Energy range in a solid where no electron states exist
This article is about solid state physics. For voltage control circuitry in electronics, see Bandgap voltage reference.
This article is about the electronic bandgap found in semiconductors. For the photonic band gap, see Photonic crystal.
Graph of carbon atoms being brought together to form a diamond crystal, demonstrating formation of the electronic band structure and band gap. The right graph shows the energy levels as a function of the spacing between atoms. When far apart (right side of graph) all the atoms have discrete valence orbitals p and s with the same energies. However, when the atoms come closer (left side), their electron orbitals begin to spatially overlap and hybridize into N molecular orbitals each with a different energy, where N is the number of atoms in the crystal. Since N is such a large number, adjacent orbitals are extremely close together in energy so the orbitals can be considered a continuous energy band. At the actual diamond crystal cell size (denoted by a), two bands are formed, called the valence and conduction bands, separated by a 5.5eV band gap. The Pauli exclusion principle limits the number of electrons in a single orbital to two, and the bands are filled beginning with the lowest energy.
In solid-state physics and solid-state chemistry, a band gap, also called a bandgap or energy gap, is an energy range in a solid where no electronic states exist. In graphs of the electronic band structure of solids, the band gap refers to the energy difference (often expressed in electronvolts) between the top of the valence band and the bottom of the conduction band in insulators and semiconductors. It is the energy required to promote an electron from the valence band to the conduction band. The resulting conduction-band electron (and the electron hole in the valence band) are free to move within the crystal lattice and serve as charge carriers to conduct electric current. It is closely related to the HOMO/LUMO gap in chemistry. If the valence band is completely full and the conduction band is completely empty, then electrons cannot move within the solid because there are no available states. If the electrons are not free to move within the crystal lattice, then there is no generated current due to no net charge carrier mobility. However, if some electrons transfer from the valence band (mostly full) to the conduction band (mostly empty), then current can flow (see carrier generation and recombination). Therefore, the band gap is a major factor determining the electrical conductivity of a solid. Substances having large band gaps (also called "wide" band gaps) are generally insulators, those with small band gaps (also called "narrow" band gaps) are semiconductor, and conductors either have very small band gaps or none, because the valence and conduction bands overlap to form a continuous band.
Every solid has its own characteristic energy-band structure. This variation in band structure is responsible for the wide range of electrical characteristics observed in various materials. Depending on the dimension, the band structure and spectroscopy can vary. The different types of dimensions are as listed: one dimension, two dimensions, and three dimensions.[1]
In semiconductors and insulators, electrons are confined to a number of bands of energy, and forbidden from other regions because there are no allowable electronic states for them to occupy. The term "band gap" refers to the energy difference between the top of the valence band and the bottom of the conduction band. Electrons are able to jump from one band to another. However, in order for a valence band electron to be promoted to the conduction band, it requires a specific minimum amount of energy for the transition. This required energy is an intrinsic characteristic of the solid material. Electrons can gain enough energy to jump to the conduction band by absorbing either a phonon (heat) or a photon (light).
A semiconductor is a material with an intermediate-sized, non-zero band gap that behaves as an insulator at T=0K, but allows thermal excitation of electrons into its conduction band at temperatures that are below its melting point. In contrast, a material with a large band gap is an insulator. In conductors, the valence and conduction bands may overlap, so there is no longer a bandgap with forbidden regions of electronic states.
The conductivity of intrinsic semiconductors is strongly dependent on the band gap. The only available charge carriers for conduction are the electrons that have enough thermal energy to be excited across the band gap and the electron holes that are left off when such an excitation occurs.
Band-gap engineering is the process of controlling or altering the band gap of a material by controlling the composition of certain semiconductor alloys, such as GaAlAs, InGaAs, and InAlAs. It is also possible to construct layered materials with alternating compositions by techniques like molecular-beam epitaxy. These methods are exploited in the design of heterojunction bipolar transistors (HBTs), laser diodes and solar cells.
The distinction between semiconductors and insulators is a matter of convention. One approach is to think of semiconductors as a type of insulator with a narrow band gap. Insulators with a larger band gap, usually greater than 4 eV,[2] are not considered semiconductors and generally do not exhibit semiconductive behaviour under practical conditions. Electron mobility also plays a role in determining a material's informal classification.
