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With the ammonothermal method, one of the most promising technologies for scalable, cost-effective production of bulk single crystals of the wide bandgap semiconductor GaN is investigated. Specifically, etch-back and growth conditions, as well as the transition from the former to the latter, are studied using a 2D axis symmetrical numerical model. In addition, experimental crystal growth results are analyzed in terms of etch-back and crystal growth rates as a function of vertical seed position. The numerical results of internal process conditions are discussed. Variations along the vertical axis of the autoclave are analyzed using both numerical and experimental data. During the transition from quasi-stable conditions of the dissolution stage (etch-back process) to quasi-stable conditions of the growth stage, significant temperature differences of 20 K to 70 K (depending on vertical position) occur temporarily between the crystals and the surrounding fluid. These lead to maximum rates of seed temperature change of 2.5 K/min to 1.2 K/min depending on vertical position. Based on temperature differences between seeds, fluid, and autoclave wall upon the end of the set temperature inversion process, deposition of GaN is expected to be favored on the bottom seed. The temporarily observed differences between the mean temperature of each crystal and its fluid surrounding diminish about 2 h after reaching constant set temperatures imposed at the outer autoclave wall, whereas approximately quasi-stable conditions are reached about 3 h after reaching constant set temperatures. Short-term fluctuations in temperature are mostly due to fluctuations in velocity magnitude, usually with only minor variations in the flow direction. [ABSTRACT FROM AUTHOR]

For the fundamental understanding and the technological development of the ammonothermal method for the synthesis and crystal growth of nitrides, an in situ monitoring technique for tracking mass transport of the nitride throughout the entire autoclave volume is desirable. The feasibility of using high-energy computed tomography for this purpose was therefore evaluated using ex situ measurements. Acceleration voltages of 600 kV were estimated to yield suitable transparency in a lab-scale ammonothermal setup for GaN crystal growth designed for up to 300 MPa operating pressure. The total scan duration was estimated to be in the order of 20 to 40 min, which was sufficient given the comparatively slow crystal growth speed in ammonothermal growth. Even shorter scan durations or, alternatively, lower acceleration voltages for improved contrast or reduced X-ray shielding requirements, were estimated to be feasible in the case of ammonoacidic growth, as the lower pressure requirements for this process variant allow for thinned autoclave walls in an adapted setup designed for improved X-ray transparency. Promising nickel-base and cobalt-base alloys for applications in ammonothermal reactors with reduced X-ray absorption in relation to the maximum operating pressure were identified. The applicability for the validation of numerical simulations of the growth process of GaN, in addition to the applicability of the technique to further nitride materials, as well as larger reactors and bulk crystals, were evaluated. [ABSTRACT FROM AUTHOR]

The effects of GaN quantum barriers with changing growth temperatures on the interfacial characteristics of GaN/InGaN single quantum well (SQW) grown on GaN templates by metalorganic vapour phase epitaxy were in situ investigated by X-ray crystal truncation rod (CTR) scattering and X-ray reflectivity measurements at growth temperature using a laboratory level X-ray diffractometer. Comparing the curve-fitting results of X-ray CTR scattering spectra obtained at growth temperature with that at room temperature, the InxGa1-xN with indium composition less than 0.11 was stabile of the indium distribution at the interface during the whole growth processes. By using several monolayers thickness GaN capping layer to protect the InGaN well layer within temperature-ramping process, the interfacial structure of the GaN/InGaN SQW was drastically improved on the basis of the curve-fitting results of X-ray CTR scattering spectra, and the narrow full width at half-maximum and strong luminous intensity were observed in room temperature photoluminescence spectra. [ABSTRACT FROM AUTHOR]

We investigate the influence of crystal defects on p-type GaN grown by metalorganic vapor phase epitaxy. Sets of p-type GaN films were grown on sapphire substrates and on free-standing GaN (F-GaN) substrates simultaneously using various Et-Cp2Mg flow rates. Although there is a difference of two orders of magnitude between the threading dislocation densities of p-type GaN grown on sapphire and F-GaN substrates, there is no significant difference in hole concentration. However, there are problems with the surface morphology of p-type GaN grown on sapphire. The deterioration of the surface was caused by the difference in nanopipe density. The electrical properties of a p-n junction diode formed on sapphire with a high density of nanopipes were observed using emission microscopy under both forward- and reverse-bias conditions. Our results demonstrate that the nanopipes are electrically inactive, and that other types of threading dislocation have more influence on the current-voltage characteristics. [ABSTRACT FROM AUTHOR]

