大尺寸HVPE反应器寄生沉积的数值模拟研究

在氢化物气相外延(HVPE)生长GaN厚膜中,反应腔壁面总会产生大量的寄生沉积,严重影响薄膜生长速率及质量.本文针对自制的大尺寸垂直式HVPE反应器,通过数值模拟与实验对比,研究了反应腔壁面沉积以及GaN生长速率的分布规律,特别是寄生沉积分布与载气流量的关系.研究发现:在基准条件下,顶壁寄生沉积速率由中心向边缘逐渐降低,与实验结果吻合;侧壁沉积出现8个高寄生沉积区域,对应喷头边缘处排布的GaCl管,说明沉积主要取决于GaCl的浓度输运;模拟得出的石墨托表面生长速率低于实验速率,但趋势一致.保持其他条件不变,增大NH3管载气N2流量,顶壁和侧壁的寄生沉积速率及分布区域均随之增大,石墨托表面生长速率随之减小而均匀性却随之提高;增大GaCl管载气N2流量,顶壁和侧壁的寄生沉积速率及分布区域均随之减小,石墨托表面生长速率随之增大而均匀性却随之降低.研究结果为大尺寸HVPE反应器生长GaN的工艺优化提供了理论依据.     

Low pressure MOVPE of GaN and GaInN/GaN heterostructures

GaN single layers and GaInN/GaN heterostructures have been grown by low pressure metalorganic vapor phase epitaxy on sapphire substrates. We found best growth conditions and the highest growth rate for GaN to be at about 1000°C, whereas the growth rate decreased for both, higher and lower temperatures. In contrast, GaInN with a significantly high In content could only be grown at lower temperatures around 700°C. Besides growth temperature and reactor pressure, the composition of the carrier gas was found to play an important role: the In incorporation rate is about doubled when reducing the hydrogen/nitrogen ratio. GaInN/GaN quantum wells show even higher In contents compared to bulk layers.     

Growth and process modeling studies of nickel-catalyzed metalorganic chemical vapor deposition of GaN nanowires

A combination of experimental and computational fluid dynamics-based reactor modeling studies were utilized to study the effects of process conditions on GaN nanowire growth by metalorganic chemical vapor deposition (MOCVD) in an isothermal tube reactor. The GaN nanowires were synthesized on (0 0 0 1) sapphire substrates using nickel thin films as a catalyst. GaN nanowire growth was observed over a furnace temperature range of 800–900 °C at V/III ratios ranging from 33 to 67 and was found to be strongly dependent on the position of the substrate relative to the group III inlet tube. The modeling studies revealed that nanowire growth consistently occurred in a region in the reactor where the GaN thin-film deposition rate was reduced and the gas phase consisted primarily of intermediate species produced by the reaction and decomposition of trimethylgallium–ammonia adduct compounds. The GaN nanowires exhibited a predominant [1 1 2¯ 0] growth direction. Photoluminescence measurements revealed an increase in the GaN near-band edge emission intensity and a reduction in the deep-level yellow luminescence with increasing growth temperature and V/III ratio.     

Growth of Epitaxial Layers of GaN from GaBr3 · 4 NH3 Complex

A method of obtaining GaN from GaBr₃ · 4 NH₃ by radiation heating of the substrate is described. The results of investigations are given concerning the growth rate of polycrystalline GaN layers on [111] oriented silicon substrates in dependence on the changes of the temperature of reaction, evaporation temperature of GaBr₃ · 4 NH₃, and the rate of gas flow. The results of X-ray investigations and light absorption coefficient are described. Some facts were observed, namely a considerable influence of the nozzle form on the kinetics of the transporting gas stream on the growth rate of GaN, as well as the fact that not the whole complex undergoes pyrolysis on the substrate at temperatures below 500°C.     

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.     

Surface chemistry and transport effects in GaN hydride vapor phase epitaxy

A simple quasi-thermodynamic model of surface chemistry in GaN hydride vapor phase epitaxy (HVPE) is presented. The model is coupled with the detailed 3D simulations of species transport in a horizontal-tube reactor and validated by the comparison with the data on the GaN growth rate obtained by laser reflectometry. Parametric study of the growth rate as a function of temperature and species flow rates has been performed over a wide range of growth conditions. The important role of species transport in an HVPE reactor is demonstrated. In particular, a strong effect of the natural concentration convection resulting in the formation of recirculation zones and in a non-uniform vapor composition is revealed by modeling. The impact of these effects on the GaN growth rate and V/III ratio on the growth surface is discussed in detail.     

On the origin of free carriers in high-conducting n-GaN

Growth experiments with GaN in the system Ga/HCl/NH₃/He at different growth temperatures show that the assumption of N-vacancies to be responsible for the high n-conductivity is questionable. The dependence of carrier concentration on growth temperature as well as the decrease in carrier concentration when additionally purified NH₃ is used indicate that donor impurities are incorporated. The most probable impurity is oxygen, substitutionally incorporated onto N-sites. The observed growth rate dependence of carrier concentration can well be explained by a kinetically controlled incorporation process.     

