Heat and mass transfer in a gas-transport reactor for multicomponent solid phase deposition

Gas temperature distribution in an epitaxial horizontal flow reactor was measured by means of a thin thermoprobe and measurement error was calculated. For a turbulent gas flow, the thickness of an equilibrium layer was estimated, the results obtained being coincident with the boundary layer thickness determined from the relationships for gas temperature distribution in the reactor. The distribution pattern of the rates of mass-transfer processes is discussed with reference to multicomponent solid phase deposition lengthwise the reactor. That the layer of nearly uniform composition can be deposited under turbulent flow conditions only is exemplified by the deposition of solid solutions of aluminium and gallium nitrides.     

反向流动垂直喷淋式MOCVD反应器生长GaN的化学反应数值模拟

本文提出了MOCVD生长GaN的表面循环反应模型,将该反应模型应用于作者新近提出的反向流动垂直喷淋式反应器,进行三维数值模拟.得出反应器内流速、温度和TMGa浓度分布,以及GaN的生长速率分布.将此计算结果与传统的反应器情况进行对比,发现在相同参数情况下,两种反应器的衬底上方温度分布都比较均匀,近衬底处温度梯度较大,高温区域被压制在离衬底较近的区域,流线均比较平滑,在衬底上方没有明显的旋涡;新型反应器内反应气体在近衬底处的浓度均匀性以及GaN在基片表面的沉积均匀性都优于传统反应器,但沉积速率小于后者,大约只有后者的1/2.     

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.     

MOCVD layer growth of ZnO using adducts of dimethyl- and diethylzinc

Reaction mixtures of the tetrahydrofuran adducts of Zn(CH₃)₂ and Zn(C₂H₅)₂ with tertiary butanol are very well suitable for the MOCVD of c-axis oriented ZnO films. The deposition process is greatly determined by the kind of the gas inlet into the vertical reactor. The growth rates present a great dependence on temperature. The incorporation of compensating copper acceptors can be achieved with the help of cyclopentadienyl (tributylphosphine)-copper (I). The structural and the electrical properties of the films are presented.     

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.     

Homoepitaxial growth of 6H–SiC thin films by metal-organic chemical vapor deposition using bis-trimethylsilylmethane precursor

Homoepitaxial silicon carbide (SiC) films were grown on 3.5° off-oriented (0 0 0 1) 6H–SiC by metal-organic chemical vapor deposition (MOCVD) using bis-trimethylsilylmethane (BTMSM, C₇H₂₀Si₂). A pronounced effect of the growth conditions such as source flow rate and growth temperature on the polytype formation and structural imperfection of the epilayer was observed. The growth behavior was explained by a step controlled epitaxy model. It was demonstrated by high-resolution X-ray diffractometry and transmission electron microscopy that high-quality 6H–SiC thin films were successfully grown at the optimized growth condition of substrate temperature 1440°C with the carrier gas flow rate of 10 sccm.     

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.     

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.     

喷淋式MOCVD反应器中AlN的生长速率和化学反应路径的数值模拟研究

利用数值模拟方法,结合反应动力学和气体输运过程,研究喷淋式MOCVD反应器中AlN的生长速率和气相反应路径与反应前体流量(NH3和H2)、进口温度、压强、腔室高度等参数的关系.研究发现:薄膜生长前体和纳米粒子前体的浓度决定了不同的生长速率和气相反应路径.在低Ⅴ/Ⅲ比(2000)、高H2流量(12 L/min)、高进口温...     

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.     

Uniformity analysis of temperature distribution in an industrial MOCVD reactor

Three‐dimensional models, coupling fluid flow and heat transfer, have been adopted to analyze influences of the process parameters on the temperature uniformity in an industrial MOCVD reactor. Important factors, such as the inlet gas flow, the susceptor rotation, the heater power, the distance between the heat shield and the susceptor (d₁), as well as the distance between the heater and the susceptor (d₂), have been investigated carefully. The system heating condition is characterized by temperature uniformity denoted as the standard deviation of temperature, and by thermal efficiency expressed as a combination parameter of the dissipated energy. The results reveal that decrease of the gas flow and the rotation rate, as well as increase of the distance d₁, could monotonically enhance the temperature uniformity. The results also show that decrease of the above three parameters could improve the thermal efficiency. Furthermore, increase of the distance d₂ enhances the temperature uniformity, and reduces the thermal efficiency slightly. The influences of the parameters on the uniformity vary at the different locations of the susceptor as divided into Zone A, Zone B and Zone C. The conclusions help the growth engineer optimize the system design and process conditions of the reactor.     

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.     

Novel reactor for high volume low-cost silicon epitaxy

The chemical vapor deposition of epitaxial layers of silicon is a widely used process in the electronic industry. It is a batch process and the relatively small capacity (i.e., 20–30 wafers) of epitaxial reactors significantly contributes to the expense of the process. We thus embarked on a research project aimed at a significant expansion of the reactor capacity. The first step was to conduct a complete characterization of the presently used reactors by means of flow visualization, temperature measurements and mass spectrometric studies; results of these studies will be briefly presented and discussed. The main conclusion from these studies was that up-scaling of present reactors is not economical. We thus designed and constructed a novel epitaxial reactor, radically different from current types. In this reactor the susceptor structure consists of parallel graphite discs. Wafers are fastened to one or both sides of these discs. The nutrient gaseous mixture is injected into spaces between discs by a specially designed gas distributor, which delivers the same amount of the mixture to all interdisc spacings, thus insuring the wafer-to-wafer thickness uniformity. A combination of the rotation of the susceptor discs with the gas distributor motion insures the on-the-wafer thickness uniformity. The above described parallel packing allows much higher reactor capacities (e.g., 50–100 wafers). It also results in a more economical reactor in terms of consumption of energy and chemicals. We shall illustrate the application of the novel reactor (known as the “RCA Rotary Disc Reactor”) to epitaxial deposition of silicon from SiCl₂H₂.     

