Group III nitride semiconductors for short wavelength light-emitting devices

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.

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