Ammonothermal epitaxy of wurtzite GaN using an NH4I mineralizer

Purely wurtzite phase needle crystals and epitaxial layers of GaN were grown by the ammonothermal method using an NH₄I mineralizer. The inclusion of zincblende phase GaN was effectively eliminated by increasing the growth temperature higher than 500 °C. Accordingly, an approximately 20-μm-thick GaN epitaxial layer was achieved on the Ga-polar face of a c-plane GaN seed wafer at 520 °C. Although the characteristic deep state emission band dominated the room temperature photoluminescence spectrum, the near-band-edge emission of GaN was observed for both the needle crystals and the epitaxial layers. These results encourage one to grow better quality GaN crystals at a high growth rate under high-temperature growth conditions.     

Optimized growth conditions of GaN epitaxial layers

Optimized growth conditions of the epitaxial GaN layers on the (0001) oriented sapphire substrates in the Ga/HCl/NH₃/H₂ system have been proposed. The corresponding growth rate varied about the value 0.5 μm · min⁻¹. The study of surface morphology and X-ray diffraction have confirmed the single crystalline character of the layers even though the surface shows a faceted structure. The c/a ratio calculated from our measured data of the lattice parameters was found 1.624 which is relatively close to the ideal close-packed wurtzite structure value. The cathodoluminescent spectra of the layers with a sufficient thickness were characterized by a peak at 3.35 eV having a halfwidth of about 0.2 eV.     

Molecular beam epitaxy as a growth technique for achieving free-standing zinc-blende GaN and wurtzite AlxGa1-xN

Currently there is a high level of interest in the development of ultraviolet (UV) light sources for solid-state lighting, optical sensors, surface decontamination and water purification. III-V semiconductor UV LEDs are now successfully manufactured using the AlGaN material system; however, their efficiency is still low. The majority of UV LEDs require Al_xGa_1-xN layers with compositions in the mid-range between AlN and GaN. Because there is a significant difference in the lattice parameters of GaN and AlN, Al_xGa_1-xN substrates would be preferable to those of either GaN or AlN for many ultraviolet device applications. However, the growth of Al_xGa_1-xN bulk crystals by any standard bulk growth techniques has not been developed so far.There are very strong electric polarization fields inside the wurtzite (hexagonal) group III-nitride structures. The charge separation within quantum wells leads to a significant reduction in the efficiency of optoelectronic device structures. Therefore, the growth of non-polar and semi-polar group III-nitride structures has been the subject of considerable interest recently. A direct way to eliminate polarization effects is to use non-polar (001) zinc-blende (cubic) III-nitride layers. However, attempts to grow zinc-blende GaN bulk crystals by any standard bulk growth techniques were not successful.Molecular beam epitaxy (MBE) is normally regarded as an epitaxial technique for the growth of very thin layers with monolayer control of their thickness. In this study we have used plasma-assisted molecular beam epitaxy (PA-MBE) and have produced for the first time free-standing layers of zinc-blende GaN up to 100 μm in thickness and up to 3-inch in diameter. We have shown that our newly developed PA-MBE process for the growth of zinc-blende GaN layers can also be used to achieve free-standing wurtzite Al_xGa_1-xN wafers. Zinc-blende and wurtzite Al_xGa_1-xN polytypes can be grown on different orientations of GaAs substrates - (001) and (111)B respectively. We have subsequently removed the GaAs using a chemical etch in order to produce free-standing GaN and Al_xGa_1-xN wafers. At a thickness of ～30 µm, free-standing GaN and Al_xGa_1-xN wafers can easily be handled without cracking. Therefore, free-standing GaN and Al_xGa_1-xN wafers with thicknesses in the 30–100 μm range may be used as substrates for further growth of GaN and Al_xGa_1-xN-based structures and devices.We have compared different RF nitrogen plasma sources for the growth of thick nitride Al_xGa_1-xN films including a standard HD25 source from Oxford Applied Research and a novel high efficiency source from Riber. We have investigated a wide range of the growth rates from 0.2 to 3 µm/h. The use of highly efficient nitrogen RF plasma sources makes PA-MBE a potentially viable commercial process, since free-standing films can be achieved in a single day.Our results have demonstrated that MBE may be competitive with the other group III-nitrides bulk growth techniques in several important areas including production of free-standing zinc-blende (cubic) (Al)GaN and of free-standing wurtzite (hexagonal) AlGaN.     

