Condensed matter physics |
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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. [1] [2] [3] [4]
An exciton can form when an electron from the valence band of a crystal is promoted in energy to the conduction band e.g., when a material absorbs a photon. Promoting the electron to the conduction band leaves a positively charged hole in the valence band. Here 'hole' represents the unoccupied quantum mechanical electron state with a positive charge, an analogue in crystal of a positron. Because of the attractive coulomb force between the electron and the hole, a bound state is formed, akin to that of the electron and proton in a hydrogen atom or the electron and positron in positronium. Excitons are composite bosons since they are formed from two fermions which are the electron and the hole.
Excitons are often treated in the two limiting cases:
(i) The small radius excitons, or Frenkel excitons, where the electron-hole relative distance is restricted to one or only a few nearest neighbour unit cells. Frenkel excitons typically occur in insulators and organic semiconductors with relatively narrow allowed energy bands and accordingly, rather heavy Effective mass.
(ii) the large radius excitons are called Wannier-Mott excitons, for which the relative motion of electron and hole in the crystal covers many unit cells. Wannier-Mott excitons are considered as hydrogen-like quasiparticles. The wavefunction of the bound state then is said to be hydrogenic, resulting in a series of energy states in analogy to a hydrogen atom. Compared to a hydrogen atom, the exciton binding energy in a crystal is much smaller and the exciton's size (radius) is much larger. This is mainly because of two effects: (a) Coulomb forces are screened in a crystal, which is expressed as a relative permittivity εr significantly larger than 1 and (b) the Effective mass of the electron and hole in a crystal are typically smaller compared to that of free electrons. Wannier-Mott excitons with binding energies ranging from a few to hundreds of meV, depending on the crystal, occur in many semiconductors including Cu2 O, GaAs, other III-V and II-VI semiconductors, transition metal dichalcogenides such as MoS2.
Excitons give rise to spectrally narrow lines in optical absorption, reflection, transmission and luminescence spectra with the energies below the free-particle band gap of an insulator or a semiconductor. Exciton binding energy and radius can be extracted from optical absorption measurements in applied magnetic fields. [5]
The exciton as a quasiparticle is characterized by the momentum (or wavevector K) describing free propagation of the electron-hole pair as a composite particle in the crystalline lattice in agreement with the Bloch theorem. The exciton energy depends on K and is typically parabolic for the wavevectors much smaller than the reciprocal lattice vector of the host lattice. The exciton energy also depends on the respective orientation of the electron and hole spins, whether they are parallel or anti-parallel. The spins are coupled by the exchange interaction, giving rise to exciton energy fine structure.
In metals and highly doped semiconductors a concept of the Gerald Mahan exciton is invoked where the hole in a valence band is correlated with the Fermi sea of conduction electrons. In that case no bound state in a strict sense is formed, but the Coulomb interaction leads to a significant enhancement of absorption in the vicinity of the fundamental absorption edge also known as the Mahan or Fermi-edge singularity.
The concept of excitons was first proposed by Yakov Frenkel in 1931, [6] when he described the excitation of an atomic lattice considering what is now called the tight-binding description of the band structure. In his model the electron and the hole bound by the coulomb interaction are located either on the same or on the nearest neighbouring sites of the lattice, but the exciton as a composite quasi-particle is able to travel through the lattice without any net transfer of charge, which led to many propositions for optoelectronic devices.
In materials with a relatively small dielectric constant, the Coulomb interaction between an electron and a hole may be strong and the excitons thus tend to be small, of the same order as the size of the unit cell. Molecular excitons may even be entirely located on the same molecule, as in fullerenes. This Frenkel exciton, named after Yakov Frenkel, has a typical binding energy on the order of 0.1 to 1 eV. Frenkel excitons are typically found in alkali halide crystals and in organic molecular crystals composed of aromatic molecules, such as anthracene and tetracene. Another example of Frenkel exciton includes on-site d-d excitations in transition metal compounds with partially filled d-shells. While d-d transitions are in principle forbidden by symmetry, they become weakly-allowed in a crystal when the symmetry is broken by structural relaxations or other effects. Absorption of a photon resonant with a d-d transition leads to the creation of an electron-hole pair on a single atomic site, which can be treated as a Frenkel exciton.
