Recent research results pertaining to InN, GaN and AlN are reviewed, focusing on the different growth techniques of Group III-nitride crystals and epitaxial films, heterostructures and devices. The chemical and thermal stability of epitaxial nitride films is discussed in relation to the problems of deposition processes and the advantages for applications in high-power and high-temperature devices. The development of growth methods like metalorganic chemical vapour deposition and plasma-induced molecular beam epitaxy has resulted in remarkable improvements in the structural, optical and electrical properties. New developments in precursor chemistry, plasma-based nitrogen sources, substrates, the growth of nucleation layers and selective growth are covered. Deposition conditions and methods used to grow alloys for optical bandgap and lattice engineering are introduced. The review is concluded with a description of recent Group III-nitride semiconductor devices such as bright blue and white light-emitting diodes, the first blue-emitting laser, high-power transistors, and a discussion of further applications in surface acoustic wave devices and sensors.

https://iopscience.iop.org/article/10.1088/0022-3727/31/20/001/pdf

Growth and applications of Group 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

20) a-plane] is thoroughly investigated. We find that for the relaxed surfaces of the binary nitrides the difference in electron affinities between m- and a-plane is less than 0.1 eV. The absolute electron affinities are found to strongly depend on the choice of XC functional. However, we find that relative alignments are less sensitive to the choice of XC functional. In particular, we find that relative alignments may be calculated based on Perdew–Becke–Ernzerhof [J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 134, 3865 (1996)] surface calculations with the HSE06 lattice parameters. For InGaN we find that the VBM is a linear function of In content and that the majority of the band-gap bowing is located in the CBM. Based on the calculated electron affinities we predict that InGaN will be suited for water splitting up to 50% In content. © 2011 American Institute of Physics. [doi:10.1063/1.3548872]

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Hybrid functional investigations of band gaps and band alignments for AlN, GaN, InN, and InGaN.

The valence‐band discontinuity at a wurtzite GaN/AlN(0001) heterojunction is measured by x‐ray photoemission spectroscopy. The method first measures the core level binding energies with respect to the valence‐band maximum in both GaN and AlN bulk films. The precise location of the valence‐band maximum is determined by aligning prominent features in the valence‐band spectrum with calculated densities of states. Tables of core level binding energies relative to the valence‐band maximum are reported for both GaN and AlN. Subsequent measurements of separations between Ga and Al core levels for thin overlayers of GaN film grown on AlN and vice versa yield a valence‐band discontinuity of ΔEV=0.8±0.3 eV in the standard type I heterojunction alignment.

Valence-band discontinuity between GaN and AlN measured by x-ray photoemission spectroscopy

We report the growth of thin carbon nitride films on Si(100) substrates at temperatures in the range of 100–700 °C using electron‐beam evaporation of graphite assisted with electron cyclotron resonance (ECR) plasma generated nitrogen species. The effect of the substrate temperature, and the nitrogen flow on the composition ratio C/N, and the C—N bonding were investigated using Fourier transform infrared spectroscopy (FTIR), x‐ray photoelectron spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and Raman spectroscopy. The FTIR spectra show that the films produced exhibit a very high visible to infrared transmittance (0.85–0.95). These spectra were dominated by amine group (NH2) with the presence of C‐N stretching modes. From both RBS and XPS, the nitrogen concentration in the film was calculated and was found in the range of 24%–48%, depending on the nitrogen partial pressure in the ECR source. Raman spectrum of the high nitrogen content thin film shows a well resolved peak at 1275 cm−1 sugg...

J. Ruan

Papers

AlN/GaN superlattices grown by gas source molecular beam epitaxy