Lateral confined epitaxy of GaN layers on Si substrates

We developed a novel, simple procedure for achieving lateral confined epitaxy (LCE). This procedure enables the growth of uncracked GaN layers on a Si substrate, using a single, continuous metalorganic chemical vapor deposition (MOCVD) run. The epitaxial growth of GaN is confined to mesas, defined by etching into the Si substrate prior to the growth. The LCE-GaN layers exhibit improved morphological and optical properties compared to the plain GaN-on-Si layers grown in the same MOCVD system. By performing a set of LCE growth runs on mesas of varying lateral dimensions, we specified the crack-free range of GaN on Si as 14.0±0.3 μm.     

MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

AlN buffer layer growth for GaN epitaxy on (1 1 1) Si: Al or N first?

AlN is generally used as buffer layer for the epitaxial growth of GaN on Si(1 1 1) substrate. In this work, we specifically address the relationship between the way the AlN growth is initiated on the Si(1 1 1) surface and the overall properties of the final GaN epitaxial layer. The growth is performed by molecular beam epitaxy with ammonia (NH₃) as nitrogen source. Two procedures have been compared: exposing the Si surface first to NH₃ or Al. The AlN nucleation is followed in real-time by reflection high-energy electron diffraction and critical stages are also investigated in real space using scanning tunnelling microscopy and transmission electron microscopy. Atomic force microscopy, X-ray diffraction and photoluminescence are also used to assess the properties of the final GaN epitaxial layer. It is shown that best results in terms of GaN overall properties are obtained when the growth is initiated by exposing the Si(1 1 1) surface to NH₃ first. This is mainly due to the fact that almost an order of magnitude decrease of the dislocation density is obtained.     

Chemical mapping of InGaN MQWs

High power LEDs fabricated from InGaN/GaN layers have received much research interest. Hence, in this paper we identify structural and chemical defects resulting from the epitaxial growth of these layers, which directly effect the performance of the device. TEM, annular dark field imaging (ADF), energy filtered TEM (EFTEM) and X-ray mapping were used to study multiple quantum wells structures capped with a p-type GaN layer. TEM and ADF studies of the samples show a number of V-defects which are roughly 100–200 nm apart along the MQW. Each V-defect incorporates a pure edge ( ) dislocation, which runs through the apex of the V-defect up to the free surface. These V-defects contain GaN with no InGaN layers, suggesting that the capping layer has filled in the open V-defects.     

Thick GaN layers on sapphire with various buffer layers

Thick GaN layers deposited in HVPE system on composite substrates made on sapphire substrates in Metalorganic Vapour Phase Epitaxy (MOVPE) system have been investigated. The following substrates were used: (00.1) sapphire substrates with AlN, AlN/GaN and GaN thin layers. The crystallographic structure and the quality of the epitaxial thick GaN layers were determined. Comparison of the three types of thick layers was performed. Significant differences were observed. It was found that thick GaN deposited on the simplest MOVPE‐GaN/sapphire composite substrate has comparable structure's properties as the other, more complicated. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical stress calculations in polar,semipolar and nonpolar AlGaN/GaN heterostructures of different compositions

The new comprehensive model of the process for matching epitaxial layers to substrates, in dependence of theirs crystallographic orientation, was developed to allow a theoretical prediction of the strain and stress in thin AlGaN epitaxial layers with different composition grown on GaN template. The elements of the continuous anisotropic materials strength theory was applied to develop the model. It was observed that in AlGaN/GaN heterostructures the stress was greater than the upper limit of acceptable tensile stress even for a small Al content and also that the stress could greatly vary, in a value and a direction, depending on substrate crystallographic orientation and an Al content in AlGaN layer. The obtained results theoretically explained the commonly observed technological problems occurring during the growth of AlGaN layers even with a small Al content.     