In semiconductors, the dielectric constant is generally large. Consequently, electric field screening tends to reduce the Coulomb interaction between electrons and holes. The result is a Wannier–Mott exciton, [7] which has a radius larger than the lattice spacing. Small effective mass of electrons that is typical of semiconductors also favors large exciton radii. As a result, the effect of the lattice potential can be incorporated into the effective masses of the electron and hole. Likewise, because of the lower masses and the screened Coulomb interaction, the binding energy is usually much less than that of a hydrogen atom, typically on the order of 0.01eV. This type of exciton was named for Gregory Wannier and Nevill Francis Mott. Wannier–Mott excitons are typically found in semiconductor crystals with small energy gaps and high dielectric constants, but have also been identified in liquids, such as liquid xenon. They are also known as large excitons.
In single-wall carbon nanotubes, excitons have both Wannier–Mott and Frenkel character. This is due to the nature of the Coulomb interaction between electrons and holes in one-dimension. The dielectric function of the nanotube itself is large enough to allow for the spatial extent of the wave function to extend over a few to several nanometers along the tube axis, while poor screening in the vacuum or dielectric environment outside of the nanotube allows for large (0.4 to 1.0eV) binding energies.
Often more than one band can be chosen as source for the electron and the hole, leading to different types of excitons in the same material. Even high-lying bands can be effective as femtosecond two-photon experiments have shown. At cryogenic temperatures, many higher excitonic levels can be observed approaching the edge of the band, [8] forming a series of spectral absorption lines that are in principle similar to hydrogen spectral series.
In a bulk semiconductor, a Wannier exciton has an energy and radius associated with it, called exciton Rydberg energy and exciton Bohr radius respectively. [9] For the energy, we have
where is the Rydberg unit of energy (cf. Rydberg constant), is the (static) relative permittivity, is the reduced mass of the electron and hole, and is the electron mass. Concerning the radius, we have
where is the Bohr radius.
For example, in GaAs, we have relative permittivity of 12.8 and effective electron and hole masses as 0.067m0 and 0.2m0 respectively; and that gives us meV and nm.
In two-dimensional (2D) materials, the system is quantum confined in the direction perpendicular to the plane of the material. The reduced dimensionality of the system has an effect on the binding energies and radii of Wannier excitons. In fact, excitonic effects are enhanced in such systems. [10]
For a simple screened Coulomb potential, the binding energies take the form of the 2D hydrogen atom [11]
In most 2D semiconductors, the Rytova–Keldysh form is a more accurate approximation to the exciton interaction [12] [13] [14]
where is the so-called screening length, is the vacuum permittivity, is the elementary charge, the average dielectric constant of the surrounding media, and the exciton radius. For this potential, no general expression for the exciton energies may be found. One must instead turn to numerical procedures, and it is precisely this potential that gives rise to the nonhydrogenic Rydberg series of the energies in 2D semiconductors. [10]
Monolayers of a transition metal dichalcogenide (TMD) are a good and cutting-edge example where excitons play a major role. In particular, in these systems, they exhibit a bounding energy of the order of 0.5 eV [2] with a Coulomb attraction between the hole and the electrons stronger than in other traditional quantum wells. As a result, optical excitonic peaks are present in these materials even at room temperatures. [2]
In nanoparticles which exhibit quantum confinement effects and hence behave as quantum dots (also called 0-dimensional semiconductors), excitonic radii are given by [15] [16]
where is the relative permittivity, is the reduced mass of the electron-hole system, is the electron mass, and is the Bohr radius.
Hubbard excitons are linked to electrons not by a Coulomb's interaction, but by a magnetic force. Their name derives by the English physicist John Hubbard.
Hubbard excitons were observed for the first time in 2023 through the Terahertz time-domain spectroscopy. Those particles have been obtained by applying a light to a Mott antiferromagnetic insulator. [17]
An intermediate case between Frenkel and Wannier excitons is the charge-transfer (CT) exciton. In molecular physics, CT excitons form when the electron and the hole occupy adjacent molecules. [18] They occur primarily in organic and molecular crystals; [19] in this case, unlike Frenkel and Wannier excitons, CT excitons display a static electric dipole moment. CT excitons can also occur in transition metal oxides, where they involve an electron in the transition metal 3d orbitals and a hole in the oxygen 2p orbitals. Notable examples include the lowest-energy excitons in correlated cuprates [20] or the two-dimensional exciton of TiO2. [21] Irrespective of the origin, the concept of CT exciton is always related to a transfer of charge from one atomic site to another, thus spreading the wave-function over a few lattice sites.