The band-gap energy of semiconductors tends to decrease with increasing temperature. When temperature increases, the amplitude of atomic vibrations increase, leading to larger interatomic spacing. The interaction between the lattice phonons and the free electrons and holes will also affect the band gap to a smaller extent.[3] The relationship between band gap energy and temperature can be described by Varshni's empirical expression (named after Y. P. Varshni),
Furthermore, lattice vibrations increase with temperature, which increases the effect of electron scattering. Additionally, the number of charge carriers within a semiconductor will increase, as more carriers have the energy required to cross the band-gap threshold and so conductivity of semiconductors also increases with increasing temperature.[5] The external pressure also influences the electronic structure of semiconductors and, therefore, their optical band gaps.[6]
In a regular semiconductor crystal, the band gap is fixed owing to continuous energy states. In a quantum dot crystal, the band gap is size dependent and can be altered to produce a range of energies between the valence band and conduction band.[7] It is also known as quantum confinement effect.
It was mentioned earlier that the dimensions have different band structure and spectroscopy. For non-metallic solids, which are one dimensional, have optical properties that are dependent on the electronic transitions between valence and conduction bands. In addition, the spectroscopic transition probability is between the initial and final orbital and it depends on the integral.[1] φi is the initial orbital, φf is the final orbital, ʃ φf*ûεφi is the integral, ε is the electric vector, and u is the dipole moment.[1]
Two-dimensional structures of solids behave because of the overlap of atomic orbitals.[1] The simplest two-dimensional crystal contains identical atoms arranged on a square lattice.[1] Energy splitting occurs at the Brillouin zone edge for one-dimensional situations because of a weak periodic potential, which produces a gap between bands. The behavior of the one-dimensional situations does not occur for two-dimensional cases because there are extra freedoms of motion. Furthermore, a bandgap can be produced with strong periodic potential for two-dimensional and three-dimensional cases.[1]
Based on their band structure, materials are characterised with a direct band gap or indirect band gap. In the free-electron model, k is the momentum of a free electron and assumes unique values within the Brillouin zone that outlines the periodicity of the crystal lattice. If the momentum of the lowest energy state in the conduction band and the highest energy state of the valence band of a material have the same value, then the material has a direct bandgap. If they are not the same, then the material has an indirect band gap and the electronic transition must undergo momentum transfer to satisfy conservation. Such indirect "forbidden" transitions still occur, however at very low probabilities and weaker energy.[6][8][9] For materials with a direct band gap, valence electrons can be directly excited into the conduction band by a photon whose energy is larger than the bandgap. In contrast, for materials with an indirect band gap, a photon and phonon must both be involved in a transition from the valence band top to the conduction band bottom, involving a momentum change. Therefore, direct bandgap materials tend to have stronger light emission and absorption properties and tend to be better suited for photovoltaics (PVs), light-emitting diodes (LEDs), and laser diodes;[10] however, indirect bandgap materials are frequently used in PVs and LEDs when the materials have other favorable properties.
LEDs and laser diodes usually emit photons with energy close to and slightly larger than the band gap of the semiconductor material from which they are made. Therefore, as the band gap energy increases, the LED or laser color changes from infrared to red, through the rainbow to violet, then to UV.[11]
The Shockley–Queisser limit gives the maximum possible efficiency of a single-junction solar cell under un-concentrated sunlight, as a function of the semiconductor band gap. If the band gap is too high, most daylight photons cannot be absorbed; if it is too low, then most photons have much more energy than necessary to excite electrons across the band gap, and the rest is wasted. The semiconductors commonly used in commercial solar cells have band gaps near the peak of this curve, as it occurs in silicon-based cells. The Shockley–Queisser limit has been exceeded experimentally by combining materials with different band gap energies to make, for example, tandem solar cells.
The optical band gap (see below) determines what portion of the solar spectrum a photovoltaic cell absorbs.[12] Strictly, a semiconductor will not absorb photons of energy less than the band gap; whereas most of the photons with energies exceeding the band gap will generate heat. Neither of them contribute to the efficiency of a solar cell. One way to circumvent this problem is based on the so-called photon management concept, in which case the solar spectrum is modified to match the absorption profile of the solar cell.[13]
List of band gaps
Below are band gap values for some selected materials.[14] For a comprehensive list of band gaps in semiconductors, see List of semiconductor materials.
In materials with a large exciton binding energy, it is possible for a photon to have just barely enough energy to create an exciton (bound electron–hole pair), but not enough energy to separate the electron and hole (which are electrically attracted to each other). In this situation, there is a distinction between "optical band gap" and "electronic band gap" (or "transport gap"). The optical bandgap is the threshold for photons to be absorbed, while the transport gap is the threshold for creating an electron–hole pair that is not bound together. The optical bandgap is at lower energy than the transport gap.
