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

Hydrogen storage in Mg: A most promising material

Wide-band-gap GaN and Ga-rich InGaN alloys, with energy gaps covering the blue and near-ultraviolet parts of the electromagnetic spectrum, are one group of the dominant materials for solid state lighting and lasing technologies and consequently, have been studied very well. Much less effort has been devoted to InN and In-rich InGaN alloys. A major breakthrough in 2002, stemming from much improved quality of InN films grown using molecular beam epitaxy, resulted in the bandgap of InN being revised from 1.9 eV to a much narrower value of 0.64 eV. This finding triggered a worldwide research thrust into the area of narrow-band-gap group-III nitrides. The low value of the InN bandgap provides a basis for a consistent description of the electronic structure of InGaN and InAlN alloys with all compositions. It extends the fundamental bandgap of the group III-nitride alloy system over a wider spectral region, ranging from the near infrared at ∼1.9 μm (0.64 eV for InN) to the ultraviolet at ∼0.36 μm (3.4 eV for GaN...

When group-III nitrides go infrared: New properties and perspectives

In this review, the structural, mechanical, thermal, and chemical properties of substrates used for gallium nitride (GaN) epitaxy are compiled, and the properties of GaN films deposited on these substrates are reviewed. Among semiconductors, GaN is unique; most of its applications uses thin GaN films deposited on foreign substrates (materials other than GaN); that is, heteroepitaxial thin films. As a consequence of heteroepitaxy, the quality of the GaN films is very dependent on the properties of the substrate—both the inherent properties such as lattice constants and thermal expansion coefficients, and process induced properties such as surface roughness, step height and terrace width, and wetting behavior. The consequences of heteroepitaxy are discussed, including the crystallographic orientation and polarity, surface morphology, and inherent and thermally induced stress in the GaN films. Defects such as threading dislocations, inversion domains, and the unintentional incorporation of impurities into the epitaxial GaN layer resulting from heteroepitaxy are presented along with their effect on device processing and performance. A summary of the structure and lattice constants for many semiconductors, metals, metal nitrides, and oxides used or considered for GaN epitaxy is presented. The properties, synthesis, advantages and disadvantages of the six most commonly employed substrates (sapphire, 6H-SiC, Si, GaAs, LiGaO 2 , and AlN) are presented. Useful substrate properties such as lattice constants, defect densities, elastic moduli, thermal expansion coefficients, thermal conductivities, etching characteristics, and reactivities under deposition conditions are presented. Efforts to reduce the defect densities and to optimize the electrical and optical properties of the GaN epitaxial film by substrate etching, nitridation, and slight misorientation from the (0 0 0 1) crystal plane are reviewed. The requirements, the obstacles, and the results to date to produce zincblende GaN on 3C-SiC/Si(0 0 1) and GaAs are discussed. Tables summarizing measures of the GaN quality such as XRD rocking curve FWHM, photoluminescence peak position and FWHM, and electron mobilities for GaN epitaxial layers produced by MOCVD, MBE, and HVPE for each substrate are given. The initial results using GaN substrates, prepared as bulk crystals and as free-standing epitaxial films, are reviewed. Finally, the promise and the directions of research on new potential substrates, such as compliant and porous substrates are described.

Substrates for gallium nitride epitaxy

Using hybrid functional calculations we investigate the effects of carbon on the electrical and optical properties of GaN. In contrast to the currently accepted view that C substituting for N (CN) is a shallow acceptor, we find that CN has an ionization energy of 0.90 eV. Our calculated absorption and emission lines also indicate that CN is a likely source for the yellow luminescence that is frequently observed in GaN, solving the longstanding puzzle of the nature of the C-related defect involved in yellow emission. Our results suggest that previous experimental data, analyzed under the assumption that CN acts as a shallow acceptor, should be re-examined.

Carbon impurities and the yellow luminescence in GaN

A new type of electrochromic mirror electrode based on reversible uptake of hydrogen in nickel magnesium alloy films is reported. Thin,magnesium-rich Ni-Mg films prepared on glass substrates by cosputtering from Ni and Mg targets are mirror-like in appearance and have low visible transmittance. Upon exposure to hydrogen gas or on reduction in alkaline electrolyte, the films take up hydrogen and become transparent. When hydrogen is removed, the mirror properties are recovered. The transition is believed to result from reversible formation of Mg2NiH4 and MgH2. A thin overlayer of palladium was found to enhance the kinetics of hydrogen insertion and extraction,and to protect the metal surface against oxidation.

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Switchable mirrors based on nickel–magnesium films

InN films with free electron concentrations ranging from mid-1017 to mid-1020 cm−3 have been studied using optical absorption, Hall effect, and secondary ion mass spectrometry. The optical absorption edge covers a wide energy range from the intrinsic band gap of InN of about 0.7 to about 1.7 eV which is close to the previously accepted band gap of InN. The electron concentration dependence of the optical absorption edge energy is fully accounted for by the Burstein–Moss shift. Results of secondary ion mass spectrometry measurements indicate that O and H impurities cannot fully account for the free electron concentration in the films.

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Effects of electron concentration on the optical absorption edge of InN

Carbon-doped GaN layers grown by molecular-beam epitaxy are studied with photoluminescence and positron annihilation spectroscopy. Semi-insulating layers doped with >1018 cm−3 carbon show a strong luminescence band centered at ∼2.2 eV (yellow luminescence). The absolute intensity of the 2.2 eV band is compared with the gallium vacancy concentration determined by positron annihilation spectroscopy. The results indicate that a high concentration of gallium vacancies is not necessary for yellow luminescence and that there is in fact a causal relationship between carbon and the 2.2 eV band. Markedly different deep-level ionization energies are found for the high-temperature quenching of the 2.2 eV photoluminescence in carbon-doped and reference samples. We propose that while the model of Neugebauer and Van de Walle [Appl. Phys. Lett. 69, 503 (1996)] applies for GaN of low carbon concentration, a different yellow luminescence mechanism is involved when the interstitial carbon concentration is comparable to or ...

Contributions from gallium vacancies and carbon-related defects to the “yellow luminescence” in GaN

Gallium nitride is grown by plasma-assisted molecular-beam epitaxy on (111) and (001) silicon substrates using sputter-deposited hafnium nitride buffer layers. Wurtzite GaN epitaxial layers are obtained on both the (111) and (001) HfN/Si surfaces, with crack-free thickness up to 1.2 (mu)m. Initial results for GaN grown on the (111) surface show a photoluminescence peak width of 17 meV at 11 K, and an asymmetric x-ray rocking curve width of 20 arcmin. Wurtzite GaN on HfN/Si(001) shows reduced structural quality and peculiar low-temperature luminescence features. However, growth on the (001) surface results in nearly stress-free films, suggesting that much thicker crack-free layers could be obtained.

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Lattice-matched HfN buffer layers for epitaxy of GaN on Si

The optical switching properties of gadolinium–magnesium hydride have been demonstrated in a solid-state electrochromic device. With positive polarization of the hydride electrode, the visible reflectance approaches 35% with virtually zero transmission, while with negative polarization, the visible transmission exceeds 25% at 650 nm. The switching is reversible, with intermediate optical properties between the transparent and reflecting states.

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R. Armitage

Papers

Switchable mirrors based on nickel–magnesium films

Effects of electron concentration on the optical absorption edge of InN

Contributions from gallium vacancies and carbon-related defects to the “yellow luminescence” in GaN

Lattice-matched HfN buffer layers for epitaxy of GaN on Si

Solid-state gadolinium–magnesium hydride optical switch