because of increased controllability.


Spin-on glass

Spin-on glass or spin-on dopant doping is a two-step process of applying a mixture of SiO2 and dopants (in a solvent) onto a wafer surafce by spin-coating and then stripping it and baking it at a certain temperatue in the furnace at constant nitrogen+oxygen flow.


Neutron transmutation doping

Neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
transmutation doping (NTD) is an unusual doping method for special applications. Most commonly, it is used to dope silicon n-type in high-power electronics and semiconductor detectors. It is based on the conversion of the Si-30 isotope into
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
atom by neutron absorption as follows: ^\mathrm \, (n,\gamma) \, ^\mathrm \rightarrow \, ^\mathrm + \beta^- \; (T_ = 2.62 \mathrm). In practice, the silicon is typically placed near a
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat from nu ...
to receive the neutrons. As neutrons continue to pass through the silicon, more and more phosphorus atoms are produced by transmutation, and therefore the doping becomes more and more strongly n-type. NTD is a far less common doping method than diffusion or ion implantation, but it has the advantage of creating an extremely uniform dopant distribution.


Dopant elements


Group IV semiconductors

(Note: When discussing periodic table groups, semiconductor physicists always use an older notation, not the current
IUPAC The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
group notation. For example, the
carbon group The carbon group is a periodic table group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), and flerovium (Fl). It lies within the p-block. In modern IUPAC notation, it is called group 14. In the field of semicond ...
is called "Group IV", not "Group 14".) For the
Group IV The carbon group is a periodic table group consisting of carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), and flerovium (Fl). It lies within the p-block. In modern IUPAC notation, it is called group 14. In the field of semicon ...
semiconductors such as
diamond Diamond is a Allotropes of carbon, solid form of the element carbon with its atoms arranged in a crystal structure called diamond cubic. Another solid form of carbon known as graphite is the Chemical stability, chemically stable form of car ...
,
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 tab ...
,
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 s ...
,
silicon carbide Silicon carbide (SiC), also known as carborundum (), is a hard chemical compound containing silicon and carbon. A semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder and crystal sin ...
, and
silicon–germanium SiGe ( or ), or silicon–germanium, is an alloy with any molar ratio of silicon and germanium, i.e. with a molecular formula of the form Si1−''x''Ge''x''. It is commonly used as a semiconductor material in integrated circuits (ICs) for hetero ...
, the most common dopants are acceptors from Group III or
donors A donor in general is a person, organization or government which donates something voluntarily. The term is usually used to represent a form of pure altruism, but is sometimes used when the payment for a service is recognized by all parties as rep ...
from
Group V A pnictogen ( or ; from grc, πνῑ́γω "to choke" and -gen, "generator") is any of the chemical elements in group 15 of the periodic table. Group 15 is also known as the nitrogen group or nitrogen family. Group 15 consists of the el ...
elements.
Boron Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
,
arsenic Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in many minerals, usually in combination with sulfur and metals, but also as a pure elemental crystal. Arsenic is a metalloid. It has various allotropes, but ...
,
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
, and occasionally
gallium Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in group 13 of the periodic table and is similar to the other metals of the group (aluminiu ...
are used to dope silicon. Boron is the p-type dopant of choice for silicon integrated circuit production because it diffuses at a rate that makes junction depths easily controllable. Phosphorus is typically used for bulk-doping of silicon wafers, while arsenic is used to diffuse junctions, because it diffuses more slowly than phosphorus and is thus more controllable. By doping pure silicon with
Group V A pnictogen ( or ; from grc, πνῑ́γω "to choke" and -gen, "generator") is any of the chemical elements in group 15 of the periodic table. Group 15 is also known as the nitrogen group or nitrogen family. Group 15 consists of the el ...
elements such as phosphorus, extra
valence electrons In chemistry and physics, a valence electron is an electron in the outer shell associated with an atom, and that can participate in the formation of a chemical bond if the outer shell is not closed. In a single covalent bond, a shared pair forms ...
are added that become unbounded from individual atoms and allow the compound to be an electrically conductive n-type semiconductor. Doping with Group III elements, which are missing the fourth valence electron, creates "broken bonds" (holes) in the silicon lattice that are free to move. The result is an electrically conductive p-type semiconductor. In this context, a
Group V A pnictogen ( or ; from grc, πνῑ́γω "to choke" and -gen, "generator") is any of the chemical elements in group 15 of the periodic table. Group 15 is also known as the nitrogen group or nitrogen family. Group 15 consists of the el ...
element is said to behave as an electron
donor A donor in general is a person, organization or government which donates something voluntarily. The term is usually used to represent a form of pure altruism, but is sometimes used when the payment for a service is recognized by all parties as rep ...
, and a Group III element as an acceptor. This is a key concept in the physics of a
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 diode ...
. A very heavily doped semiconductor behaves more like a good conductor (metal) and thus exhibits more linear positive thermal coefficient. Such effect is used for instance in
sensistor Sensistor is a resistor whose resistance changes with temperature. The resistance increases exponentially with temperature, that is the temperature coefficient is positive (e.g. 0.7% per degree Celsius). Sensistors are used in electronic circui ...
s. Lower dosage of doping is used in other types (NTC or PTC)
thermistor A thermistor is a type of resistor whose resistance is strongly dependent on temperature, more so than in standard resistors. The word thermistor is a portmanteau of ''thermal'' and ''resistor''. Thermistors are divided based on their conduction ...
s.


