Doping (semiconductor)

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In semiconductor production, doping is the intentional introduction of impurities into an intrinsic semiconductor for the purpose of modulating its electrical, optical and structural properties. The doped material is referred to as an extrinsic semiconductor. 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 material has an electrical conductivity value falling between that of a metal, like copper, gold, etc. and an insulator, such as glass. Their resistance decreases as their temperature increases, which is behaviour opposite to that of a metal. Their conducting properties may be altered in useful ways by the deliberate, controlled introduction of impurities ("doping") into the crystal structure. Where two differently-doped regions exist in the same crystal, a semiconductor junction is created. The behavior of charge carriers which include electrons, ions and electron holes at these junctions is the basis of diodes, transistors and all modern electronics. Some examples of semiconductors are silicon, germanium, and gallium arsenide. After silicon, gallium arsenide is the second most common semiconductor used in laser diodes, solar cells, microwave frequency integrated circuits, and others. Silicon is a critical element for fabricating most electronic circuits.


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 material itself instead of the amount of impurities. In intrinsic semiconductors the number of excited electrons and the number of holes are equal: n = p. This may even be the case after doping the semiconductor, though only if it is doped with both donors and acceptors equally. In this case, n = p still holds, and the semiconductor remains intrinsic, though doped.

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 electrical properties than the pure semiconductor crystal, which is called an intrinsic semiconductor. In an extrinsic semiconductor it is these foreign dopant atoms in the crystal lattice that mainly provide the charge carriers which carry electric current through the crystal. The doping agents used are of two types, resulting in two types of extrinsic semiconductor. An electron donor dopant is an atom which, when incorporated in the crystal, releases a mobile conduction electron into the crystal lattice. An extrinsic semiconductor which has been doped with electron donor atoms is called an n-type semiconductor, because the majority of charge carriers in the crystal are negative electrons. An electron acceptor dopant is an atom which accepts an electron from the lattice, creating a vacancy where an electron should be called a hole which can move through the crystal like a positively charged particle. An extrinsic semiconductor which has been doped with electron acceptor atoms is called a p-type semiconductor, because the majority of charge carriers in the crystal are positive holes.

Contents

In the context of phosphors and scintillators, doping is better known as activation. Doping is also used to control the color in some pigments.

Phosphor substance exhibiting luminescence

A phosphor, most generally, is a substance that exhibits the phenomenon of luminescence. Somewhat confusingly, this includes both phosphorescent materials, which show a slow decay in brightness, and fluorescent materials, where the emission decay takes place over tens of nanoseconds. Phosphorescent materials are known for their use in radar screens and glow-in-the-dark materials, whereas fluorescent materials are common in cathode ray tube (CRT) and plasma video display screens, fluorescent lights, sensors, and white LEDs.

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. Sometimes, the excited state is metastable, so the relaxation back down from the excited state to lower states is delayed : the process then corresponds to either one of two phenomena, depending on the type of transition and hence the wavelength of the emitted optical photon: delayed fluorescence or phosphorescence, also called after-glow.

In phosphors and scintillators, the activator is the element added as dopant to the crystal of the material to create desired type of nonhomogeneities.

History

The effects of semiconductor 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 contained within them. [1] [2] The doping process was formally first developed by John Robert Woodyard working at Sperry Gyroscope Company during World War II, with a US Patent issued in 1950. [3] The demands of his work on radar denied Woodyard the opportunity to pursue research on semiconductor doping.

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 important component, a crystal detector, originally made from a piece of crystalline mineral such as galena. This component is now called a diode.

Shelford Bidwell FRS was an English physicist and inventor. He is best known for his work with "telephotography", a precursor to the modern fax machine.

John Robert Woodyard (1904–1981) was an American physicist who made important contributions to the technology of microwave electronics and invented "doping" to improve the performance of semiconductors.

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

Bell Labs research and scientific development company

Nokia Bell Labs is an industrial research and scientific development company, owned by Finnish company Nokia. Its headquarters are located in Murray Hill, New Jersey, in addition to other laboratories around the rest of the United States and in other countries.

Morgan Sparks 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 directed Sandia National Laboratories.

Woodyard's prior patent proved to be the grounds of extensive litigation by Sperry Rand . [5]

Patent set of exclusive rights granted by a sovereign state to an inventor or their assignee so that he has a temporary monopoly

A patent is a form of intellectual property. A patent gives its owner the right to exclude others from making, using, selling, and importing an invention for a limited period of time, usually twenty years. The patent rights are granted in exchange for an enabling public disclosure of the invention. In most countries patent rights fall under civil law and the patent holder needs to sue someone infringing the patent in order to enforce his or her rights. In some industries patents are an essential form of competitive advantage; in others they are irrelevant.

