Numerical analysis for the growth of GaN layer in MOCVD reactor

The axi-symmetric vertical reactor is a classical reactor configuration for the growth of compound semiconductors by MOCVD. In the present study, the modified reactor is developed to produce uniform and large-volume epitaxial deposition of gallium nitride (GaN). A comprehensive knowledge of the flow, thermal and concentration fields, as well as gas surface reaction, is necessary to develop a CVD reactor. The full elliptic governing equations for continuity, momentum, energy and chemical species are solved numerically. It is investigated how thermal characteristics, reactor geometry, and the operating parameters affect flow fields, mass fraction of each reactant, and deposition rate uniformity. As results, inlet flow rate, inclination angle of wall and inlet design are proposed for optimum operational conditions.     

High pressure solution growth of GaN

An internally heated pressure vessel was used to study the decomposition reaction of GaN at temperatures above 900°C and the phase equilibria in the system Ga-N₂. As a consequence of these studies we have undertaken the crystal growth of GaN free crystals and epitaxial layers on sapphire by a VLS process. We have succeeded in the synthesis of high quality epitaxial layers showing the terrace structure typical of LPE. As a function of the growth conditions both n and p type gallium nitride were obtained, the latter only in polycrystalline form.     

Numerical investigation of crystal growth process of bulk Si and nitrides – a review

Heat and mass transfer during crystal growth of bulk Si and nitrides by using numerical analysis was studied. A three‐dimensional analysis was carried out to investigate temperature distribution and solid‐liquid interface shape of silicon for large‐scale integrated circuits and photovoltaic silicon. The analysis enables prediction of the solid‐liquid interface shape of silicon crystals. The result shows that the interface shape became bevel like structure in the case without crystal rotation. We also carried out analysis of nitrogen transfer in gallium melt during crystal growth of gallium nitride using liquid‐phase epitaxy. The result shows that the growth rate at the center was smaller than that at the center. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Systematic study of epitaxy growth uniformity in a specific MOCVD reactor

Gallium nitride (GaN) is a direct bandgap semiconductor widely used in bright light‐emitting diodes (LEDs). Thin‐film GaN is grown by metal‐organic chemical vapour deposition (MOCVD) technique. Reliability, efficiency and durability of LEDs are influenced critically by the quality of GaN films. In this report, a systematic study has been performed to investigate and optimize the growth process. Fluid flow, heat transfer and chemical reactions are calculated for a specific close‐coupled showerhead (CCS) MOCVD reactor. Influences of reactor dimensions and growth parameters have been examined after introducing the new conceptions of growth uniformity and growth efficiency. It is found that GaN growth rate is mainly affected by the concentration of (CH3)3Ga:NH3 on the susceptor, while growth uniformity is mainly influenced by the recirculating flows above the susceptor caused by natural convection. Effect of gas inlet temperature and the susceptor temperature over the growth rate can be explained by two competing mechanisms. High growth efficiency can be achieved by optimizing the reactor design.     

Growth anisotropy in the GaN/Al2O3 system

The crystallographic aspect of gallium nitride epitaxy on sapphire were investigated for the vapor phase epitaxy system GaCl/NH₃/HCl/N₂. For this purpose, thick layers of doped gallium nitride were deposited on hemispheres of Al₂O₃ single crystal with the three fold axis of the corundum structure perpendicular to the basal plane. Complete characterization of these layers has been carried out including Laue back diffraction, scanning electron microscopy and cathodoluminescence. After growth, sections were cut along the main crystallographic planes and the growth rate was measured as a function of the substrate orientation. The observed relationship for epitaxy has been interpreted in terms of three-dimensional matching between the gallium nitride and corundum structures.     

Uniformity investigation of MOCVD‐grown LED layers

Doped or undoped gallium nitride compounds (GaN/InGaN), usually grown by metal‐organic chemical vapor deposition (MOCVD) method, are at the heart of blue and green light emitting diodes (LEDs). Growth uniformities, such as the excited wavelength, luminous intensity and film thickness, critically influence their application in LED devices. In this paper, growth of GaN compounds in a MOCVD reactor, capable of a one‐time production of 36 × 2” wafers of nitrides, has been investigated. To examine growth uniformity across the wafer and from wafer to wafer, the reactor is divided into Zone A, Zone B and Zone C according to distance to the center of the graphite susceptor. Comparative analysis of each zone offers a straightforward view of the mean excitation wavelength, luminous intensity, film thickness and their standard deviations. Conformity of the growth uniformity in each zone is further checked comprehensively through averaging across‐wafer and wafer‐to‐wafer variables and their standard deviations. Zone B is found to retain excellent wavelength uniformity, since it is located at the middle of the susceptor with weaker effects of the susceptor edge and of the inlet gas flow. Zone A, at the center of the reactor, has the best mean intensity and thickness uniformities due to a well control of the infrared temperature measurement during the growth. And Zone C is worst in all uniformities and should be the main focus when optimizing the reactor. The above experimental analysis reveals the principles common to the MOCVD technique, and provides a basic for further optimization of the process window to improve the cycles with considerable reduction of the costs.     

