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History
Carrier concentration
Effect on band structure

Relationship to carrier concentration (low doping)

Techniques of doping and synthesis

Doping during crystal growth

Post-growth doping
Spin-on glass
Neutron transmutation doping
Dopant elements

Group IV semiconductors
Silicon dopants
Other semiconductors
Compensation
Doping in conductive polymers
Doping in organic molecular semiconductors
Magnetic doping
Single dopants in semiconductors
Modulation doping
See also
References
External links
Doping (semiconductor)

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From Wikipedia, the free encyclopedia

Doping of a pure silicon array. Silicon based intrinsic semiconductor becomes

extrinsic when impurities such as boron and antimony are introduced.
In semiconductor production, doping is the intentional introduction of impurities
into an intrinsic (undoped) semiconductor for the purpose of modulating its
electrical, optical and structural properties. The doped material is referred to as
an extrinsic semiconductor.

Small numbers of dopant atoms 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 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
semiconductor can be considered i-type semiconductor if it has been doped in equal
quantities of p and n.

In the context of phosphors and scintillators, doping is better known as

activation; this is not to be confused with dopant activation 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 detectors and selenium rectifiers. For instance, in
1885 Shelford Bidwell, and in 1930 the German scientist Bernhard Gudden, each
independently reported that the properties of semiconductors were due to the
impurities they contained.[1][2] A doping process was formally developed by John
Robert Woodyard working at Sperry Gyroscope Company during World War II. 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.[3] The demands of his work on
radar prevented Woodyard from pursuing further research on semiconductor doping.

Similar work was performed at Bell Labs by Gordon K. Teal and Morgan Sparks, with a
US Patent issued in 1953.[4]

Woodyard's prior patent proved to be the grounds of extensive litigation by Sperry

Rand.[5]

Carrier concentration
The concentration of the dopant used affects many electrical properties. Most
important is the material's charge carrier concentration. In an intrinsic
semiconductor under thermal equilibrium, the concentrations of electrons and holes
are equivalent. That is,

n
=
p
=
n
i
.

{\displaystyle n=p=n_{i}.\ }
In a non-intrinsic semiconductor under thermal equilibrium, the relation becomes
(for low doping):

n
0
⋅
p
0
=
n
i
2

{\displaystyle n_{0}\cdot p_{0}=n_{i}^{2}\ }

where n0 is the concentration of conducting electrons, p0 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's ni, for example, is roughly 1.08×1010 cm−3 at 300 kelvins,
about room temperature.[6]

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 metals and are often used in integrated circuits
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, 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

Band diagram of PN junction operation in forward bias mode showing reducing

depletion width. Both p and n junctions are doped at a 1×1015/cm3 doping level,
leading to built-in potential of ~0.59 V. Reducing depletion width can be inferred
from the shrinking charge profile, as fewer dopants are exposed with increasing
forward bias.
Doping a semiconductor in a good crystal introduces allowed energy states within
the band gap, but very close to the energy band that corresponds to the dopant
type. In other words, electron donor impurities create states near the conduction
band while electron acceptor 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 or EB and is relatively small. For example, the EB
for boron 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 carriers in the
conduction or valence bands.
Dopants also have the important effect of shifting the energy bands relative to the
Fermi level. 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, stacking layers of materials
with different properties leads to many useful electrical properties induced by
band bending, 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. 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 devices.

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):

n
e
=
N
C
(
T
)
exp
⁡
(
(
E
F
−
E
C
)
/
k
T
)
,
n
h
=
N
V
(
T
)
exp
⁡
(
(
E
V
−
E
F
)
/
k
T
)
,
{\displaystyle n_{e}=N_{\rm {C}}(T)\exp((E_{\rm {F}}-E_{\rm {C}})/kT),\quad
n_{h}=N_{\rm {V}}(T)\exp((E_{\rm {V}}-E_{\rm {F}})/kT),}
where EF is the Fermi level, EC is the minimum energy of the conduction band, and
EV is the maximum energy of the valence band. These are related to the value of the
intrinsic concentration via[7]

n
i
2
=
n
h
n
e
=
N
V
(
T
)
N
C
(
T
)
exp
⁡
(
(
E
V
−
E
C
)
/
k
T
)
,
{\displaystyle n_{i}^{2}=n_{h}n_{e}=N_{\rm {V}}(T)N_{\rm {C}}(T)\exp((E_{\rm {V}}-
E_{\rm {C}})/kT),}
an expression which is independent of the doping level, since EC – EV (the band
gap) does not change with doping.

The concentration factors NC(T) and NV(T) are given by

N
C
(
T
)
=
2
(
2
π
m
e
∗
k
T
/
h
2
)
3
/
2
N
V
(
T
)
=
2
(
2
π
m
h
∗
k
T
/
h
2
)
3
/
2
.
{\displaystyle N_{\rm {C}}(T)=2(2\pi m_{e}^{*}kT/h^{2})^{3/2}\quad N_{\rm {V}}
(T)=2(2\pi m_{h}^{*}kT/h^{2})^{3/2}.}
where me* and mh* are the density of states effective masses of electrons and
holes, respectively, quantities that are roughly constant over temperature.[7]

Techniques of doping and synthesis

Doping during crystal growth
Some dopants are added as the (usually silicon) boule is grown by Czochralski
method, giving each wafer an almost uniform initial doping.[8]

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, hydrogen sulfide is added, and sulfur is incorporated into the
structure.[9] This process is characterized by a constant concentration of sulfur
on the surface.[10] 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.[11]
Post-growth doping
To define circuit elements, selected areas — typically controlled by
photolithography[12] — are further doped by such processes as diffusion[13] and ion
implantation, 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. First, a mixture of
SiO2 and dopants (in a solvent) is applied to a wafer surface by spin-coating. Then
it is stripping and baked at a certain temperature in a furnace with constant
nitrogen+oxygen flow.[14]