Carrier concentration

The concentration of dopant 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,

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. In a conducting medium, an electric field can exert force on these free particles, causing a net motion of the particles through the medium; this is what constitutes an electric current. In different conducting media, different particles serve to carry charge:

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 thermal equilibrium with itself if the temperature within the system is spatially uniform and temporally constant.

Electron subatomic particle with negative electric charge

The electron is a subatomic particle, symbol
e
or
β
, whose electric charge is negative one elementary charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no known components or substructure. The electron has a mass that is approximately 1/1836 that of the proton. Quantum mechanical properties of the electron include an intrinsic angular momentum (spin) of a half-integer value, expressed in units of the reduced Planck constant, ħ. As it is a fermion, no two electrons can occupy the same quantum state, in accordance with the Pauli exclusion principle. Like all elementary particles, electrons exhibit properties of both particles and waves: they can collide with other particles and can be diffracted like light. The wave properties of electrons are easier to observe with experiments than those of other particles like neutrons and protons because electrons have a lower mass and hence a longer de Broglie wavelength for a given energy.

In a non-intrinsic semiconductor under thermal equilibrium, the relation becomes (for low doping):

where n0 is the concentration of conducting electrons, p0 is the electron 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 1×10 /cm 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. PN band.gif
Band diagram of PN junction operation in forward bias mode showing reducing depletion width. Both p and n junctions are doped at a 1×10 /cm 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):

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]

an expression which is independent of the doping level, since ECEV (the band gap) does not change with doping.

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

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

The synthesis of n-type semiconductors may involve the use of vapor-phase epitaxy. In vapor-phase epitaxy, a gas containing the negative dopant is passed over the substrate wafer. In the case of n-type GaAs doping, hydrogen sulfide is passed over the gallium arsenide, and sulfur is incorporated into the structure. [8] This process is characterized by a constant concentration of sulfur on the surface. [9] 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. [10] The reaction conditions typically range from 600 to 800 °C for the n-doping with group VI elements, [8] and the time is typically 6–12 hours depending on the temperature.

Process

Some dopants are added as the (usually silicon) boule is grown, giving each wafer an almost uniform initial doping. [11] 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.

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.)

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 unbonded 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. [14] Lower dosage of doping is used in other types (NTC or PTC) thermistors.

Silicon dopants

Other semiconductors

[22]

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 given portion of the material by applying successively higher doses of dopants, so-called counterdoping. Most modern semiconductors are made by successive selective counterdoping steps to create the necessary P and N type areas. [23]

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

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.

  1. 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.
  2. 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. [24] Besides, molecular dopants are also benefitted from their relatively large size comparing metal ion dopants (such as Li+ and Mo6+), which makes them have excellent spatial confinement in order to be used in multilayer structure, such as OLED s and Organic solar cell s. The typical p-type dopants are F4-TCNQ [25] and Mo(tfd)3. [26] However, as the similar problem encountered in doping conductive polymers, air-stable n-dopants suitable for materials with low electron affinity(EA) are still elusive. Recently, photo-activation with the combination of cleavable dimeric dopants, such as [RuCpMes]2, suggest a new path to realize effective n-doping in those low-EA materials. [24]

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 alloys can generate different properties as first predicted by White, Hogan, Suhl and Nakamura. [27] [28] 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. [29]

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). [30]

Neutron transmutation doping

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. It is based on the conversion of the Si-30 isotope into phosphorus atom by neutron absorption as follows:

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. [31] [32]

Modulation doping

Modulation doping is a synthesis technique in which the dopants are spatially separated from the carriers. In this way, carrier-donor scattering is suppressed, allowing very high mobility to be attained.

See also

Related Research Articles

Semiconductor devices are electronic components that exploit the electronic properties of semiconductor material, principally silicon, germanium, and gallium arsenide, as well as organic semiconductors. Semiconductor devices have replaced thermionic devices in most applications. They use electronic conduction in the solid state as opposed to the gaseous state or thermionic emission in a high vacuum.

Czochralski process

The Czochralski process is a method of crystal growth used to obtain single crystals of semiconductors, metals, salts and synthetic gemstones. The process is named after Polish scientist Jan Czochralski, who invented the method in 1915 while investigating the crystallization rates of metals. He made this discovery by accident, while studying the crystallization rate of metals: instead of dipping his pen into his inkwell, he dipped it in molten tin, and drew a tin filament, which later proved to be a single crystal.