We report on the characteristics of a-plane GaN films directly grown on optimized silicon-dioxide-patterned r-plane sapphire substrates. Various shapes and sizes of silicon dioxide patterns were considered with the aim of achieving fully coalescent a-plane GaN films with a smooth surface and high crystalline quality. The omega full widths at half maximum of the (11–20) X-ray rocking curve values of optimized a-plane GaN films with regular hexagonal patterns of 1μm window width and 6μm mask width were measured to be 597arc sec along the c-axis direction and 457arc sec along the m-axis direction. Atomic force microscopy images revealed a significant reduction in the density of submicron pits in the mask region. Plan-view and cross-sectional transmission electron microscopy images showed that basal stacking faults and threading dislocation densities were reduced from ~5.7×105 cm−1 and ~1×109 cm−2 in the window region to ~1.8×105 cm−1 and ~2.1×108 cm−2 in the mask region, respectively. [ABSTRACT FROM AUTHOR]

Carbon doping was investigated in (1-1 0 1) GaN, where the topmost surface is terminated by nitrogen. Intentional doping was performed supplying C2H2 as the source precursor during the MOVPE growth under N2 ambient. The sample showing p-type conduction exhibited a strong but broad peak at 361 nm in a low-temperature cathode luminescence spectrum. FTIR analyses were performed on these samples and a new absorption peak at 945 cm-1 was found along with an AlN-A1(LO) phonon mode at 888 cm-1. SIMS analyses showed unintentionally highly doped Al in the sample. The 945 cm-1 peak was assigned to a local vibration mode related to an Al-C bond. [ABSTRACT FROM AUTHOR]

The selective growth of wurtzite GaN was performed on a (1 1 1)silicon substrate by metalorganic vapor phase epitaxy. By limiting the size of GaN to the area of 0.5 mm×0.5 mm, a single GaN crystal without cracks was obtained. As a result, the full-width at half-maximum of the (0 0 0 4) X-ray-rocking curve as well as that of the band edge emission were much reduced as compared to the samples grown by a conventional method. [Copyright &y& Elsevier]

Numerical simulations are a valuable tool for the design and optimization of crystal growth processes because experimental investigations are expensive and access to internal parameters is limited. These technical limitations are particularly large for ammonothermal growth of bulk GaN, an important semiconductor material. This review presents an overview of the literature on simulations targeting ammonothermal growth of GaN. Approaches for validation are also reviewed, and an overview of available methods and data is given. Fluid flow is likely in the transitional range between laminar and turbulent; however, the time-averaged flow patterns likely tend to be stable. Thermal boundary conditions both in experimental and numerical research deserve more detailed evaluation, especially when designing numerical or physical models of the ammonothermal growth system. A key source of uncertainty for calculations is fluid properties under the specific conditions. This originates from their importance not only in numerical simulations but also in designing similar physical model systems and in guiding the selection of the flow model. Due to the various sources of uncertainty, a closer integration of numerical modeling, physical modeling, and the use of measurements under ammonothermal process conditions appear to be necessary for developing numerical models of defined accuracy. [ABSTRACT FROM AUTHOR]

Thermal boundary conditions for numerical simulations of ammonothermal GaN crystal growth are investigated. A global heat transfer model that includes the furnace and its surroundings is presented, in which fluid flow and thermal field are treated as conjugate in order to fully account for convective heat transfer. The effects of laminar and turbulent flow are analyzed, as well as those of typically simultaneously present solids inside the autoclave (nutrient, baffle, and multiple seeds). This model uses heater powers as a boundary condition. Machine learning is applied to efficiently determine the power boundary conditions needed to obtain set temperatures at specified locations. Typical thermal losses are analyzed regarding their effects on the temperature distribution inside the autoclave and within the autoclave walls. This is of relevance because autoclave wall temperatures are a convenient choice for setting boundary conditions for simulations of reduced domain size. Based on the determined outer wall temperature distribution, a simplified model containing only the autoclave is also presented. The results are compared to those observed using heater-long fixed temperatures as boundary condition. Significant deviations are found especially in the upper zone of the autoclave due to the important role of heat losses through the autoclave head. [ABSTRACT FROM AUTHOR]