In almost all inorganic semiconductors, such as silicon, gallium arsenide, etc., there is very little interaction between electrons and holes (very small exciton binding energy), and therefore the optical and electronic bandgap are essentially identical, and the distinction between them is ignored. However, in some systems, including organic semiconductors and single-walled carbon nanotubes, the distinction may be significant.
Band gaps for other quasi-particles
In photonics, band gaps or stop bands are ranges of photon frequencies where, if tunneling effects are neglected, no photons can be transmitted through a material. A material exhibiting this behaviour is known as a photonic crystal. The concept of hyperuniformity[22] has broadened the range of photonic band gap materials, beyond photonic crystals. By applying the technique in supersymmetric quantum mechanics, a new class of optical disordered materials has been suggested,[23] which support band gaps perfectly equivalent to those of crystals or quasicrystals.
A semiconductor is a material that is between the conductor and insulator in ability to conduct electrical current. In many cases their conducting properties may be altered in useful ways by introducing impurities ("doping") into the crystal structure. When 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 most modern electronics. Some examples of semiconductors are silicon, germanium, gallium arsenide, and elements near the so-called "metalloid staircase" on the periodic table. After silicon, gallium arsenide is the second-most common semiconductor and is used in laser diodes, solar cells, microwave-frequency integrated circuits, and others. Silicon is a critical element for fabricating most electronic circuits.
An electron and an electron hole that are attracted to each other by the Coulomb force can form a bound state called an exciton. It is an electrically neutral quasiparticle that exists mainly in condensed matter, including insulators, semiconductors, some metals, but also in certain atoms, molecules and liquids. The exciton is regarded as an elementary excitation that can transport energy without transporting net electric charge.
Cathodoluminescence is an optical and electromagnetic phenomenon in which electrons impacting on a luminescent material such as a phosphor, cause the emission of photons which may have wavelengths in the visible spectrum. A familiar example is the generation of light by an electron beam scanning the phosphor-coated inner surface of the screen of a television that uses a cathode-ray tube. Cathodoluminescence is the inverse of the photoelectric effect, in which electron emission is induced by irradiation with photons.
A laser diode is a semiconductor device similar to a light-emitting diode in which a diode pumped directly with electrical current can create lasing conditions at the diode's junction.
Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a zinc blende crystal structure.
Wide-bandgap semiconductors are semiconductor materials which have a larger band gap than conventional semiconductors. Conventional semiconductors like Silicon and Selenium have a bandgap in the range of 0.7 – 1.5 electronvolt (eV), whereas wide-bandgap materials have bandgaps in the range above 2 eV. Generally, wide-bandgap semiconductors have electronic properties which fall in between those of conventional semiconductors and insulators.
A quantum well is a potential well with only discrete energy values.
In solid-state physics, the electronic band structure of a solid describes the range of energy levels that electrons may have within it, as well as the ranges of energy that they may not have.
A semimetal is a material with a small energy overlap between the bottom of the conduction band and the top of the valence band, but they do not overlap in momentum space. According to electronic band theory, solids can be classified as insulators, semiconductors, semimetals, or metals. In insulators and semiconductors the filled valence band is separated from an empty conduction band by a band gap. For insulators, the magnitude of the band gap is larger than that of a semiconductor. Because of the slight overlap between the conduction and valence bands, semimetals have no band gap and a small density of states at the Fermi level. A metal, by contrast, has an appreciable density of states at the Fermi level because the conduction band is partially filled.
In solid-state physics of semiconductors, carrier generation and carrier recombination are processes by which mobile charge carriers are created and eliminated. Carrier generation and recombination processes are fundamental to the operation of many optoelectronic semiconductor devices, such as photodiodes, light-emitting diodes and laser diodes. They are also critical to a full analysis of p-n junction devices such as bipolar junction transistors and p-n junction diodes.
Indium gallium arsenide (InGaAs) is a ternary alloy of indium arsenide (InAs) and gallium arsenide (GaAs). Indium and gallium are group III elements of the periodic table while arsenic is a group V element. Alloys made of these chemical groups are referred to as "III-V" compounds. InGaAs has properties intermediate between those of GaAs and InAs. InGaAs is a room-temperature semiconductor with applications in electronics and photonics.
