Gallium oxide (Ga2O3) is emerging as a viable candidate for certain classes of power electronics, solar blind UV photodetectors, solar cells, and sensors with capabilities beyond existing technologies due to its large bandgap. It is usually reported that there are five different polymorphs of Ga2O3, namely, the monoclinic (β-Ga2O3), rhombohedral (α), defective spinel (γ), cubic (δ), or orthorhombic (e) structures. Of these, the β-polymorph is the stable form under normal conditions and has been the most widely studied and utilized. Since melt growth techniques can be used to grow bulk crystals of β-GaO3, the cost of producing larger area, uniform substrates is potentially lower compared to the vapor growth techniques used to manufacture bulk crystals of GaN and SiC. The performance of technologically important high voltage rectifiers and enhancement-mode Metal-Oxide Field Effect Transistors benefit from the larger critical electric field of β-Ga2O3 relative to either SiC or GaN. However, the absence of clear demonstrations of p-type doping in Ga2O3, which may be a fundamental issue resulting from the band structure, makes it very difficult to simultaneously achieve low turn-on voltages and ultra-high breakdown. The purpose of this review is to summarize recent advances in the growth, processing, and device performance of the most widely studied polymorph, β-Ga2O3. The role of defects and impurities on the transport and optical properties of bulk, epitaxial, and nanostructures material, the difficulty in p-type doping, and the development of processing techniques like etching, contact formation, dielectrics for gate formation, and passivation are discussed. Areas where continued development is needed to fully exploit the properties of Ga2O3 are identified.

A review of Ga2O3 materials, processing, and devices

The use of micro-Raman spectroscopy to monitor non-invasively GaN, AlGaN and AlN material parameters for process and growth monitoring/control is demonstrated. Concepts to determine the crystalline quality, the stress, the free carrier concentration, the aluminium composition and the temperature from the Raman modes are reviewed. Raman monitoring of processing and growth is illustrated on selected examples: the high-temperature processing of ion-implanted and non-implanted GaN layers, the Raman monitoring of AlGaN/GaN heterostructure field-effect transistors and the in situ Raman monitoring of GaN growth at elevated temperatures. Ultraviolet Raman spectroscopy has been employed to characterize material properties of GaN surface layers and GaN/AlGaN interfaces. Raman mapping is illustrated on bulk AlN crystals to investigate stress fields related to growth striations and defects. Copyright © 2001 John Wiley & Sons, Ltd.

Raman spectroscopy of GaN, AlGaN and AlN for process and growth monitoring/control

Successful ex situ and in situ cleaning procedures for AlN and GaN surfaces have been investigated and achieved. Exposure to HF and HCl solutions produced the lowest coverages of oxygen on AlN and GaN surfaces, respectively. However, significant amounts of residual F and Cl were detected. These halogens tie up dangling bonds at the nitride surfaces hindering reoxidation. The desorption of F required temperatures >850 °C. Remote H plasma exposure was effective for removing halogens and hydrocarbons from the surfaces of both nitrides at 450 °C, but was not efficient for oxide removal. Annealing GaN in NH3 at 700–800 °C produced atomically clean as well as stoichiometric GaN surfaces.

Cleaning of AlN and GaN surfaces

A critical point in device fabrication based on GaN is the controlled doping and the incorporation of impurities like, e.g., oxygen. We have explored the adsorption of oxygen at the wurtzite (0001) and (0001) GaN surfaces employing density-functional theory. Our results show that both surface orientations are very active towards oxygen adsorption, explaining the high oxygen concentrations typically observed in GaN. However, the (0001) and (0001) surfaces behave differently and oxygen incorporation is expected to be higher at the (0001) surface. The different reactivity is explained in terms of the specific structural configurations.

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The adsorption of oxygen at gan surfaces

The photocatalytic activity of (Ga1-xZnx)(N1-xOx) loaded with Rh−Cr mixed-oxide (Rh2-yCryO3) nanoparticles for overall water splitting under visible-light irradiation (λ > 400 nm) is investigated with respect to reaction pH and gas pressure. The photocatalytic performance of the catalyst is found to be strongly dependent on the pH of the reactant solution but largely independent of gas pressure. The present photocatalyst exhibits stable and high photocatalytic activity in an aqueous solution of pH 4.5 for 72 h. The photocatalytic performance is much lower at pH 3.0 and pH 6.2, attributable to corrosion of the cocatalyst and hydrolysis of the catalyst. The dispersion of Rh2-yCryO3 as a cocatalyst on the (Ga1-xZnx)(N1-xOx) surface promotes hydrogen evolution, which is considered to be the rate-determining step for overall water splitting on this catalyst.

Efficient Overall Water Splitting under Visible-Light Irradiation on (Ga1-xZnx)(N1-xOx) Dispersed with Rh−Cr Mixed-Oxide Nanoparticles: Effect of Reaction Conditions on Photocatalytic Activity

The oxidation of single crystal gallium nitride in dry air has been investigated. X-ray photoelectron spectroscopy (XPS) revealed minimal oxide growth at 450 and 750 °C for up to 25 h. However, at 900 °C the growth of an oxide approximately 5000 A thick was observed after 25 h. This oxide was determined to be the monoclinic β-Ga2O3 using glancing angle x-ray diffraction. XPS spectra of the Ga 3d and Ga 2p core levels indicated peak shifts of 1.2 and 1.3 eV, respectively, from Ga–O to Ga–N bonding. The Ga L3M45M45 core level binding energy was also investigated and β-Ga2O3 and GaN each presented a characteristic peak shape.

X-ray photoelectron spectroscopy and x-ray diffraction study of the thermal oxide on gallium nitride

Thermal oxidation of GaN was conducted at 700–900°C with O2, N2, and Ar as carrier gases for 525–630 Torr of H2O vapor. Upon oxidation of both GaN powders and n-GaN epilayers, the monoclinic β-Ga2O3 phase was identified using glancing angle x-ray diffraction. The chemical composition of the oxide was verified using x-ray photoelectron spectroscopy. In experiments conducted using GaN powder, the oxide grew most rapidly when O2 was the carrier gas for H2O. The same result was obtained on n-type GaN epilayers. Furthermore, the thickness of the oxide grown in H2O with O2 as the carrier gas was found to be proportional to the oxidation time at all temperatures studied, and an activation energy of 210±10 kJ/mol was obtained. Scanning electron microscopy revealed a smoother surface after wet oxidation than was reported previously for dry oxidation. However, cross-sectional transmission electron microscopy revealed that the wet oxide/GaN interface was irregular and non-ideal for devicefabrication, even more so than the dry oxide/GaN interface. This observation was consistent with poor electrical properties.

D. L. Waltemyer

Papers

X-ray photoelectron spectroscopy and x-ray diffraction study of the thermal oxide on gallium nitride

Wet thermal oxidation of GaN