Silicon dopants

*Acceptors, p-type **Boron is a p-type dopant. Its
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 p ...
rate allows easy control of junction depths. Common in
CMOS Complementary metal–oxide–semiconductor (CMOS, pronounced "sea-moss", ) is a type of metal–oxide–semiconductor field-effect transistor (MOSFET) fabrication process that uses complementary and symmetrical pairs of p-type and n-type MOSFE ...
technology. Can be added by diffusion of
diborane Diborane(6), generally known as diborane, is the chemical compound with the formula B2H6. It is a toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Diborane is a key boron compound with a variety of applications. It has attracte ...
gas. The only acceptor with sufficient solubility for efficient emitters in transistors and other applications requiring extremely high dopant concentrations. Boron diffuses about as fast as phosphorus. **Aluminum, used for deep p-diffusions. Not popular in VLSI and ULSI. Also a common unintentional impurity. **Gallium is a dopant used for long-wavelength infrared photoconduction silicon detectors in the 8–14 μm atmospheric window. Gallium-doped silicon is also promising for solar cells, due to its long minority carrier lifetime with no lifetime degradation; as such it is gaining importance as a replacement of boron doped substrates for solar cell applications. **Indium is a dopant used for long-wavelength infrared photoconduction silicon detectors in the 3–5 μm atmospheric window. *Donors, n-type **Phosphorus is a n-type dopant. It diffuses fast, so is usually used for bulk doping, or for well formation. Used in solar cells. Can be added by diffusion of
phosphine Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula , classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting ...
gas. Bulk doping can be achieved by
nuclear transmutation Nuclear transmutation is the conversion of one chemical element or an isotope into another chemical element. Nuclear transmutation occurs in any process where the number of protons or neutrons in the nucleus of an atom is changed. A transmutatio ...
, by irradiation of pure silicon with
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
s in a
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat from nu ...
. Phosphorus also traps gold atoms, which otherwise quickly diffuse through silicon and act as recombination centers. **Arsenic is a n-type dopant. Its slower diffusion allows using it for diffused junctions. Used for buried layers. Has similar atomic radius to silicon, high concentrations can be achieved. Its diffusivity is about a tenth of phosphorus or boron, so it is used where the dopant should stay in place during subsequent thermal processing. Useful for shallow diffusions where well-controlled abrupt boundary is desired. Preferred dopant in VLSI circuits. Preferred dopant in low resistivity ranges. **Antimony is a n-type dopant. It has a small diffusion coefficient. Used for buried layers. Has diffusivity similar to arsenic, is used as its alternative. Its diffusion is virtually purely substitutional, with no interstitials, so it is free of anomalous effects. For this superior property, it is sometimes used in VLSI instead of arsenic. Heavy doping with antimony is important for power devices. Heavily antimony-doped silicon has lower concentration of oxygen impurities; minimal autodoping effects make it suitable for epitaxial substrates. **Bismuth is a promising dopant for long-wavelength infrared photoconduction silicon detectors, a viable n-type alternative to the p-type gallium-doped material. **Lithium is used for doping silicon for
radiation hardened Radiation hardening is the process of making electronic components and circuits resistant to damage or malfunction caused by high levels of ionizing radiation ( particle radiation and high-energy electromagnetic radiation), especially for enviro ...
solar cells. The lithium presence anneals defects in the lattice produced by protons and neutrons. Lithium can be introduced to boron-doped p+ silicon, in amounts low enough to maintain the p character of the material, or in large enough amount to counterdope it to low-resistivity n type. *Other **Germanium can be used for
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 ...
engineering. Germanium layer also inhibits diffusion of boron during the annealing steps, allowing ultrashallow p-MOSFET junctions. Germanium bulk doping suppresses large void defects, increases internal
gettering A getter is a deposit of reactive material that is placed inside a vacuum system to complete and maintain the vacuum. When gas molecules strike the getter material, they combine with it chemically or by . Thus the getter removes small amounts of ...
, and improves wafer mechanical strength. **Silicon, germanium and xenon can be used as ion beams for pre- amorphization of silicon wafer surfaces. Formation of an amorphous layer beneath the surface allows forming ultrashallow junctions for p-MOSFETs. **Nitrogen is important for growing defect-free silicon crystal. Improves mechanical strength of the lattice, increases bulk microdefect generation, suppresses vacancy agglomeration. **Gold and platinum are used for minority carrier lifetime control. They are used in some infrared detection applications. Gold introduces a donor level 0.35 eV above the valence band and an acceptor level 0.54 eV below the conduction band. Platinum introduces a donor level also at 0.35 eV above the valence band, but its acceptor level is only 0.26 eV below conduction band; as the acceptor level in n-type silicon is shallower, the space charge generation rate is lower and therefore the leakage current is also lower than for gold doping. At high injection levels platinum performs better for lifetime reduction. Reverse recovery of bipolar devices is more dependent on the low-level lifetime, and its reduction is better performed by gold. Gold provides a good tradeoff between forward voltage drop and reverse recovery time for fast switching bipolar devices, where charge stored in base and collector regions must be minimized. Conversely, in many power transistors a long minority carrier lifetime is required to achieve good gain, and the gold/platinum impurities must be kept low.