At surfaces it is possible for so called image states to occur, where the hole is inside the solid and the electron is in the vacuum. These electron-hole pairs can only move along the surface.
Dark excitons are those where the electrons have a different momentum from the holes to which they are bound that is they are in an optically forbidden transition which prevents them from photon absorption and therefore to reach their state they need phonon scattering. They can even outnumber normal bright excitons formed by absorption alone. [22] [23] [24]
Alternatively, an exciton may be described as an excited state of an atom, ion, or molecule, if the excitation is wandering from one cell of the lattice to another.
When a molecule absorbs a quantum of energy that corresponds to a transition from one molecular orbital to another molecular orbital, the resulting electronic excited state is also properly described as an exciton. An electron is said to be found in the lowest unoccupied orbital and an electron hole in the highest occupied molecular orbital, and since they are found within the same molecular orbital manifold, the electron-hole state is said to be bound. Molecular excitons typically have characteristic lifetimes on the order of nanoseconds, after which the ground electronic state is restored and the molecule undergoes photon or phonon emission. Molecular excitons have several interesting properties, one of which is energy transfer (see Förster resonance energy transfer) whereby if a molecular exciton has proper energetic matching to a second molecule's spectral absorbance, then an exciton may transfer (hop) from one molecule to another. The process is strongly dependent on intermolecular distance between the species in solution, and so the process has found application in sensing and molecular rulers.
The hallmark of molecular excitons in organic molecular crystals are doublets and/or triplets of exciton absorption bands strongly polarized along crystallographic axes. In these crystals an elementary cell includes several molecules sitting in symmetrically identical positions, which results in the level degeneracy that is lifted by intermolecular interaction. As a result, absorption bands are polarized along the symmetry axes of the crystal. Such multiplets were discovered by Antonina Prikhot'ko [25] [26] and their genesis was proposed by Alexander Davydov. It is known as 'Davydov splitting'. [27] [28]
Excitons are lowest excited states of the electronic subsystem of pure crystals. Impurities can bind excitons, and when the bound state is shallow, the oscillator strength for producing bound excitons is so high that impurity absorption can compete with intrinsic exciton absorption even at rather low impurity concentrations. This phenomenon is generic and applicable both to the large radius (Wannier–Mott) excitons and molecular (Frenkel) excitons. Hence, excitons bound to impurities and defects possess giant oscillator strength. [29]
In crystals, excitons interact with phonons, the lattice vibrations. If this coupling is weak as in typical semiconductors such as GaAs or Si, excitons are scattered by phonons. However, when the coupling is strong, excitons can be self-trapped. [30] [31] Self-trapping results in dressing excitons with a dense cloud of virtual phonons which strongly suppresses the ability of excitons to move across the crystal. In simpler terms, this means a local deformation of the crystal lattice around the exciton. Self-trapping can be achieved only if the energy of this deformation can compete with the width of the exciton band. Hence, it should be of atomic scale, of about an electron volt.
Self-trapping of excitons is similar to forming strong-coupling polarons but with three essential differences. First, self-trapped exciton states are always of a small radius, of the order of lattice constant, due to their electric neutrality. Second, there exists a self-trapping barrier separating free and self-trapped states, hence, free excitons are metastable. Third, this barrier enables coexistence of free and self-trapped states of excitons. [32] [33] [34] This means that spectral lines of free excitons and wide bands of self-trapped excitons can be seen simultaneously in absorption and luminescence spectra. While the self-trapped states are of lattice-spacing scale, the barrier has typically much larger scale. Indeed, its spatial scale is about where is effective mass of the exciton, is the exciton-phonon coupling constant, and is the characteristic frequency of optical phonons. Excitons are self-trapped when and are large, and then the spatial size of the barrier is large compared with the lattice spacing. Transforming a free exciton state into a self-trapped one proceeds as a collective tunneling of coupled exciton-lattice system (an instanton). Because is large, tunneling can be described by a continuum theory. [35] The height of the barrier . Because both and appear in the denominator of , the barriers are basically low. Therefore, free excitons can be seen in crystals with strong exciton-phonon coupling only in pure samples and at low temperatures. Coexistence of free and self-trapped excitons was observed in rare-gas solids, [36] [37] alkali-halides, [38] and in molecular crystal of pyrene. [39]
Excitons are the main mechanism for light emission in semiconductors at low temperature (when the characteristic thermal energy kT is less than the exciton binding energy), replacing the free electron-hole recombination at higher temperatures.