An overview of gallium nitride growth chemistry and its effect on reactor design: Application to a planetary radial-flow CVD system

In this paper, gallium nitride (GaN) growth chemistry is characterized by two competing reaction pathways. An overview of GaN gas-phase and surface-phase chemistry is used to generate a comprehensive model for epitaxial GaN growth from the commonly used precursors, trimethylgallium ((CH₃)₃Ga) and ammonia (NH₃). The role of reactor geometry in controlling the selectivity among the competing reaction pathways is explored in the context of a planetary radial-flow CVD system. Finally, application of a geometrically based uniformity criterion is presented for film uniformity optimization.     

Bismuth a new dopant for GaN films grown by molecular beam epitaxy—surfactant effects,formation of GaN1−xBix alloys and co-doping with arsenic

We have investigated the influence of an additional bismuth flux during growth on the properties of GaN films prepared by plasma-assisted molecular beam epitaxy (MBE). A wide range of bismuth fluxes have been used, the highest Bi flux was larger than the flux of Ga. We have demonstrated that using a Bi flux during the growth of GaN by MBE at a temperature ∼800°C improves the surface morphology of the films and decreases the deep emission. We have demonstrated for the first time the growth of GaN_1−xBi_x alloys by MBE, the Bi concentration was small and increased with decreasing growth temperature. We have studied the influence of an additional bismuth flux on the growth of As-doped GaN layers and observed an increase of blue emission from the layers at some optimum range of Bi fluxes. All the results allow us to conclude that Bi may be a potential new dopant for the growth of GaN by MBE.     

Cross‐sectional and surface Raman mapping of thick GaN layers

Raman scattering spectroscopy was utilized for investigation of the structural properties of thick GaN layers. These layers with thickness ∼ 40 μm have been grown by HVPE technique on the sapphire substrates. The investigations have been focused on the strain distribution in GaN layer cross‐section as a function of distance from an interface sapphire/GaN and mapping of the surface and of the inner layer, near the sapphire/GaN interface. From the observed phonon shifts in the Raman spectra strain differences lower than 6.4×10^–4 corresponding to stress differences of 240 MPa were estimated across the thick GaN epitaxial layer. The measurements exhibit that strain in the layer causes changes in the Raman spectra and allow determining the relaxation process in the crystal. The obtained results confirmed, that the mode frequencies in the measured Raman spectra in both directions (parallel or perpendicular to the growth direction) for layer thicknesses over 30 µm are comparable with typical values for bulk material and match the low strain in the structure due to relaxation processes. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Growth Kinetics and Surface Morphology of GaN Epitaxial Layers on Sapphire

The growth kinetics of GaN on Sapphire was analyed on the base of some experimental data such as: the growth rate temperature depandence, on the base of some experimental data such as: the growth rate temperature dependence, the grwoth rate dependence on the gas flow velocity, the growth rate depandence on the crystallographic and spatial orientation of the substrate. The limiting stage of the epitaxy process was established at different growth conditions. The morphology of GaN epitaxial layers obtained at these conditions is described.     

Doping mechanism and properties of Zn-doped GaN-epitaxial layers

The role of oxygen in the process of doping GaN by Zn is established. It is shown theoretically and experimentally that Zn is dissolved in GaN in the form of complexes Zn O when oxygen or water vapour is present in the ambient of the growth reactor. Most of the complexes are neutral. Only the small part of Zn introduced is situated in electrically active positions. This fact can explain the enormously high Zn concentration which is necessary to obtain the compensation of GaN native donors. The electrical and luminescence properties of GaN epitaxial layers doped by Zn are given and the relation of these properties to the growth and doping conditions are considered.     

Liquid phase epitaxial growth of Ga1−xAlxAs on channeled substrates

The growth mechanism of liquid phase epitaxial layers of Ga_1?xAl_xAs on preferentially etched GaAs substrates has been investigated. It has been found that enhanced diffusion of As atoms due to a local concentration gradient, which is set up by non-uniform growth at channels, plays a critical role in determining the growth morphology. The relation between growth morphology and growth conditions is discussed by using a simple growth model.     