Other semiconductors

In the following list the "(substituting X)" refers to all of the materials preceding said parenthesis. *
Gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
** n-type: tellurium, sulfur (substituting As); tin, silicon, germanium (substituting Ga) ** p-type: beryllium, zinc, chromium (substituting Ga); silicon, germanium, carbon (substituting As) *
Gallium phosphide Gallium phosphide (GaP), a phosphide of gallium, is a compound semiconductor material with an indirect band gap of 2.24 eV at room temperature. Impure polycrystalline material has the appearance of pale orange or grayish pieces. Undoped single cry ...
** n-type: tellurium, selenium, sulfur (substituting phosphorus) ** p-type: zinc, magnesium (substituting Ga); tin (substituting P) ** isoelectric: nitrogen (substituting P) is added to enable luminescence in older green
LED A light-emitting diode (LED) is a semiconductor Electronics, device that Light#Light sources, emits light when Electric current, current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy i ...
s (GaP has
indirect band gap In semiconductor physics, the band gap of a semiconductor can be of two basic types, a direct band gap or an indirect band gap. The minimal-energy state in the conduction band and the maximal-energy state in the valence band are each characteriz ...
) *
Gallium nitride Gallium nitride () is a binary III/ V direct bandgap semiconductor commonly used in blue light-emitting diodes since the 1990s. The compound is a very hard material that has a Wurtzite crystal structure. Its wide band gap of 3.4 eV affords it ...
,
Indium gallium nitride Indium gallium nitride (InGaN, ) is a semiconductor material made of a mix of gallium nitride (GaN) and indium nitride (InN). It is a ternary group III/group V direct bandgap semiconductor. Its bandgap can be tuned by varying the amount of indi ...
,
Aluminium gallium nitride Aluminium gallium nitride (AlGaN) is a semiconductor material. It is any alloy of aluminium nitride and gallium nitride. The bandgap of AlxGa1−xN can be tailored from 3.4eV (xAl=0) to 6.2eV (xAl=1). AlGaN is used to manufacture light-emitting d ...
** n-type: silicon (substituting Ga), germanium (substituting Ga, better lattice match), carbon (substituting Ga, naturally embedding into
MOVPE Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. ...
-grown layers in low concentration) ** p-type: magnesium (substituting Ga) - challenging due to relatively high
ionisation 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 i ...
above the
valence band In solid-state physics, the valence band and conduction band are the bands closest to the Fermi level, and thus determine the electrical conductivity of the solid. In nonmetals, the valence band is the highest range of electron energies in w ...
edge, strong
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 p ...
of
interstitial An interstitial space or interstice is a space between structures or objects. In particular, interstitial may refer to: Biology * Interstitial cell tumor * Interstitial cell, any cell that lies between other cells * Interstitial collagenase ...
Mg, hydrogen complexes passivating of Mg acceptors and by Mg self-compensation at higher concentrations) *
Cadmium telluride Cadmium telluride (CdTe) is a stable crystalline compound formed from cadmium and tellurium. It is mainly used as the semiconducting material in cadmium telluride photovoltaics and an infrared optical window. It is usually sandwiched with ca ...
** n-type: indium, aluminium (substituting Cd); chlorine (substituting Te) ** p-type: phosphorus (substituting Te); lithium, sodium (substituting Cd) *
Cadmium sulfide Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid.Egon Wiberg, Arnold Frederick Holleman (2001''Inorganic Chemistry'' Elsevier It occurs in nature with two different crystal structures as the rare m ...
** n-type: gallium (substituting Cd); iodine, fluorine (substituting S) ** p-type: lithium, sodium (substituting Cd)


