Solid-state gallium NMR characterization of cubic gallium nitride prepared by the reaction of gallium arsenide with ammonia

The reaction of cubic gallium arsenide (GaAs) with ammonia yielded gallium nitride (GaN). Powder X-ray diffraction patterns of the GaN products showed that they are a mixture of c- and w-GaN, while their Ga MAS NMR spectra revealed that they have the other phase of GaN besides c- and w-GaN and the high reaction temperature (≥900 °C) induces nitrogen deficiency in GaN. The peaks at 353 and 347 ppm in the ⁷¹Ga MAS NMR spectra were tentatively assigned to c-GaN and an intermediate of w- and c-GaN in the stacking order, respectively. The observed ⁷¹Ga chemical shifts of GaN, GaP, GaAs and GaSb in cubic phase were well correlated with the reciprocal of their band gaps.     

Initial stages of the ion-beam assisted epitaxial GaN film growth on 6H-SiC(0001)

Ultra-thin gallium nitride (GaN) films were deposited using the ion-beam assisted molecular-beam epitaxy technique. The influence of the nitrogen ion to gallium atom flux ratio (I/A ratio) during the early stages of GaN nucleation and thin film growth directly, without a buffer layer on super-polished 6H-SiC(0001) substrates was studied. The deposition process was performed at a constant substrate temperature of 700 °C by evaporation of Ga and irradiation with hyperthermal nitrogen ions from a constricted glow-discharge ion source. The hyperthermal nitrogen ion flux was kept constant and the kinetic energy of the ions did not exceed 25 eV. The selection of different I/A ratios in the range from 0.8 to 3.2 was done by varying the Ga deposition rate between 5 × 10¹³ and 2 × 10¹⁴ at. cm^− 2 s^− 1. The crystalline surface structure during the GaN growth was monitored in situ by reflection high-energy electron diffraction. The surface topography of the films as well as the morphology of separated GaN islands on the substrate surface was examined after film growth using a scanning tunneling microscope without interruption of ultra-high vacuum. The results show, that the I/A ratio has a major impact on the properties of the resulting ultra-thin GaN films. The growth mode, the surface roughness, the degree of GaN coverage of the substrate and the polytype mixture depend notably on the I/A ratio.     

Growth of c-GaN films on GaAs(100) using hot-wire CVD

Cubic gallium nitride (GaN) films were grown on nitrided layers of GaAs(100) by hot-wire chemical vapor deposition. The nitrided layer was also formed by NH_x radicals generated on a tungsten hot-wire surface. Nitridation conditions for the growth of GaN with a cubic-type structure were investigated. As a result, GaN film with a preponderant cubic phase was grown on the GaAs surface layer nitrided at a substrate temperature of 550 °C, a filament temperature of 1200 °C and an ammonia (NH₃) pressure of 1 Torr.     

Synthesis of oriented GaN phase on GaAs during surface heterosegregation

We examine the potentialities of heterosegregation processes in the synthesis of surface phases, as exemplified by the preparation of oriented GaN on single-crystal GaAs. A new phase has been obtained for the first time by reacting liquid gallium resulting from surface autosegregation on gallium arsenide with nitrogen gas at temperatures from 970 to 1050°C. The nanomorphology, elemental composition, and phase composition of the surface GaN layer produced by surface reactions have been assessed by high-resolution scanning electron microscopy, digital optical microscopy, and X-ray microanalysis.     

NEXAFS and XPS study of GaN formation on ion-bombarded GaAs surfaces

Interaction of low-energy nitrogen ions (0.3-2 keV N₂⁺) with GaAs (100) surfaces has been studied by X-ray photoemission spectroscopy (XPS) around N 1s and Ga 3d core-levels and near-edge X-ray absorption fine structure (NEXAFS) around the N K-edge, using synchrotron radiation. At the lowest bombardment energy, nitrogen forms bonds with both Ga and As, while Ga-N bonds form preferentially at higher energies. Thermal annealing at temperatures above 350 °C promotes formation of GaN on the surface, but it is insufficient to remove disorder introduced by ion implantation. We have identified nitrogen interstitials and anti-sites in NEXAFS spectra, while interstitial molecular nitrogen provides a clear signature in both XPS and NEXAFS. The close similarity between NEXAFS spectra from thin GaN films and ion-bombarded GaAs samples supports our proposition about formation of thin GaN films on ion-bombarded GaAs.     