Hybrid solar cells combine advantages of both organic and inorganic semiconductors. Hybrid photovoltaics have organic materials that consist of conjugated polymers that absorb light as the donor and transport holes. Inorganic materials are used as the acceptor and electron transport. These devices have a potential for low-cost by roll-to-roll processing and scalable solar power conversion.
A quantum dot solar cell (QDSC) is a solar cell design that uses quantum dots as the captivating photovoltaic material. It attempts to replace bulk materials such as silicon, copper indium gallium selenide (CIGS) or cadmium telluride (CdTe). Quantum dots have bandgaps that are adjustable across a wide range of energy levels by changing their size. In bulk materials, the bandgap is fixed by the choice of material(s). This property makes quantum dots attractive for multi-junction solar cells, where a variety of materials are used to improve efficiency by harvesting multiple portions of the solar spectrum.
Multi-junction (MJ) solar cells are solar cells with multiple p–n junctions made of different semiconductor materials. Each material's p–n junction will produce electric current in response to different wavelengths of light. The use of multiple semiconducting materials allows the absorbance of a broader range of wavelengths, improving the cell's sunlight to electrical energy conversion efficiency.
In physics, the radiative efficiency limit is the maximum theoretical efficiency of a solar cell using a single p-n junction to collect power from the cell where the only loss mechanism is radiative recombination in the solar cell. It was first calculated by William Shockley and Hans-Joachim Queisser at Shockley Semiconductor in 1961, giving a maximum efficiency of 30% at 1.1 eV. The limit is one of the most fundamental to solar energy production with photovoltaic cells, and is one of the field's most important contributions.
In semiconductors, 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 characterized by a certain crystal momentum (k-vector) in the Brillouin zone. If the k-vectors are different, the material has an "indirect gap". The band gap is called "direct" if the crystal momentum of electrons and holes is the same in both the conduction band and the valence band; an electron can directly emit a photon. In an "indirect" gap, a photon cannot be emitted because the electron must pass through an intermediate state and transfer momentum to the crystal lattice.
Two-photon photovoltaic effect is an energy collection method based on two-photon absorption (TPA). The TPP effect can be thought of as the nonlinear equivalent of the traditional photovoltaic effect involving high optical intensities. This effect occurs when two photons are absorbed at the same time resulting in an electron-hole pair.
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 which electrons are normally present at absolute zero temperature, while the conduction band is the lowest range of vacant electronic states. On a graph of the electronic band structure of a semiconducting material, the valence band is located below the Fermi level, while the conduction band is located above it.
Light-emitting diodes (LEDs) produce light by the recombination of electrons and electron holes in a semiconductor, a process called "electroluminescence". The wavelength of the light produced depends on the energy band gap of the semiconductors used. Since these materials have a high index of refraction, design features of the devices such as special optical coatings and die shape are required to efficiently emit light. A LED is a long-lived light source, but certain mechanisms can cause slow loss of efficiency of the device or sudden failure. The wavelength of the light emitted is a function of the band gap of the semiconductor material used; materials such as gallium arsenide, and others, with various trace doping elements, are used to produce different colors of light. Another type of LED uses a quantum dot which can have its properties and wavelength adjusted by its size. Light-emitting diodes are widely used in indicator and display functions, and white LEDs are displacing other technologies for general illumination purposes.
References
1 2 3 4 5 6 Cox, P.A. (1987). The Electronic Structure and Chemistry of Solids. pp.102–114.
↑ Babu, V. Suresh (2010). Solid State Devices and Technology, 3rd Edition. Peason.
1 2 Yu, P.Y.; Cardona, M. (1996). "Chapter 6". Fundamentals of semiconductors. Springer. ISBN3-540-61461-3.
1 2 Fox, M. (2008). "Chapters 1–3". Optical properties of solids. Oxford Univ. Press. ISBN978-0-19-850613-3.
↑ Sze, S.M. (1981). "Chapters 12–14". Physics of semiconductor devices. John Wiley & Sons. ISBN0471056618.
↑ Dean, K J (August 1984). "Waves and Fields in Optoelectronics: Prentice-Hall Series in Solid State Physical Electronics". Physics Bulletin. 35 (8): 339. doi:10.1088/0031-9112/35/8/023.
1 2 Goetzberger, A.; Knobloch, J.; Voss, B. (1998). Crystalline silicon solar cells. John Wiley & Sons. ISBN0-471-97144-8.
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