Epitaxy crystal growth process

Epitaxy refers to the deposition of a crystalline overlayer on a crystalline substrate.

p–n junction semiconductor–semiconductor junction, formed at the boundary between a p-type and n-type semiconductor

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 contains an excess of electrons in the outer shells of the electrically neutral atoms there. This allows electrical current to pass through the junction only in one direction. The p-n junction is created by doping, for example by ion implantation, diffusion of dopants, or by epitaxy. If two separate pieces of material were used, this would introduce a grain boundary between the semiconductors that would severely inhibit its utility by scattering the electrons and holes.

In solid-state physics, the electron mobility characterizes how quickly an electron can move through a metal or semiconductor, when pulled by an electric field. There is an analogous quantity for holes, called hole mobility. The term carrier mobility refers in general to both electron and hole mobility.

This article is about ionizing radiation detectors. For information about semiconductor detectors in radio, see Detector (radio), Crystal detector, Diode#Semiconductor diodes, and Rectifier.

High-electron-mobility transistor

A High-electron-mobility transistor (HEMT), also known as heterostructure FET (HFET) or modulation-doped FET (MODFET), is a field-effect transistor incorporating a junction between two materials with different band gaps as the channel instead of a doped region. A commonly used material combination is GaAs with AlGaAs, though there is wide variation, dependent on the application of the device. Devices incorporating more indium generally show better high-frequency performance, while in recent years, gallium nitride HEMTs have attracted attention due to their high-power performance. Like other FETs, HEMTs are used in integrated circuits as digital on-off switches. FETs can also be used as amplifiers for large amounts of current using a small voltage as a control signal. Both of these uses are made possible by the FET’s unique current-voltage characteristics. HEMT transistors are able to operate at higher frequencies than ordinary transistors, up to millimeter wave frequencies, and are used in high-frequency products such as cell phones, satellite television receivers, voltage converters, and radar equipment. They are widely used in satellite receivers, in low power amplifiers and in the defense industry.

Magnetic semiconductors are semiconductor materials that exhibit both ferromagnetism and useful semiconductor properties. If implemented in devices, these materials could provide a new type of control of conduction. Whereas traditional electronics are based on control of charge carriers, practical magnetic semiconductors would also allow control of quantum spin state. This would theoretically provide near-total spin polarization, which is an important property for spintronics applications, e.g. spin transistors.

Gallium phosphide chemical compound

Gallium phosphide (GaP), a phosphide of gallium, is a compound semiconductor material with an indirect band gap of 2.26 eV at 300 K. The polycrystalline material has the appearance of pale orange pieces. Undoped single crystal wafers appear clear orange, but strongly doped wafers appear darker due to free-carrier absorption. It is odorless and insoluble in water.

Acceptor (semiconductors)

In semiconductor physics, an acceptor is a dopant atom that when added to a semiconductor can form a p-type region.

Donor (semiconductors) dopant atom that, when added to a semiconductor, can form a n-type region

In semiconductor physics, a donor is a dopant atom that, when added to a semiconductor, can form a n-type region.

In solid-state physics, a metal–semiconductor (M–S) junction is a type of junction in which a metal comes in close contact with a semiconductor material. It is the oldest practical semiconductor device. M–S junctions can either be rectifying or non-rectifying. The rectifying metal–semiconductor junction forms a Schottky barrier, making a device known as a Schottky diode, while the non-rectifying junction is called an ohmic contact.

Covalent superconductors are superconducting materials where the atoms are linked by covalent bonds. The first such material was boron-doped synthetic diamond grown by the high-pressure high-temperature (HPHT) method. The discovery had no practical importance, but surprised most scientists as superconductivity had not been observed in covalent semiconductors, including diamond and silicon.

A dopant, also called a doping agent, is a trace impurity element that is inserted into a substance to alter the electrical or optical properties of the substance. In the case of crystalline substances, the atoms of the dopant very commonly take the place of elements that were in the crystal lattice of the base material. The crystalline materials are frequently either crystals of a semiconductor such as silicon and germanium for use in solid-state electronics, or transparent crystals for use in the production of various laser types; however, in some cases of the latter, noncrystalline substances such as glass can also be doped with impurities.

Monolayer doping (MLD) is a well controlled, wafer-scale surface doping technique first developed at the University of California, Berkeley, in 2007. This work is aimed for attaining controlled doping of semiconductor materials with atomic accuracy, especially at nanoscale, which is not easily obtained by other existing technologies. This technique is currently used for fabricating ultrashallow junctions (USJs) as the heavily doped source/drain (S/D) contacts of metal-oxide-semiconductor field effect transistors (MOSFETs) as well as enabling dopant profiling of nanostructures.

When optical fibers are exposed to ionizing radiation such as energetic electrons, protons, neutrons, X-rays, Ƴ-radiation, etc., they undergo 'damage'. The term 'damage' primarily refers to the additional loss of the propagating optical signal leading to decreased power at the output end which could lead to premature failure of the component and or system.

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