Improved growth of GaN layers on ultra thin silicon nitride/Si (1 1 1) by RF-MBE

High-quality GaN epilayers were grown on Si (1 1 1) substrates by molecular beam epitaxy using a new growth process sequence which involved a substrate nitridation at low temperatures, annealing at high temperatures, followed by nitridation at high temperatures, deposition of a low-temperature buffer layer, and a high-temperature overgrowth. The material quality of the GaN films was also investigated as a function of nitridation time and temperature. Crystallinity and surface roughness of GaN was found to improve when the Si substrate was treated under the new growth process sequence. Micro-Raman and photoluminescence (PL) measurement results indicate that the GaN film grown by the new process sequence has less tensile stress and optically good. The surface and interface structures of an ultra thin silicon nitride film grown on the Si surface are investigated by core-level photoelectron spectroscopy and it clearly indicates that the quality of silicon nitride notably affects the properties of GaN growth.     

Synthesis of GaN nanoparticles from NH4[Ga(OH)2CO3] under a flow of ammonia gas

In this investigation, we report the synthesis of gallium nitride (GaN) nanoparticles from ammonium-carbonato-dihydroxo-gallate (NH₄[Ga(OH)₂CO₃]) in the flow of NH₃ gas in a temperature range of 500-900 °C. The GaN nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR). The FTIR and XPS revealed that the conversion of NH₄[Ga(OH)₂CO₃] to GaN under a flow of ammonia proceeds stepwise via amorphous gallium oxynitrides (GaO_xN_y) intermediates. Nanosized GaN particles with an average diameter of approximately 20-40 nm were obtained. The results obtained demonstrate that the large-quantity nanosized GaN particles can be synthesized from NH₄[Ga(OH)₂CO₃] powders.     

Investigation on the role of indium in the removal of metallic gallium from soft and hard sputtered GaN (0001) surfaces

Cleaning of GaN by argon sputtering and subsequent annealing introduces metallic gallium on the GaN surface. Once formed, this metallic gallium can be difficult to remove. It has a strong influence on the Fermi level position in the band gap and poses a problem for subsequent epitaxial growth on the surface. We present a method of removing metallic gallium from moderately damaged GaN surfaces by deposition of indium and formation of an In-Ga alloy that can be desorbed by annealing at ~ 550 °C. After the In-Ga alloy has desorbed, photoemission spectra show that the Ga3d bulk component becomes narrower indicating a smoother and more homogeneous surface. This is also reflected in a sharper low energy electron diffraction pattern. On heavily damaged GaN surfaces, caused by hard sputtering, larger amount of metallic gallium forms after annealing at 600 °C. This gallium readily alloys with deposited indium, but the alloy does not desorb until a temperature of 840 °C is reached and even then, traces of both indium and metallic gallium could be found on the surface.     

Radical-beam gettering epitaxy of GaN layers on nitrogen-ion-implanted GaAs substrates

Thin GaN films have been grown on N⁺-ion-implanted single-crystal GaAs(111) substrates by radical-beam gettering epitaxy, and their structural perfection has been assessed by high-resolution x-ray diffraction. At growth temperatures from 770 to 970 K, the layers consist of hexagonal GaN and have mirror-smooth surfaces. Nitrogen-ion implantation into the substrate favors the formation of a sharp film/substrate interface owing to radiation-enhanced gallium diffusion. Analysis of the GaN/GaAs structures by Auger electron and x-ray photoelectron spectroscopies in combination with depth profiling indicates that the GaN layer is enriched in gallium. The N: Ga atomic ratio in the films is 0.98: 1, which is attributable to radiation-enhanced gallium diffusion.     

GaN buffer layer growth by MOCVD using a thermodynamic non-equilibrium model

In this work, a gallium nitride (GaN) buffer layer was grown on a sapphire substrate (α-Al₂O₃) in a horizontal reactor by low pressure metal-organic chemical vapor deposition (LP-MOCVD). Trimethylgallium (TMGa) and ammonia (NH₃) were precursors of gallium and nitrogen, respectively, and hydrogen (H₂) was used as carrier gas. TMGa and NH₃ fluxes were kept constant, with flow rates of 3.36 μmole/min and 0.05 standard liter/min, respectively. The fluence of hydrogen was also kept constant with the flux rate of 4.5 standard liter/min. GaN was deposited at 550 °C and 100 mbar. According to the X-ray diffraction spectra, a buffer layer was formed with a wurtzite structure, which is the stable phase. The thermodynamic affinities were estimated as A₁ = 175.9 kJ/mole and A₂ = 62.88 kJ/mole.     

