We present a comprehensive, up-to-date compilation of band parameters for the technologically important III–V zinc blende and wurtzite compound semiconductors: GaAs, GaSb, GaP, GaN, AlAs, AlSb, AlP, AlN, InAs, InSb, InP, and InN, along with their ternary and quaternary alloys. Based on a review of the existing literature, complete and consistent parameter sets are given for all materials. Emphasizing the quantities required for band structure calculations, we tabulate the direct and indirect energy gaps, spin-orbit, and crystal-field splittings, alloy bowing parameters, effective masses for electrons, heavy, light, and split-off holes, Luttinger parameters, interband momentum matrix elements, and deformation potentials, including temperature and alloy-composition dependences where available. Heterostructure band offsets are also given, on an absolute scale that allows any material to be aligned relative to any other.

Band parameters for III–V compound semiconductors and their alloys

First-principles calculations have evolved from mere aids in explaining and supporting experiments to powerful tools for predicting new materials and their properties. In the first part of this review we describe the state-of-the-art computational methodology for calculating the structure and energetics of point defects and impurities in semiconductors. We will pay particular attention to computational aspects which are unique to defects or impurities, such as how to deal with charge states and how to describe and interpret transition levels. In the second part of the review we will illustrate these capabilities with examples for defects and impurities in nitride semiconductors. Point defects have traditionally been considered to play a major role in wide-band-gap semiconductors, and first-principles calculations have been particularly helpful in elucidating the issues. Specifically, calculations have shown that the unintentional n-type conductivity that has often been observed in as-grown GaN cannot be a...

First-principles calculations for defects and impurities: Applications to III-nitrides

We present a comprehensive and up-to-date compilation of band parameters for all of the nitrogen-containing III–V semiconductors that have been investigated to date. The two main classes are: (1) “conventional” nitrides (wurtzite and zinc-blende GaN, InN, and AlN, along with their alloys) and (2) “dilute” nitrides (zinc-blende ternaries and quaternaries in which a relatively small fraction of N is added to a host III–V material, e.g., GaAsN and GaInAsN). As in our more general review of III–V semiconductor band parameters [I. Vurgaftman et al., J. Appl. Phys. 89, 5815 (2001)], complete and consistent parameter sets are recommended on the basis of a thorough and critical review of the existing literature. We tabulate the direct and indirect energy gaps, spin-orbit and crystal-field splittings, alloy bowing parameters, electron and hole effective masses, deformation potentials, elastic constants, piezoelectric and spontaneous polarization coefficients, as well as heterostructure band offsets. Temperature an...

Band parameters for nitrogen-containing semiconductors

Gallium nitride (GaN) and its allied binaries InN and AIN as well as their ternary compounds have gained an unprecedented attention due to their wide-ranging applications encompassing green, blue, violet, and ultraviolet (UV) emitters and detectors (in photon ranges inaccessible by other semiconductors) and high-power amplifiers. However, even the best of the three binaries, GaN, contains many structural and point defects caused to a large extent by lattice and stacking mismatch with substrates. These defects notably affect the electrical and optical properties of the host material and can seriously degrade the performance and reliability of devices made based on these nitride semiconductors. Even though GaN broke the long-standing paradigm that high density of dislocations precludes acceptable device performance, point defects have taken the center stage as they exacerbate efforts to increase the efficiency of emitters, increase laser operation lifetime, and lead to anomalies in electronic devices. The p...