Neutron transmutation doping

See also: Neutron activation
Neutron 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 atom by neutron absorption as follows:

30
S
i
(
n
,
γ
)
31
S
i
→
31
P
+
β
−
(
T
1
/
2
=
2.62
h
)
.
{\displaystyle ^{30}\mathrm {Si} \,(n,\gamma )\,^{31}\mathrm {Si} \
rightarrow \,^{31}\mathrm {P} +\beta ^{-}\;(T_{1/2}=2.62\mathrm {h} ).}In practice,
the silicon is typically placed near a nuclear reactor 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.[15]
[16]

Dopant elements
Group IV semiconductors
(Note: When discussing periodic table groups, semiconductor physicists always use
an older notation, not the current IUPAC group notation. For example, the carbon
group is called "Group IV", not "Group 14".)

For the Group IV semiconductors such as diamond, silicon, germanium, silicon

carbide, and silicon–germanium, the most common dopants are acceptors from Group
III or donors from Group V elements. Boron, arsenic, phosphorus, and occasionally
gallium 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 elements such as phosphorus, extra valence
electrons 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 element is said to
behave as an electron donor, and a Group III element as an acceptor. This is a key
concept in the physics of 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 sensistors.[17] Lower dosage of doping is used in other types (NTC or
PTC) thermistors.

Silicon dopants
Acceptors, p-type
Boron is a p-type dopant. Its diffusion rate allows easy control of junction
depths. Common in CMOS technology. Can be added by diffusion of diborane 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.[18]
Gallium is a dopant used for long-wavelength infrared photoconduction silicon
detectors in the 8–14 μm atmospheric window.[19] 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.[18]
Indium is a dopant used for long-wavelength infrared photoconduction silicon
detectors in the 3–5 μm atmospheric window.[19]
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 gas. Bulk doping can be achieved by nuclear transmutation, by irradiation
of pure silicon with neutrons in a nuclear reactor. 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.[18]
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.[18]
Bismuth is a promising dopant for long-wavelength infrared photoconduction silicon
detectors, a viable n-type alternative to the p-type gallium-doped material.[20]
Lithium is used for doping silicon for radiation hardened solar cells. The lithium
presence anneals defects in the lattice produced by protons and neutrons.[21]
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.[22]
Other
Germanium can be used for band gap engineering. Germanium layer also inhibits
diffusion of boron during the annealing steps, allowing ultrashallow p-MOSFET
junctions.[23] Germanium bulk doping suppresses large void defects, increases
internal gettering, and improves wafer mechanical strength.[18]
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.[18]
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.[24]
Other semiconductors
[25] In the following list the "(substituting X)" refers to all of the materials
preceding said parenthesis.

Gallium arsenide
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
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 LEDs (GaP has indirect band gap)
Gallium nitride, Indium gallium nitride, Aluminium gallium nitride
n-type: silicon (substituting Ga), germanium (substituting Ga, better lattice
match), carbon (substituting Ga, naturally embedding into MOVPE-grown layers in low
concentration)
p-type: magnesium (substituting Ga) - challenging due to relatively high ionisation
energy above the valence band edge, strong diffusion of interstitial Mg, hydrogen
complexes passivating of Mg acceptors and by Mg self-compensation at higher
concentrations)
Cadmium telluride
n-type: indium, aluminium (substituting Cd); chlorine (substituting Te)
p-type: phosphorus (substituting Te); lithium, sodium (substituting Cd)
Cadmium sulfide
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.[26] 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 is always decreased by compensation
because mobility is affected by the sum of the donor and acceptor ions.

Doping in conductive polymers

Main article: Conductive polymer
Conductive polymers can be doped by adding chemical reactants to oxidize, 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) process.

Chemical doping involves exposing a polymer such as melanin, typically a thin film,
to an oxidant such as iodine or bromine. Alternatively, the polymer can be exposed
to a reductant; this method is far less common, and typically involves alkali
metals.
Electrochemical doping involves suspending a polymer-coated, working electrode in
an electrolyte solution in which the polymer is insoluble along with separate
counter and reference electrodes. An electric potential difference is created
between the electrodes that causes a charge and the appropriate counter ion from
the electrolyte 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 is oxygen-rich, thus
creating an oxidizing 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 (e.g., argon). Electrochemical n-doping is far more common in research, because
it is easier to exclude oxygen from a solvent in a sealed flask. 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.[27] 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 OLEDs and Organic solar cells. Typical p-type
dopants include F4-TCNQ[28] and Mo(tfd)3.[29] However, similar to the problem
encountered in doping conductive polymers, air-stable n-dopants suitable for
materials with low electron affinity (EA) are still elusive. Recently,
photoactivation with a combination of cleavable dimeric dopants, such as
[RuCp∗Mes]2, suggests a new path to realize effective n-doping in low-EA materials.
[27]

Magnetic doping
Main article: Magnetic semiconductor
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 alloys can
generate different properties as first predicted by White, Hogan, Suhl and
Nakamura.[30][31] The inclusion of dopant elements to impart dilute magnetism is of
growing significance in the field of magnetic semiconductors. The presence of
disperse ferromagnetic species is key to the functionality of emerging spintronics,
a class of systems that utilise electron spin in addition to charge. Using density
functional theory (DFT) the temperature dependent magnetic behaviour of dopants
within a given lattice can be modeled to identify candidate semiconductor systems.
[32]

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).[33]

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), 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 to be attained.

See also
Extrinsic semiconductor
Intrinsic semiconductor
List of semiconductor materials
Monolayer doping
p-n junction
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Doping (semiconductor)

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