Epitaxy of gallium nitride in semi-polar direction on Si(210) substrate

The idea of a new method for growing gallium nitride (GaN) epilayers in semi-polar direction by hydride-chloride vapor-phase epitaxy (HVPE) is disclosed. We propose to use Si(210) substrates with the first buffer layer of silicon carbide (3C-SiC) and the second buffer layer of aluminum nitride (AlN). It is experimentally demonstrated for the first time that, under conditions of anisotropic deformation in the GaN/AlN/3C-SiC/Si(210) structure, a GaN epilayer exhibits growth in semi-polar directions.     

Preparation of single phase gallium nitride from single crystal gallium arsenide

An analysis has been conducted on the final products obtained in attempts to prepare single phase gallium nitride from single crystal gallium arsenide. When the intermediate oxide phase was nitrided in pure ammonia it was found that (i) the lowest temperature at which rate of conversion of-Ga₂O₃ to GaN became significant was in the range 600 to 700°C, (ii) over the temperature range 700 to 1000°C GaN was found to be the only crystalline phase present, (iii) above 1100°C-Ga₂O₃ was the main constituent. In comparison, when the oxide phase was nitrided in a 50% NH₃-50% N₂ atmosphere it was found that (i) the lowest temperature at which conversion to GaN occurred lay between 700 and 750°C, (ii) there was only a narrow range of temperatures, 750 to 870°C, in which the final products were found to contain GaN as the only crystalline phase, (iii) samples nitrided above 870°C exhibited both GaN and-Ga₂O₃ phases, the proportion of-Ga₂O₃ increasing with increasing temperature.     

Basal plane-oriented gallium nitride films on fused silica via acetate dip coating

c-axis-oriented gallium nitride (wurtzite GaN) thin films were fabricated by nitridation of acetate derived precursor films deposited on fused silica substrates without any buffer layer on the top of the substrate. The acetate derived precursors were obtained by (i) preparing a gallium-acetate sol by reacting Ga metal with acetic acid, (ii) coating cleared fused silica substrate with the sol and (iii) after drying the coated films at 100 °C, annealing them in air at 300°, 500° and 900 °C. Only films showing crystallization of α-GaO(OH) (300 °C) and (α + β)-Ga₂O₃ (500 °C) were selected for nitridation. In spite of the amorphous nature of the substrate, the GaN films showed a strong preferred orientation for the basal plane (002) under selected conditions of precursor annealing (300°, 500 °C) and subsequent nitridation (under flowing NH₃) temperature and time. In other cases formation of an additional plane, i.e. (101) was indicated as a weaker peak in X-ray diffraction (XRD) patterns. The precursors and nitride films were characterized by Fourier transform infrared spectroscopy, UV-Visible spectroscopy, XRD, high resolution transmission electron microscopy and atomic force microscopy analyses.     

缓冲层对氮化镓二维生长的影响

报道了在射频等离子体（RF-Plasma)辅助的分子束外延（MBE）技术中，使用白宝石（0001）衬底，采用低温缓冲层工艺外延氮化镓（GaN)。通过原子力显微镜（AFM）的表面形貌比较及X射线双晶衍射（XRD）ω扫描摇摆曲线的分析，讨论了低温缓冲层成核机理及缓冲层生长温度与形成准二维生长的关系，确立了缓冲层的三维成核，准二维生长的生长机理，并在此基础上实现了氮化镓外延层更好地二维生长，进一步提高了氮化镓外延层的晶体质量。     

Epitaxial growth of gallium nitride by ion-beam-assisted evaporation

The epitaxial growth of gallium nitride thin film was obtained on the inclined Si(111) substrates by the process of ion-beam-assisted evaporation (IBAE) at the low temperature of 500 °C. The film composition determined by Rutherford backscattering spectrometry shows that the synthesized film is a stoichiometric nitride. The epitaxial quality of GaN film is enhanced by minimizing the bombardment-induced film damage by decreasing the ion flux. However, the crystallinity of the GaN film becomes very poor when the ion flux is not sufficient to densify the film. The optimum flux ratio of N⁺₂ to Ga and the energy of incident N⁺₂ ions for the epitaxial growth were found to be 3.4 and 50 eV, respectively. The GaN film deposited on the 4 °-inclined Si (111) with respect to substrate surface shows much better crystalline quality compared with that on the 0 ° inclined Si(111) due to many stable nucleation sites. A thin amorphous layer exists at the interface between GaN and Si(111) substrate and acts as a buffer zone enabling the subsequent epitaxial growth of GaN by relaxing the large misfit strain (23%) in the early stage of film growth. The epitaxial GaN film shows an orientational relation with the Si(111) substrate.     