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Luminescence properties of defects in GaN

The III-nitrides include the semiconductors AlN, GaN and InN, which have band gaps spanning the entire UV and visible ranges. Thin films of III-nitrides are used to make UV, violet, blue and green light-emitting diodes and lasers, as well as solar cells, high-electron mobility transistors (HEMTs) and other devices. However, the film growth process gives rise to unusually high strain and high defect densities, which can affect the device performance. X-ray diffraction is a popular, non-destructive technique used to characterize films and device structures, allowing improvements in device efficiencies to be made. It provides information on crystalline lattice parameters (from which strain and composition are determined), misorientation (from which defect types and densities may be deduced), crystallite size and microstrain, wafer bowing, residual stress, alloy ordering, phase separation (if present) along with film thicknesses and superlattice (quantum well) thicknesses, compositions and non-uniformities. These topics are reviewed, along with the basic principles of x-ray diffraction of thin films and areas of special current interest, such as analysis of non-polar, semipolar and cubic III-nitrides. A summary of useful values needed in calculations, including elastic constants and lattice parameters, is also given. Such topics are also likely to be relevant to other highly lattice-mismatched wurtzite-structure materials such as heteroepitaxial ZnO and ZnSe.

https://iopscience.iop.org/article/10.1088/0034-4885/72/3/036502/pdf

X-ray diffraction of III-nitrides

The group III nitrides (AlN, GaN and InN) represent an important trio of semiconductors because of their direct band gaps which span the range 1.95-6.2 eV, including the whole of the visible region and extending well out into the ultraviolet (UV) range. They form a complete series of ternary alloys which, in principle, makes available any band gap within this range and the fact that they also generate efficient luminescence has been the main driving force for their recent technological development. High brightness visible light-emitting diodes (LEDs) are now commercially available, a development which has transformed the market for LED-based full colour displays and which has opened the way to many other applications, such as in traffic lights and efficient low voltage, flat panel white light sources. Continuously operating UV laser diodes have also been demonstrated in the laboratory, exciting tremendous interest for high-density optical storage systems, UV lithography and projection displays. In a remarkably short space of time, the nitrides have therefore caught up with and, in some ways, surpassed the wide band gap II-VI compounds (ZnCdSSe) as materials for short wavelength optoelectronic devices. The purpose of this paper is to review these developments and to provide essential background material in the form of the structural, electronic and optical properties of the nitrides, relevant to these applications. We have been guided by the fact that the devices so far available are based on the binary compound GaN (which is relatively well developed at the present time), together with the ternary alloys AlGaN and InGaN, containing modest amounts of Al or In. We therefore concentrate, to a considerable extent, on the properties of GaN, then introduce those of the alloys as appropriate, emphasizing their use in the formation of the heterostructures employed in devices. The nitrides crystallize preferentially in the hexagonal wurtzite structure and devices have so far been based on this material so the majority of our paper is concerned with it, however, the cubic, zinc blende form is known for all three compounds, and cubic GaN has been the subject of sufficient work to merit a brief account in its own right. There is significant interest based on possible technological advantages, such as easier doping, easier cleaving (for laser facets) and easier contacting. It also appears, at present, that the cubic form gives higher electron and hole mobilities than the hexagonal form. The dominant hexagonal structure is similar to that found in a number of II-VI compounds such as CdS and they can therefore be taken as role models. In particular, the lower symmetry gives rise to three separate valence bands at the zone centre and exciton spectra associated with each of these have been reported by many workers for GaN. Interpretation is complicated by the presence of strain in many samples due to the fact that most material consists of epitaxial thin films grown on non-lattice-matched substrates (bulk GaN crystals not being widely available). However, much progress has been made in understanding the physics of these films and we discuss the current position with regard to band gaps, effective masses, exciton binding energies, phonon energies, dielectric constants, etc. Apart from a lack of knowledge of the anticipated valence band anisotropy, it can be said that GaN is now rather well documented. Less detail is available for AlN or InN and we make no attempt to provide similar data for them. The structure of the paper is based on a historical introduction, followed by a brief account of the various crystal growth methods used to produce bulk GaN and epitaxial films of GaN and the ternary alloys. This is then followed by an account of the structural properties of hexagonal GaN as measured by x-ray diffraction and electron microscopy, phonon properties from infrared and Raman spectroscopy, electrical properties, with emphasis on n- and p-type doping, and optical properties, measured mainly by photoluminescence. A brief comparative account of cubic GaN properties follows. Discussion of alloy properties in the context of their use in quantum well and superlattice structures forms an introduction to the device sections which close the paper. These include details of the technology necessary for etching, contacting and forming laser facets, as an introduction to recent results on LEDs and laser diodes. Having described the current position, we speculate briefly on likely future developments.