Abstract: A novel activation process for Mg-implanted GaN was demonstrated. As opposed to the conventional thermal annealing process, an H2/NH3 alternating supply annealing process achieved better optical activation, stronger near-ultraviolet luminescence and weaker yellow luminescence in the photoluminescence spectroscopy. After this process, small hexagonal hillocks were observed on the surface, which indicated that crystal regrowth was induced by this process, consisting of decomposition of GaN by H2 supplies and re-crystallization by NH3 supplies. It was revealed that the implanted Mg could easily be located at the activation site by means of crystal regrowth by this process. [Copyright &y& Elsevier]

Abstract: Mg doping was attempted in (11¯01)GaN grown on a patterned (001)Si by selective metal-organic vapor phase epitaxy (MOVPE). The source material for the Mg doping was EtCp2Mg and the electrical properties were studied on samples with different doping levels. All samples showed p-type conduction. However, the hole concentration was decreased by the Mg doping at low doping levels followed by an increase at high doping levels. The activation energy was around 106–130meV depending on the doping level, which was larger than that found in undoped or carbon-doped samples. The AFM images showed gradual change in the surface structure in accordance with the Mg-doping level. The variation of the optical spectra was discussed in relation to the Mg-doping levels. [Copyright &y& Elsevier]

Abstract: The incorporation of carbon using CCl4 or C2H2 in metal–organic vapor phase epitaxy is studied on facets of a GaN stripe formed by selective area growth. The optical spectra of the sample were examined by cathode luminescence spectroscopy (CL). An edge emission peak specific to the facet was tentatively assigned to the acceptor bound exciton (ABE). The peak intensity was enhanced by the increase of the carbon doping and determined by the ratio of the carbon source and the NH3 flow rate. The CL image showed that the doping had been achieved uniformly on the facets but affected by the stress/strain due to the large lattice mismatch against the Si substrate. [Copyright &y& Elsevier]

Highlights • Ga-polar untwinned (1 0 −1 3) GaN was obtained by directional sputtering. • FWHM values are less than 550 aresec. • Al nucleation layer in directional sputtering affects the GaN layer much. Abstract Directional sputtering of Al and AlN on (1 0 −1 0) sapphire was used to obtain metal-polar (1 0 −1 3) templates. After overgrowth with AlN and GaN using metal-organic vapor phase epitaxy, we obtained untwinned (1 0 −1 3) GaN layers. Full width at half maximum of the X-ray rocking curve of symmetric (1 0 −1 3) GaN is less than 550 arcsec along both [3 0 −3 −2] GaN and [1 −2 1 0] GaN directions. Ga-polarity of the layers was confirmed by high-resolution scanning transmission electron microscopy. Careful optimization of time and temperature of the initial Al sputtered layer was a key parameter to achieve high quality GaN templates. [ABSTRACT FROM AUTHOR]

Abstract: Semi-polar (112¯2) GaN layers were selectively grown by metal organic chemical vapor phase epitaxy on patterned Si (311) substrates without SiO2 amorphous mask. The (112¯2) GaN layers could be selectively grown only on Si (111) facets when the stripe mask width was narrower than 1μm even without SiO2. Inhomogeneous spatial distribution of donor bound exciton (DBE) peak in low-temperature cathodoluminescence (CL) spectra was explained by the difference of growth mode before and after the coalescence of stripes. It was found that the emission intensity related crystal defects is drastically decreased in case of selective growth without SiO2 masks as compared to that obtained with SiO2 masks. [Copyright &y& Elsevier]

Abstract: Adopting anisotropy etching method, a (111) facet of Si is obtained on a Si substrate and selective area growth (SAG) of GaN is performed with metal-organic vapor phase epitaxy on the facet. The epitaxial lateral overgrowth of (11¯01), (112¯2) GaN is investigated on (001) and (113) Si substrate, respectively, and the incorporation properties of Si, C, and Mg elements are discussed in relation to the atomic configuration on the surface. Analyzing the optical and electrical properties of C-doped (11¯01) GaN layer, it is shown that carbon creates a shallow acceptor level. On the thus prepared (11¯01) GaN layer, a light emitting diode (LED) with a C-doped p-type layer is fabricated. [Copyright &y& Elsevier]