High-temperature strength of bulk single crystals of III-V nitrides

A Vickers indentation method was used to determine the hardness of AlN and GaN, grown by the hydride vapor phase epitaxy technique, in the temperature range 20–1400 °C. At room temperature, the hardnesses of GaN and AlN are 10.2 and 17.7 GPa, respectively. The hardness of GaN and AlN shows a gradual decrease from RT and then a steep decrease from around 1000 °C. AlN is harder than GaN but softer than SiC. The steep decrease of the hardness means the beginning of macroscopic dislocation motion and plastic deformation. The mechanical strength of bulk single-crystal GaN is investigated at elevated temperatures directly by means of compressive deformation. The yield stress of GaN in the temperature range 900–1000 °C is around 100–200 MPa, i.e., similar to that of 6H-SiC and much higher than those of Si, Ge, GaAs.     

Fabrication of epitaxial III-nitride cantilevers on silicon (1 1 1) substrates

The molecular beam epitaxy of AlGaN/GaN epilayers on silicon (1 1 1) using an aluminum nitride buffer layer, and subsequent fabrication of free standing III-nitride cantilevers on Si(1 1 1) has been investigated. Transmission electron microscopy (TEM) of cross-section samples reveals a columnar structure consisting of the hexagonal gallium nitride polytype. Selected area diffraction indicates an epitaxial relationship between the gallium nitride and silicon substrate which is described by GaN[0 0 0 1]//Si[1 1 1] and GaN(1 1 0 0)//Si(1 1 1). Imaging of the electronic structure of an AlGaN/GaN interface has been investigated by mapping the variation in the plasmon frequency using an electron energy loss spectrometer on a dedicated scanning transmission electron microscope. Cantilevers were fabricated using a combination of etching processes. Nitride etch rates during inductively coupled plasma dry etch processing using a Cl₂/Ar plasma etchant were obtained by monitoring the optical reflectivity of the nitride films in situ. A peak GaN etch rate of 250 nm/min was measured, the etch rate was found to be strongly dependent on the d.c. self-bias. Thin beams of GaN having a length of 7 μm and 0.7 μm thickness, were fabricated and mechanically released from Si(1 1 1) substrates using a combination of two dry ICP etch processes, using Cl₂/Ar and CF₄/Ar/O₂ chemistries, and a potassium hydroxide (KOH) aqueous wet etch.     

Laser deposition of gallium nitride films

Insulating c-oriented hexagonal epitaxial gallium nitride (GaN) films have been obtained by means of pulsed laser sputtering of a gallium target in nonactivated nitrogen atmosphere. The GaN films were deposited onto (0001)-oriented sapphire substrates either directly or above a ZnO buffer layer. The laser-deposited films exhibit edge photoluminescence at 370 nm.     

Optical properties and carrier dynamics of self-assembled GaN/Al(0.11)Ga(0.89)N quantum dots

GaN quantum dots were grown on an Al(0.11)Ga(0.89)N buffer layer by using flow rate modulation epitaxy. The Stranski-Krastanov growth mode was identified by an atomic force microscopy study. The thickness of the wetting layer is about 7.2 monolayers. The temperature dependent photoluminescence studies showed that at low temperature the localization energy, which accounts for de-trapping of excitons, decreases with the reducing dot size. The decrease in emission efficiency at high temperature is attributed to the activation of carriers from the GaN dot to the nitrogen vacancy (V(N)) state of the Al(0.11)Ga(0.89)N barrier layer. The activation energy decreases with reducing dot size.     

A systematic study on group III-nitride thin films with low temperature deposited via MOCVD

Wide bandgap semiconductor materials provide superior electrical, optical, and thermal properties that classical semiconductors, Si and GaAs, are unable to achieve. However, most commercially available substrates have large lattice and thermal expansion mismatches to III-nitrides films. Thus a high quality buffer layer, grown at low temperatures, is essential in growing high quality III-nitride films. This research provides a throughout study on III-nitrides, such as AlN, GaN and AlGaN thin films, which were grown at low temperatures (400–600 °C). Growth rate, stoichiometry and crystal structure of low temperature growth films will be reported by using several advanced post-growth analysis techniques. Temperature, pressure, and V/III molar ratio were also investigated to determine their effect on the film properties. From the study, a better understanding of the relationships between film properties and growth parameters will be achieved.