Hydrogenated amorphous silicon with substrate-dependent structure

Hydrogenated amorphous silicon (a-Si:H) thin films grown at 250°C on (1 0 0) crystalline substrate using plasma-enhanced chemical vapor deposition (PECVD) with SiH₄/H₂ gas flow ratio equal to 5/1 (sccm) are investigated by transmission electron microscopy. It is found that the thin film is totally amorphous when grown on a glass substrate. But when the substrate is changed to crystalline silicon, some crystalline grains are found embedded in the amorphous structure in certain regions even if the thickness of the film reaches 600 nm. It is suggested that the amorphous silicon film grown on a crystalline silicon substrate at a temperature of 250°C without heavy H₂ dilution is a mixed network of a small amount of crystalline silicon and the major portion of amorphous silicon.     

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.     

A study of growth and morphological features of TiOxNy thin films prepared by MOCVD

The growth and morphological features of MOCVD TiO_xN_y films have been characterized to evaluate the effect of various process parameters on film growth. XRD analysis of the films deposited at 600°C on Si(1 1 1) and mica show a TiN(1 1 1) peak at 2θ=36.6°, but only anatase peaks are detected below 550°C. Above 650°C, both anatase and rutile peaks are detected. The presence of ammonia is not effective below 550°C as the deposited film is mostly TiO₂. Also, ammonia does not play any role in homogeneous nucleation in the gas phase, as evident by the deposition of anatase/rutile particles above 650°C. The following changes in the morphological features are observed by varying process parameters. By increasing the ratio of titanium-isopropoxide to ammonia flow, the cluster shape changes from angular to rounded; dilution of the flow results in larger elongated clusters; increase in flow rate at constant precursor to ammonia ratios, changes the cluster shape from rounded to elongated and the cluster size deceases. Deposition at higher temperatures results in finer clusters with a slower growth rate and eventually results in a very thin film with particle deposition at 650°C and above.     

基于原子层沉积的氧化锆薄膜工艺优化研究

利用原子层沉积技术(Atomic layer deposition, ALD)进行ZrO2薄膜工艺研究,获得了低温下ZrO2薄膜ALD的最佳工艺条件.分析了在低温下前驱体脉冲时间,吹扫时间生长工艺条件对薄膜性能的影响.以四(二甲基氨)基锆(TDMAZ)和H2O为前驱体,制备了均匀性良好,表面粗糙度低,可见光透过率高,水汽阻挡效果良好的ZrO2薄膜.     

On chemically vapour-deposited Si/Ge growth in a multi-wafer deposition process at atmospheric pressure

In multi-wafer deposition of Si/Ge thin films from silane, germane mixtures at low-temperature epitaxy conditions not only the depletion of the silicon source but also of the germanium source along the reactor tube axis has to be counteracted in order to get homogeneous layer thickness as well as composition. Carrier gas throughput must be minimized to have a sufficient effective chemical reaction rate at low temperature. Thus it cannot be used to flatten layer growth along the susceptor. Yet the addition of a chemically reactive gas, as for instance hydrogen chloride, is suitable to ensure a nearly constant content of the layer forming source gases along the reactor tube. On the other hand hydrogen chloride may infiltrate additional contaminants leading for instance to high oxygen concentration in the deposited layer. However, oxygen soluted or precipitated changes particular features of Si/Ge behaviour for instance during the thin film growth, the following technological stress of the wafer, or the running electronic structures of microelectronic devices.     

Effect of gallium incorporation on the physical properties of ZnO films grown by spray pyrolysis

Gallium-doped zinc oxide thin films were deposited by the spray pyrolysis technique onto Corning 7059 glass substrates at a temperature of 350°C using a precursor solution of zinc acetate in isopropyl alcohol. The films were prepared using different gallium concentrations keeping the other deposition parameters such as air and solution flow rates and solution concentration constant. The variations of the structural, electrical and optical properties with the doping concentration were investigated. X-ray diffraction data showed that the films were polycrystalline with the (0 0 2) preferred orientation. The texture coefficient and grain size were evaluated for different doping concentrations. The films with 5.0 at% gallium had a resistivity of 1.5×10⁻³ Ω cm and a transmittance of 85% with an energy band gap of 3.35 eV.     

A new model for low pressure chemical vapor deposition of SiO2 films by ozone augmented tetraethoxysilane

A simple model has been developed to analyze the low pressure chemical vapor deposition (LPCVD) of SiO₂ films from tetraethoxysilane (TEOS) and ozone. It is found that the model correlates well the experimental data taken at 30 to 90 Torr which is the range of the Applied Materials 5000 reactor. The model shows from correlations of experimental data that gas phase reaction reduces the deposition rate and that this effect becomes more significant at temperatures above about 365°C. The model also explains successfully the trend in experimental data on Arrhenius plots for pressures from 30 to 90 Torr. These data indicate that the temperature, T_m, at which the deposition rate is a maximum, decreases as the pressure is increased. This occurs because the effect of parasitic gas phase reactions becomes more important at higher pressure. Furthermore, thetrends predicted buy our model are consistent with the experimental data taken under atmospheric pressure chemical vapor deposition (APCVD), even though these conditions are outside the range of applicability of this model which assumes low pressure and therefore very high rates of diffusion.