Bulk GaN single crystals: growth conditions by flux method

Hexagonal GaN platelet crystals with a size of 1–4 mm have been grown by a Li-based flux method. The influence of growth conditions such as the molar ratio of starting materials, temperature, pressure, the position of Li₃N in the crucible on the growth of GaN single crystals was studied. The quality of GaN single crystal was checked by optical microscope and X-ray rocking curve.     

Numerical design of Metal‐Organic Vapour Phase Epitaxy process for gallium nitride epitaxial growth

The paper presents the results of numerical simulations and experimental measurements of the epitaxial growth of gallium nitride in Metal Organic Vapor Phase Epitaxy within a AIX‐200/4RF‐S reactor. The aim was to develop optimal process conditions for obtaining the most homogeneous crystal layer. Since there are many factors influencing the chemical reactions on the crystal growth area such as: temperature, pressure, gas composition or reactor geometry, it is difficult to design an optimal process. In this study various process pressures and hydrogen volumetric flow rates have been considered. Due to the fact that it is not economically viable to test every combination of possible process conditions experimentally, detailed 3D modeling has been used to get an overview of the influence of process parameters. Numerical simulations increased the understanding of the epitaxial process by calculating the heat and mass transfer distribution during the growth of gallium nitride. Appropriate chemical reactions were included in the numerical model which allowed for the calculation of the growth rate of the substrate. The results obtained have been applied to optimize homogeneity of GaN film thickness and its growth rate.     

Low-temperature characteristics of the current gain of GaN/InGaN double-heterojunction bipolar transistors

We investigated the temperature dependence of the current gain of npn-type GaN/InGaN double-heterojunction bipolar transistors (DHBTs) in the low-temperature region. The current gain increased with decrease in device temperature due to the reduction of the recombination current in the p-type base layer. The current gain reached as high as 5000 at 40 K, which is the highest among nitride-based HBTs. For conventional HBTs made of InP or GaAs, the current gain decreased with decreasing device temperature. However, no reduction of the current gain was observed in this study, suggesting that the minority carrier mobility in the p-type InGaN base layer has negative temperature dependence, presumably because the ionized impurity scattering is relatively unaffected owing to the carrier freezeout and the high activation energy of Mg in the p-InGaN base layer.     

Influence of growth temperature on growth of InGaAs nanowires in selective-area metal–organic vapor-phase epitaxy

Indium-rich InGaAs nanowires were grown on an InP (111)B substrate by catalyst-free selective-area metal–organic vapor phase epitaxy, and the growth-temperature dependence of growth rate and composition was studied. In particular, nanowire growth rate rapidly decreases as growth temperature increases. This tendency is opposite (for a similar temperature range) to that found in a previous study on selective-area growth of gallium-rich InGaAs nanowires. This difference between indium-rich and gallium-rich nanowires suggests that the influence of growth temperature on the growth of InGaAs nanowires is dependent on the group-III supply ratio. On the basis of previous experimental observations in InAs and GaAs nanowires, temperature dependence of nanowire growth rate and its dependence on group-III supply ratio are predicted. A guideline to determine the optimum growth conditions of InGaAs nanowires is also discussed.     

Effects of morphologies on the field emission characteristics of GaN nanorods grown on Si (0 0 1) by MBE

GaN nanorods were grown on Si (0 0 1) substrates with a native oxide layer by molecular beam epitaxy. The changes in the morphologies and their effects on the field emission characteristics of GaN nanorods were investigated by varying growth conditions, namely, growth time of low-temperature GaN buffer layer, growth time of GaN nanorods, Ga flux during growth of GaN nanorods, and growth temperature of GaN nanorods. GaN nanorods with a low aspect ratio measured by diode configuration showed better field emission characteristics than those with a high aspect ratio, which may be due to the effects of screening and the surface depletion layer. In addition, the distance between the GaN nanorods and the anode played an important role in the field emission characteristics such as turn-on field, field enhancement factor, and field distribution on the emitter surface.     