The existence of exciton states may be inferred from the absorption of light associated with their excitation. Typically, excitons are observed just below the band gap.
When excitons interact with photons a so-called polariton (or more specifically exciton-polariton) is formed. These excitons are sometimes referred to as dressed excitons.
Provided the interaction is attractive, an exciton can bind with other excitons to form a biexciton, analogous to a dihydrogen molecule. If a large density of excitons is created in a material, they can interact with one another to form an electron-hole liquid, a state observed in k-space indirect semiconductors.
Additionally, excitons are integer-spin particles obeying Bose statistics in the low-density limit. In some systems, where the interactions are repulsive, a Bose–Einstein condensed state, called excitonium, is predicted to be the ground state. Some evidence of excitonium has existed since the 1970s but has often been difficult to discern from a Peierls phase. [40] Exciton condensates have allegedly been seen in a double quantum well systems. [41] In 2017 Kogar et al. found "compelling evidence" for observed excitons condensing in the three-dimensional semimetal 1T-TiSe2. [42]
Normally, excitons in a semiconductor have a very short lifetime due to the close proximity of the electron and hole. However, by placing the electron and hole in spatially separated quantum wells with an insulating barrier layer in between so called 'spatially indirect' excitons can be created. In contrast to ordinary (spatially direct), these spatially indirect excitons can have large spatial separation between the electron and hole, and thus possess a much longer lifetime. [43] This is often used to cool excitons to very low temperatures in order to study Bose–Einstein condensation (or rather its two-dimensional analog). [44]
Photoluminescence is light emission from any form of matter after the absorption of photons. It is one of many forms of luminescence and is initiated by photoexcitation, hence the prefix photo-. Following excitation, various relaxation processes typically occur in which other photons are re-radiated. Time periods between absorption and emission may vary: ranging from short femtosecond-regime for emission involving free-carrier plasma in inorganic semiconductors up to milliseconds for phosphoresence processes in molecular systems; and under special circumstances delay of emission may even span to minutes or hours.
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 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 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 to the conduction band, then current can flow. Therefore, the band gap is a major factor determining the electrical conductivity of a solid. Substances having large band gaps are generally insulators, those with small 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.
Quantum dots (QDs) or semiconductor nanocrystals are semiconductor particles a few nanometres in size with optical and electronic properties that differ from those of larger particles via quantum mechanical effects. They are a central topic in nanotechnology and materials science. When a quantum dot is illuminated by UV light, an electron in the quantum dot can be excited to a state of higher energy. In the case of a semiconducting quantum dot, this process corresponds to the transition of an electron from the valence band to the conductance band. The excited electron can drop back into the valence band releasing its energy as light. This light emission (photoluminescence) is illustrated in the figure on the right. The color of that light depends on the energy difference between the conductance band and the valence band, or the transition between discrete energy states when the band structure is no longer well-defined in QDs.
In condensed matter physics, a quasiparticle is a concept used to describe a collective behavior of a group of particles that can be treated as if they were a single particle. Formally, quasiparticles and collective excitations are closely related phenomena that arise when a microscopically complicated system such as a solid behaves as if it contained different weakly interacting particles in vacuum.
A polaron is a quasiparticle used in condensed matter physics to understand the interactions between electrons and atoms in a solid material. The polaron concept was proposed by Lev Landau in 1933 and Solomon Pekar in 1946 to describe an electron moving in a dielectric crystal where the atoms displace from their equilibrium positions to effectively screen the charge of an electron, known as a phonon cloud. This lowers the electron mobility and increases the electron's effective mass.
In solid-state physics, the electron mobility characterises how quickly an electron can move through a metal or semiconductor when pushed or 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.
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.
A Wigner crystal is the solid (crystalline) phase of electrons first predicted by Eugene Wigner in 1934. A gas of electrons moving in a uniform, inert, neutralizing background will crystallize and form a lattice if the electron density is less than a critical value. This is because the potential energy dominates the kinetic energy at low densities, so the detailed spatial arrangement of the electrons becomes important. To minimize the potential energy, the electrons form a bcc lattice in 3D, a triangular lattice in 2D and an evenly spaced lattice in 1D. Most experimentally observed Wigner clusters exist due to the presence of the external confinement, i.e. external potential trap. As a consequence, deviations from the b.c.c or triangular lattice are observed. A crystalline state of the 2D electron gas can also be realized by applying a sufficiently strong magnetic field. However, it is still not clear whether it is the Wigner crystallization that has led to observation of insulating behaviour in magnetotransport measurements on 2D electron systems, since other candidates are present, such as Anderson localization.