https://iopscience.iop.org/article/10.1088/0034-4885/61/1/001/pdf

Group III nitride semiconductors for short wavelength light-emitting devices

We report on the growth of GaN with a zinc‐blende, wurtzite, or a mixed phase structure on (001)GaP and (001)GaAs substrates by a low‐temperature modified molecular beam epitaxy technique. By systematically varying the incident arsenic overpressure, films grown at a moderate substrate temperature of ≊620 °C show predominately wurtzite α‐GaN, zinc‐blende β‐GaN, or a mixed phase of the two. Films containing only the metastable phase β‐GaN were achieved by using a relatively high growth temperature of ≊700 °C and with an arsenic overpressure of ≊2.4×10−5 Torr. X‐ray diffraction measurements indicate an improved crystalline quality for the layers grown at ≊700 °C compared to those grown at ≊620 °C as evident by a narrower full width at half‐maximum of 35 min for β‐GaN, which is among the narrowest reported to date.

Selective growth of zinc‐blende, wurtzite, or a mixed phase of gallium nitride by molecular beam epitaxy

The growth and properties of group III nitrides

We report measurements of photoluminescence, photoluminescence excitation spectroscopy and photoluminescence time decay on three MOVPE-grown InGaN/GaN multiple quantum well structures with 13% In in the wells and well widths Lz = 1.25, 2.5 and 5.0 nm. The PL spectra are dominated by single emission peaks, together with phonon sidebands spaced by a GaN LO phonon energy (92 meV). The peak energies are red-shifted with respect to energies calculated for exciton recombination in square quantum wells and the wide well sample also shows a significant Stokes shift between emission and absorption. Recombination lifetimes measured at 6 K are energy dependent, increasing as the photon energy is scanned downwards through the emission line. They also depend strongly on well width. On the low energy side of the 5 nm well emission line we measure lifetimes as long as 100 ns. Raising the temperature from 6 to 300 K results in a strong reduction of emission intensity for all samples and reduction of the lifetimes, though by a much smaller factor. The peak positions shift slightly to lower energy but by far less than the shift in the band edge. We consider three different theoretical models in an attempt to interpret this data, an exponential tail state model, a model of localization due to In/Ga segregation within the wells and the quantum confined Stark effect model. The QCSE model appears able to explain most of the data reasonably well, though there is evidence to suggest that, in addition, some degree of localization occurs.

https://iopscience.iop.org/article/10.1088/0268-1242/15/6/302/pdf

Photoluminescence studies of InGaN/GaN multi-quantum wells

We report new lines in the photoluminescence (PL) spectrum of lightly Be-doped GaN. The low-temperature PL spectrum of the lightly doped sample is dominated by a transition at 3.385 eV with first and second LO phonon replicas. Power-resolved PL measurements showed that the peak at 3.385 eV narrowed in width and shifted to higher energies with increasing excitation intensity. Thus the transition is attributed to donor-to-acceptor recombination, involving a Be acceptor of optical ionization energy of between 90 and 100 meV. This is much shallower than the acceptor level of 250 meV induced by Mg doping. Increasing the doping, however, resulted in a quenching of the band-edge luminescence and the appearance of a broad transition centred around 2.4 eV which we assign to a complex involving Be. Undulations on the peak were consistent with interference effects. On increasing the doping level even further all luminescence was quenched.

https://iopscience.iop.org/article/10.1088/0268-1242/13/5/010/pdf

J.W. Orton

Papers

Group III nitride semiconductors for short wavelength light-emitting devices

Selective growth of zinc‐blende, wurtzite, or a mixed phase of gallium nitride by molecular beam epitaxy

The growth and properties of group III nitrides

Photoluminescence studies of InGaN/GaN multi-quantum wells

Photoluminescence of MBE grown wurtzite Be-doped GaN