Microstructure of Epitaxial GaN Layers Synthesized on Nanoprofiled Si(001) Substrates

Crystallography Reports - The microstructure of gallium nitride epitaxial layers synthesized by hydride vapor phase epitaxy (HVPE) and metalorganic chemical vapour deposition (MOCVD) on...     

Synthesis of dense polycrystalline GaN of high purity by the chemical vapor reaction process

A process for producing high-purity, dense polycrystalline gallium nitride is proposed. Dense polycrystalline gallium nitride was produced by the reaction of ammonia, gallium metal, and a halide source in a quartz boat containing metallic gallium. The process is called the chemical vapor reaction process. The hard crust-like pieces of polycrystalline GaN obtained are of high purity, can be used as source material for single-crystal growth by the ammonothermal technique, sublimation, sputtering, and pulse laser deposition.     

Ammonothermal crystal growth of gallium nitride – A brief discussion of critical issues

The acidic ammonothermal technique is used to develop a technology for production of free-standing gallium nitride (GaN) crystals to match the demand driven by the device technology for the wide-band-gap semiconductor group-III element nitrides. Here we report on advances toward a deeper understanding of parameters that govern mass transport and seeded crystallization of GaN under the conditions of acidic ammonothermal crystal growth with the ultimate goal to improve the process control. Comparison with the basic ammonothermal environment has been made.     

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.     

Review: GaN growth by ammonia based methods – density functional theory study

Recent results in Density Functional Theory (DFT) simulations of ammonia‐based growth of gallium nitride on GaN (0001) are reviewed. These simulations are important to the following GaN growth methods that use ammonia as active nitrogen source: ammonothermal, MOVPE, HVPE and also ammonia‐source MBE. In the simulations of GaN growth, the two main approaches were discussed: (1) equilibrium, based on chemical potentials of the components, and (2) dynamic, based on consideration of atomistic processes on the surface. These two approaches are unified by the kinetic procedure of determination of the chemical potential levels for nitrogen and hydrogen as a function of partial pressure of ammonia. Here the DFT modeling of GaN(0001) surface employing the technique of the simulation of subsurface electric field is described and employed. The results of DFT modeling include the ammonia and molecular hydrogen adsorption on GaN(0001) surface that allows to determine some basic features of ammonia‐based growth of GaN. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The heteroepitaxial growth of KDP/ADP

Crystal growth rules of mixture crystals KADP (potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate (ADP)) have been analyzed based on the solubility product principle. The heteroepitaxial layers have been obtained by immersing KDP (ADP) substrate into the ADP (KDP) saturated solution at 313 K. The micromorphology indicates that small growing points on different planes show the self‐similar property compared to the bulk crystal's morphology. The process of epitaxial growth depends on not only form the lattice match but also form crystallizing kinetics which is the main influencing factor. Moreover, it can infer from the micromorphology on the surface of the mixed crystal that the dissolving of substrates will form mixed solution on epitaxial surface. What's more, corrosion phenomenon gets more and more evident with increasing times of epitaxial growth and it will be harder to form transparent epitaxial layers due to the increasing tension of epitaxial layers. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Marangoni Convective Effect during Crystal Growth in Space

GaSb:Te and GaInSb samples have been solidified under microgravity conditions during the D2 Spacelab mission. Experimental design and parameters are described. Analysis of the thermal data taken during the flight, associated to numerical simulations of heat transfer in the experiment, with the help of FIDAP, gave the experimental conditions (thermal gradients and growth rate). Quantitative chemical analyses of the samples show a chemical segregation characteristic of strong mixing in the melt during crystal growth. Silica crucibles with an internal screw thread groove on the inner wall were used in order to get dewetting of samples from the crucible. It was therefore supposed that Marangoni convection on the free surface associated to the groove might have been the source of convection. This hypothesis has been studied by numerical simulation using FIDAP and the velocity field obtained is in agreement with a strong perturbation of the solutal boundary layer ahead the solid-liquid interface. This can explain the observed chemical segregation.     

Crystal growth of gallium nitride

A review is given of the methods which have been used to grow single crystals and epitaxial layers of gallium nitride. In view of the problems in growing bulk crystals, the main emphasis is on heteroepitaxy. Sapphire has been the most popular substrate material, but leads to severe stress because of lattice and expansion mismatch. The use of an intermediate AlN layer appears to alleviate this problem. Chemical vapor deposition using gallium chloride and ammonia has given the highest quality layers to date, but a native donor remains a persistent problem. The use of high pressures of nitrogen offers promise as a means of reducing the native donor concentration. Atomic layer epitaxy is an alternative technique which looks promising for film deposition under well-controlled conditions. The properties of GaN and device considerations are included briefly in this review.     