Sound amplification by stimulated emission of radiation (SASER) refers to a device that emits acoustic radiation. It focuses sound waves in a way that they can serve as accurate and high-speed carriers of information in many kinds of applications—similar to uses of laser light.
In quantum biology, the Davydov soliton is a quasiparticle representing an excitation propagating along the self-trapped amide I groups within the α-helices of proteins. It is a solution of the Davydov Hamiltonian.
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.
In condensed matter physics, biexcitons are created from two free excitons, analogous to di-positronium in vacuum.
Förster coupling is the resonant energy transfer between excitons within adjacent QD's. The first studies of Forster were performed in the context of the sensitized luminescence of solids. Here, an excited sensitizer atom can transfer its excitation to a neighbouring acceptor atom, via an intermediate virtual photon. This same mechanism has also been shown to be responsible for exciton transfer between QD's and within molecular systems and biosystems, all of which may be treated in a similar formulation.
Emmanuel I. Rashba is a Soviet-American theoretical physicist of Jewish origin who worked in Ukraine, Russia and in the United States. Rashba is known for his contributions to different areas of condensed matter physics and spintronics, especially the Rashba effect in spin physics, and also for the prediction of electric dipole spin resonance (EDSR), that was widely investigated and became a regular tool for operating electron spins in nanostructures, phase transitions in spin-orbit coupled systems driven by change of the Fermi surface topology, Giant oscillator strength of impurity excitons, and coexistence of free and self-trapped excitons. The principal subject of spintronics is all-electric operation of electron spins, and EDSR was the first phenomenon predicted and experimentally observed in this field.
Kirill Borisovich Tolpygo was a Soviet physicist and a corresponding member of the National Academy of Sciences of Ukraine. He was recognized for his works on condensed matter theory; the theory of phonon spectra in crystals; electronic structure and defects in insulators and semiconductors; and biophysics. He created the Department of Theoretical Physics and the Department of Biophysics at Donetsk National University. Tolpygo was a teacher, mentor and scientific adviser to graduate students. Tolpygo was awarded the Order of the Great Patriotic War.
The semiconductor Bloch equations describe the optical response of semiconductors excited by coherent classical light sources, such as lasers. They are based on a full quantum theory, and form a closed set of integro-differential equations for the quantum dynamics of microscopic polarization and charge carrier distribution. The SBEs are named after the structural analogy to the optical Bloch equations that describe the excitation dynamics in a two-level atom interacting with a classical electromagnetic field. As the major complication beyond the atomic approach, the SBEs must address the many-body interactions resulting from Coulomb force among charges and the coupling among lattice vibrations and electrons.
The semiconductor luminescence equations (SLEs) describe luminescence of semiconductors resulting from spontaneous recombination of electronic excitations, producing a flux of spontaneously emitted light. This description established the first step toward semiconductor quantum optics because the SLEs simultaneously includes the quantized light–matter interaction and the Coulomb-interaction coupling among electronic excitations within a semiconductor. The SLEs are one of the most accurate methods to describe light emission in semiconductors and they are suited for a systematic modeling of semiconductor emission ranging from excitonic luminescence to lasers.
The Elliott formula describes analytically, or with few adjustable parameters such as the dephasing constant, the light absorption or emission spectra of solids. It was originally derived by Roger James Elliott to describe linear absorption based on properties of a single electron–hole pair. The analysis can be extended to a many-body investigation with full predictive powers when all parameters are computed microscopically using, e.g., the semiconductor Bloch equations or the semiconductor luminescence equations.
The Wannier equation describes a quantum mechanical eigenvalue problem in solids where an electron in a conduction band and an electronic vacancy within a valence band attract each other via the Coulomb interaction. For one electron and one hole, this problem is analogous to the Schrödinger equation of the hydrogen atom; and the bound-state solutions are called excitons. When an exciton's radius extends over several unit cells, it is referred to as a Wannier exciton in contrast to Frenkel excitons whose size is comparable with the unit cell. An excited solid typically contains many electrons and holes; this modifies the Wannier equation considerably. The resulting generalized Wannier equation can be determined from the homogeneous part of the semiconductor Bloch equations or the semiconductor luminescence equations.
Giant oscillator strength is inherent in excitons that are weakly bound to impurities or defects in crystals.
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