Study of the metastable region in the growth of GaN using the Na flux method

It was revealed that the metastable region, in which liquid phase epitaxy (LPE) of GaN single crystals proceeds without the generation of polycrystals, expands with growth temperature in the Na flux method. The metastable region appears when LPE growth proceeds at temperatures above 1073 K, although generation of polycrystals inevitably occurs on a crucible at temperatures less than 1073 K. The highest growth rate of 14 μm/h in a small experimental setup was achieved at a temperature of 1163 K with a nitrogen pressure of 5.5 MPa due to complete suppression of the growth of polycrystals on a crucible, even though the supersaturation at this condition reached a fairly high level.Also, an LPE crystal with a flat surface could easily be obtained under high-temperature conditions.     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

Alternative precursors for MOVPE growth of InN and GaN at low temperature

We report on the use of dimethylhydrazine (DMHy) and tertiarybuthylhydrazine (TBHy), as alternative nitrogen precursor for GaN low-temperature growth, as well as to improve the InN growth rate. Lowering the GaN growth temperature, would allow growing InN/GaN heterostructures by MOVPE, without damaging the InN layers. Increasing the low InN MOVPE growth rate is of major importance to grow reasonably thick InN layers. In this respect, triethylindium (TEIn) was also used as an alternative to trimethylindium (TMIn).     

High quality MOCVD GaN film grown on sapphire substrates using HT-AlN buffer layer

In this work we report on the growth and characterization of high quality MOCVD GaN film grown on Al₂O₃ substrates by using a HT (>1150 °C)-AlN buffer layer. We have investigated the most favorable growth conditions in terms of temperature, thickness and growth rate of AlN buffer layer in order to optimize the high temperature GaN layer. The improved morphological and structural properties of GaN layer were verified by AFM and XRD measurements. The optimized GaN layer presents a smooth surface with a rms value of 1.4 Å. The full width at half maximum (FWHM) for 800 nm thick GaN films is 144″. Furthermore PL measurements and C–V analysis confirm that in GaN layer grown on HT-AlN buffer layer defect density is drastically reduced.     

Vapor phase growth of GaN using GaN powder sources and thermogravimetric investigations of the evaporating behaviour of the source material

The growth of GaN from the vapor phase is a promising technique for producing both bulk GaN crystals and GaN layers. For establishing a growth method from the vapor phase the source material and reactor setup are of great importance. Highly pure and self synthesized GaN powder was chosen as source material. The evaporation behaviour of the GaN powder was studied by means of thermogravimetry (TG). A vertical growth reactor was set up according to the results of numerical simulations of the temperature distributions and flow patterns. Freely nucleated GaN platelets of some millimetres in length were grown. Furthermore, thin GaN layers were deposited directly on a sapphire substrate. This nucleation layer was successfully overgrown by low pressure solution growth. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth mechanisms in excimer laser photolytic deposition of gallium nitride at 500°C

The mechanisms of controlling laser-induced chemical vapour deposition of GaN at substrate temperatures between 350 and 650°C have been investigated. Ultraviolet (193 nm) photolytic decomposition of trimethylgallium (TMGa) and ammonia (NH₃) precursors was examined in this range. Laser-induced fluorescence studies support the view that the dissociated intermediate fragments GaCH₃ and NH are the reacting species in GaN film formation, irrespective of substrate temperature. It was found that two crystal phases coexist in films grown at substrate temperatures below 500°C, wurtzite crystal structure with (0002) orientation forms at substrate temperatures above 500°C. The growth rate increases with both NH₃/TMGa ratio, and TMGa flow rate, while the temperature dependence shows a thermal activation energy of 0.2 eV which is smaller by a factor of five than that of films prepared by conventional thermal CVD. The large NH₃/TMGa ratios needed to achieve stoichiometry are interpreted in terms of the two-photon dissociation cross section of NH₃.     

用数学模型计算生长大尺寸光学晶体加热系统结构 第2部分—在φ4 00mmCaF_2晶体生长中计算辐射-传导热交换的方法和结果(英文)

大尺寸氟化物晶体的生长是基于对晶体炉热交换的实验研究和计算结果 ,在晶体生长过程的不同阶段解决了复杂结构生长容器的边界条件和温场的二维计算任务。我们在这里给出了晶体生长过程中温场设置和转变的具体数据。所有的计算都是根据晶体、熔体 ,容器材料的光学特性与光谱和温度的关系以及它们的热物理值与温度的关系做出的。这些结果包括了迄今有关氟化物晶体生长系统和过程的最精确的数据 ,可用于生长技术工艺的发展以及晶体生长炉和容器的设计。     

New dopant precursors for n-type and p-type GaN

Tetraethylsilane (TeESi) and bis(ethylcyclopentadienyl)Mg (ECp₂Mg) were employed as Si and Mg dopant precursors for MOVPE growth of n-type and p-type GaN films, respectively. In Si doping, the electron concentration was observed to increase with the increase of the TeESi flow rate. The temperature dependence of the Hall mobility showed good agreement with n-type GaN films grown using different dopant precursors (SiH₄, GeH₄, Si₂H₆). The donor activation energy was estimated to be 27 meV, which is almost the same as the literature values. In Mg doping, we also found that the Mg concentration increases as the ECp₂Mg flow rate increases. All of Mg-doped samples in this study showed p-type conduction after annealing. The acceptor activation energy was estimated to be 170 meV, which was close to the reported values.