Compensation

In most cases many types of impurities will be present in the resultant doped semiconductor. If an equal number of donors and acceptors are present in the semiconductor, the extra core electrons provided by the former will be used to satisfy the broken bonds due to the latter, so that doping produces no free carriers of either type. This phenomenon is known as ''compensation'', and occurs at the p-n junction in the vast majority of semiconductor devices. Partial compensation, where donors outnumber acceptors or vice versa, allows device makers to repeatedly reverse (invert) the type of a certain layer under the surface of a bulk semiconductor by diffusing or implanting successively higher doses of dopants, so-called counterdoping. Most modern semiconductor devices are made by successive selective counterdoping steps to create the necessary P and N type areas under the surface of bulk silicon. This is an alternative to successively growing such layers by epitaxy. Although compensation can be used to increase or decrease the number of donors or acceptors, the electron and hole
mobility Mobility may refer to: Social sciences and humanities * Economic mobility, ability of individuals or families to improve their economic status * Geographic mobility, the measure of how populations and goods move over time * Mobilities, a contemp ...
is always decreased by compensation because mobility is affected by the sum of the donor and acceptor ions.


Doping in conductive polymers

Conductive polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage of conductive polymer ...
s can be doped by adding chemical reactants to
oxidize Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
, or sometimes reduce, the system so that electrons are pushed into the conducting orbitals within the already potentially conducting system. There are two primary methods of doping a conductive polymer, both of which use an oxidation-reduction (i.e.,
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
) process. # Chemical doping involves exposing a polymer such as
melanin Melanin (; from el, μέλας, melas, black, dark) is a broad term for a group of natural pigments found in most organisms. Eumelanin is produced through a multistage chemical process known as melanogenesis, where the oxidation of the amino ...
, typically a
thin film A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ap ...
, to an
oxidant An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxid ...
such as
iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...
or
bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table (halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simila ...
. Alternatively, the polymer can be exposed to a
reductant In chemistry, a reducing agent (also known as a reductant, reducer, or electron donor) is a chemical species that "donates" an electron to an (called the , , , or ). Examples of substances that are commonly reducing agents include the Earth meta ...
; this method is far less common, and typically involves
alkali metals The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
. # Electrochemical doping involves suspending a polymer-coated, working
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
in an
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
solution in which the polymer is
insoluble In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solubil ...
along with separate counter and reference electrodes. An electric
potential difference Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to m ...
is created between the electrodes that causes a charge and the appropriate counter
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
from the
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
to enter the polymer in the form of electron addition (i.e., n-doping) or removal (i.e., p-doping). N-doping is much less common because the
Earth's atmosphere The atmosphere of Earth is the layer of gases, known collectively as air, retained by Earth's gravity that surrounds the planet and forms its planetary atmosphere. The atmosphere of Earth protects life on Earth by creating pressure allowing for ...
is
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
-rich, thus creating an
oxidizing Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
environment. An electron-rich, n-doped polymer will react immediately with elemental oxygen to ''de-dope'' (i.e., reoxidize to the neutral state) the polymer. Thus, chemical n-doping must be performed in an environment of
inert gas An inert gas is a gas that does not readily undergo chemical reactions with other chemical substances and therefore does not readily form chemical compounds. The noble gases often do not react with many substances and were historically referred to ...
(e.g.,
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as abu ...
). Electrochemical n-doping is far more common in research, because it is easier to exclude oxygen from a
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
in a sealed
flask Flask may refer to: Container * Hip flask, a small container used to carry a small amount of liquid * Laboratory flask, laboratory glassware for holding larger volumes than simple test tubes ** Erlenmeyer flask, a common laboratory flask wit ...
. However, it is unlikely that n-doped conductive polymers are available commercially.