衬底的Al化处理对AlN性能的影响

研究了衬底的Al化处理对采用MOCVD法在c面蓝宝石衬底上高温生长AlN外延层的影响机制.通过原位监测监控整个外延生长过程,同时对AlN外延层的表面形貌和晶体质量以及应变状态进行表征研究.结果表明衬底的Al化处理导致AlN外延层的表面更加平整但是晶体质量下降,同时对外延层的应变也有很明显的影响.     

三氯氢硅和氢气系统的气相沉积三维模拟

建立了氢气和三氯氢硅系统的多晶硅气相沉积反应模型,通过Chemkin4.0耦合气相反应、表面反应机理,利用流体力学软件Fluent 6.3.26数值求解.根据模拟结果绘制了进气温度、进气组成、沉积表面温度以及反应压力与硅沉积速率的关系曲线,阐述了这些条件对于硅沉积速率的影响,同时把模拟结果与文献中的实验数据和计算结果进行对比.结果表明,硅沉积速率随反应温度和反应压力的提高而提高,随进气温度的提高而提高,当氢气摩尔组成低于0.8时,与氢气物质的量组成成正比,氢气物质的量组成大于0.8时,与氢气摩尔组成成反比.     

Process design for the shape control of crystals grown by Kyropoulos or SAPMAC method

A mathematical model has been proposed to design the process for growing a shaped crystals by Kyropoulos method or SAPMAC method. Crystal shape evolution behaviours under various processes were analysed. The results show that the crystal would go through a transitory shoulder‐expanding stage after which the crystal diameter rapidly decreases under a constant pulling rate and a constant heater temperature. Reducing pulling rate and heater temperature could depress the decrease of crystal diameter after the shoulder‐expanding stage so that enhance the length of crystal. However, the crystal diameter is more sensitive to pulling rate than to heater temperature, and an equal‐diameter crystal can not be grown in non‐undercooled melt by soley reducing the heater temperature. That means that adjusting the pulling rate is the most effective and convenient approach for controlling crystal diameter evolution and simultaneously decreasing both the pulling rate and the heater temperature is the optimal process for growing an equal‐diameter crystal. Moreover, a numerical approach for quantifactional designing crystal shape and corresponding growth processes was proposed according to the model, an example of crystal shape design was given out. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Improved reproducibility in zinc oxide single crystal growth using chemical vapor transport

The crystal growth process of zinc oxide (ZnO) by chemical vapor transport (CVT) using carbon as the transport agent is developed. The comparison between the chemical reaction rate and the diffusion velocity is our primary point of view. In ordinary CVT systems, the transport rate is diffusion-limited because the chemical reactions of both source and growth sides reach an equilibrium extremely faster than the diffusion velocity. Nevertheless, in our system, the transport rate is kinetics-limited because the estimated chemical reaction rates are slower than the diffusion velocity. Configurations of ampoules have been devised to decrease the diffusion velocity and to change from the kinetics-limited transport to the diffusion-limited one. Then the reproducibility of ZnO single crystal growth was considerably improved.     

Kinetic aspects in the vapour phase epitaxy of III–V compounds

Successful exploitation of the unique properties of III–V compound semiconductors has resulted in development of several new devices for optoelectronic and solid state microwave applications. These achievements, however, would not have been possible without major advances in the technology for epitaxial growth of such materials. Further improvements in device performances together with new applications of III–V compounds must be closely coupled with even more progress toward achievement of material with properties approaching the theoretical values. Chemical vapour deposition has emerged as the most common technique for epitaxial growth. Although significant improvements can be obtained through empirical methods of investigation of such processes, it is recognized that in the long run a firm fundamental understanding is essential. This realization provides the motivation for detailed, basic studies of the kinetics and thermodynamics of epitaxial growth by chemical vapour deposition. This review will examine the progress, both past and projected, in measurement and interpretation of the kinetics of vapour phase deposition of III–V epitaxial layers. The scope will be limited to near-atmospheric pressure, open flow epitaxial systems utilizing chemical transport. To date, most of the studies have concerned GaAs, GaP, InAs, InP, and their alloys. It has been demonstrated for GaAs, and for some of the other compounds as well, that, depending on the growth conditions, epitaxial deposition may proceed in two fundamentally different rate-limiting regimes. At low temperatures the rate is limited by a surface process; while at higher temperatures mass transport limitations appear to prevail. For mass-transport-limited deposition the sensitivity of the growth rate to various operating parameters can, in many cases, be predicted from theoretical considerations. Investigation of kinetically limited growth offers a path toward a fundamental understanding of the atomistic surface events that result in epitaxial growth. The progress in these areas will be discussed; in addition, experimental and theoretical tasks for future studies will be recommended.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.