Interface of GaN grown on Ge(1 1 1) by plasma assisted molecular beam epitaxy

Early efforts to grow GaN layers on germanium substrates by plasma assisted molecular beam epitaxy led to GaN domains, rotated by 8° relative to each other. Increased insight in the growth of GaN on germanium resulted in the suppression of these domain and consequently high quality layers. In this study the interface of these improved layers is investigated with transmission electron microscopy. The GaN layers show high crystal quality and an atomically abrupt interface with the Ge substrate. A thin, single crystalline Ge₃N₄ layer is observed in between the GaN layer and Ge substrate. This Ge₃N₄ layer remains present even at growth temperatures (850 °C) far above the decomposition temperature of Ge₃N₄ in vacuum (600 °C). Triangular voids in the Ge substrate are observed after growth. Reducing the Ga flux at the onset of GaN growth helps to reduce the triangular defect size. This indicates that the formation of voids in the Ge substrate strongly depends on the presence of Ga atoms at the onset of growth. However complete elimination was not achieved. The formation of voids in the germanium substrate leads to diffusion of Ge into the GaN layer. Therefore we examined the diffusion of Ge atoms into the GaN layer and Ga atoms into the Ge substrate. It was found that the diffusion of Ge into the GaN layer and Ga into the Ge substrate can be influenced by the growth temperature but cannot be completely suppressed. Our results suggest that Ga atoms diffuse through small imperfections in the Ge₃N₄ interlayer and locally etch the Ge substrate, leading to the diffusion of Ga and Ge atoms.     

Strain-reduced GaN thick-film grown by hydride vapor phase epitaxy utilizing dot air-bridged structure

A 300 μm GaN thick-film, in diameter 1.5 in, was demonstrated without any crack by hydride vapor phase epitaxy (HVPE) growth. The technique used in relaxing the residual stress caused by differences of thermal expansion coefficients (TEC) and lattice constants between GaN and sapphire substrate to prevent GaN film from crack is called a dot air-bridged structure. After the laser lift-off process, 300-μm-thick freestanding GaN wafer, in diameter 1.5 in, could be fabricated. The compressive stress in the dot air-bridged structure was measured by micro-Raman spectroscopy with the E₂(high) phonon mode. The compressive stress could be reduced to as small as 0.04 GPa, which could prevent the crack during the epitaxial process for GaN growth by HVPE. It is important to obtain a large-area crack-free GaN thick-film, which can be used for fabricating freestanding GaN wafer.     

LPE growth and characterization of InP/InGaAsP ridge-waveguide lasers at 1.3 μm-wavelength

This paper presents the fabrication and the lasing characteristics of 1.3 μm-wavelength ridge-waveguide laser. The epitaxial material used in this study was grown applying the step-cooling technique of liquid phase epitaxy (LPE). The growth conditions for InGaAsP layers lattice-matched to the (001) InP-substrate are reported for lattice compositions corresponding to photoluminescence peak wavelengths of 1.07, 1.14, and 1.31 μm. We have used a conventional multiple-bin sliding boat to grow the LPE layers and a second apparatus for achieving batches of melts of uniform compositions. In the LPE apparatus the various batch melts (In–Sn In–Zn; In–Ga–As of different composition) were saturated with phosphorus using the seed dissolution technique. The epitaxial layers were grown by a single phase technique at a constant temperature. This LPE growth technique is useful for the fabrication of double-heterostructure wafers with an uniform alloy composition and a well-defined layer thickness. Using these epitaxial materials, metal-clad ridge-waveguide (MCRW) lasers have been prepared with stripe widths of 3.5 μm. CW threshold currents of 18 mA at room temperature are achieved for 200 μm long cavities. These lasers have T₀ values ranging from 50 to 70 K and well linear L-I-characteristics.     

6H-SiC衬底片的表面处理

相比于蓝宝石,6H-SiC是制作GaN高功率器件更有前途的衬底.本文研究了表面处理如研磨、化学机械抛光对6H-SiC衬底表面特性的影响.用显微镜、原子力显微镜、拉曼光谱、卢瑟福背散射谱表征了衬底表面.结果表明经过两步化学机械抛光后提高了表面质量.经第二步化学机械抛光后的衬底具有优异的表面形貌、高透射率和极小的损伤层,其表面粗糙度RMS是0.12nm.在该衬底上用MOCVD方法长出了高质量的GaN外延膜.