Doping in organic molecular semiconductors

Molecular dopants are preferred in doping molecular semiconductors due to their compatibilities of processing with the host, that is, similar evaporation temperatures or controllable solubility. Additionally, the relatively large sizes of molecular dopants compared with those of metal ion dopants (such as Li+ and Mo6+) are generally beneficial, yielding excellent spatial confinement for use in multilayer structures, such as
OLED An organic light-emitting diode (OLED or organic LED), also known as organic electroluminescent (organic EL) diode, is a light-emitting diode (LED) in which the emissive electroluminescent layer is a film of organic compound that emits light i ...
s and
Organic solar cell An organic solar cell (OSC) or plastic solar cell is a type of photovoltaic that uses organic electronics, a branch of electronics that deals with conductive organic polymers or small organic molecules, for light absorption and charge transport t ...
s. Typical p-type dopants include F4-TCNQ and Mo(tfd)3. However, similar to the problem encountered in doping conductive polymers, air-stable n-dopants suitable for materials with low
electron affinity The electron affinity (''E''ea) of an atom or molecule is defined as the amount of energy released when an electron attaches to a neutral atom or molecule in the gaseous state to form an anion. ::X(g) + e− → X−(g) + energy Note that this is ...
(EA) are still elusive. Recently, photoactivation with a combination of cleavable dimeric dopants, such as uCpMessub>2, suggests a new path to realize effective n-doping in low-EA materials.


Magnetic doping

Research on magnetic doping has shown that considerable alteration of certain properties such as specific heat may be affected by small concentrations of an impurity; for example, dopant impurities in semiconducting
ferromagnetic Ferromagnetism is a property of certain materials (such as iron) which results in a large observed magnetic permeability, and in many cases a large magnetic coercivity allowing the material to form a permanent magnet. Ferromagnetic materials ...
alloys can generate different properties as first predicted by White, Hogan, Suhl and Nakamura. The inclusion of dopant elements to impart dilute magnetism is of growing significance in the field of
Magnetic semiconductor Magnetic semiconductors are semiconductor materials that exhibit both ferromagnetism (or a similar response) and useful semiconductor properties. If implemented in devices, these materials could provide a new type of control of conduction. Where ...
s. The presence of disperse ferromagnetic species is key to the functionality of emerging
Spintronics Spintronics (a portmanteau meaning spin transport electronics), also known as spin electronics, is the study of the intrinsic spin of the electron and its associated magnetic moment, in addition to its fundamental electronic charge, in solid-st ...
, a class of systems that utilise electron spin in addition to charge. Using
Density functional theory Density-functional theory (DFT) is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure (or nuclear structure) (principally the ground state) of many-body ...
(DFT) the temperature dependent magnetic behaviour of dopants within a given lattice can be modeled to identify candidate semiconductor systems.


Single dopants in semiconductors

The sensitive dependence of a semiconductor's properties on dopants has provided an extensive range of tunable phenomena to explore and apply to devices. It is possible to identify the effects of a solitary dopant on commercial device performance as well as on the fundamental properties of a semiconductor material. New applications have become available that require the discrete character of a single dopant, such as single-spin devices in the area of quantum information or single-dopant transistors. Dramatic advances in the past decade towards observing, controllably creating and manipulating single dopants, as well as their application in novel devices have allowed opening the new field of solotronics (solitary dopant optoelectronics).


Modulation doping

Electrons or holes introduced by doping are mobile, and can be spatially separated from dopant atoms they have dissociated from. Ionized donors and acceptors however attract electrons and holes, respectively, so this spatial separation requires abrupt changes of dopant levels, of band gap (e.g. a
quantum well A quantum well is a potential well with only discrete energy values. The classic model used to demonstrate a quantum well is to confine particles, which were initially free to move in three dimensions, to two dimensions, by forcing them to occupy ...
), or built-in electric fields (e.g. in case of noncentrosymmetric crystals). This technique is called modulation doping and is advantageous owing to suppressed carrier-donor scattering, allowing very high
mobility Mobility may refer to: Social sciences and humanities * Economic mobility, ability of individuals or families to improve their economic status * Geographic mobility, the measure of how populations and goods move over time * Mobilities, a contemp ...
to be attained.


See also

*
Extrinsic semiconductor An extrinsic semiconductor is one that has been '' doped''; during manufacture of the semiconductor crystal a trace element or chemical called a doping agent has been incorporated chemically into the crystal, for the purpose of giving it different ...
*
Intrinsic semiconductor An intrinsic (pure) semiconductor, also called an undoped semiconductor or i-type semiconductor, is a pure semiconductor without any significant dopant species present. The number of charge carriers is therefore determined by the properties of the ...
*
List of semiconductor materials Semiconductor materials are nominally small band gap insulators. The defining property of a semiconductor material is that it can be compromised by doping it with impurities that alter its electronic properties in a controllable way. Because of ...
* Monolayer doping * p-n junction


References


External links

*{{Commonscatinline Semiconductor properties Semiconductor device fabrication