Modelling of Cu thin film growth by MOCVD process in a vertical reactor

Transport phenomena in a vertical reactor for metalorganic chemical vapor deposition (MOCVD) of copper thin films have been analyzed by numerical simulation of the process. The equations of the mathematical model were solved numerically using the Galerkin finite element method, Newton-Raphson iterations and the frontal algorithm for the gas flow structure, temperature distribution and concentration distribution of the reacting species. Deposition rates of copper thin films using Cu(hfac)VTMS as a precursor were estimated from numerical solutions. Standard process conditions were selected as: a reactor pressure of 1 Torr, a substrate temperature and inlet gas temperature of 200°C and 70°C, respectively, and an inlet gas flow rate of 50 sccm. Under standard conditions, the deposition rates of copper were in the range of 160–230 Å/min. The effects of the process conditions, reactor geometry and shower head structure on the deposition rate and thickness uniformity were examined. It has been demonstrated that numerical simulation can be used for improving the film thickness uniformity and the utilization of source gas.     

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.     

Modeling particle growth and deposition in a tubular CVD reactor

A computational model is developed to simulate the particle formation, growth, and deposition in a tubular CVD reactor. The model takes into account the momentum, heat, and mass transfers, chemical reaction, Brownian coagulation, Brownian diffusion, thermal diffusion, and thermophoresis that occur within the reactor. The chemical system is illustrated by the formation of TiO₂ particles through oxidation of TiCl₄. A set of coupled partial differential equations is solved with the finite volume method to give spatial distributions of velocities, pressure, temperature, TiCl₄ concentration, and sizes of TiO₂ particles, from which the deposition mass fluxes and size distributions of exit TiO₂ particles can be readily evaluated. In the model, the growth of particles is simulated by the discrete-sectional model, which can cover particle growth from monomers up to the submicron size. Among other things, the simulation predicts a maximum deposition flux near the reactor entrance and a rebound in deposition flux near the reactor exit, which have been observed in several experimental studies. The model also reveals a delay in evolution of size distribution near the reactor wall as compared to that of the bulk. This delay signifies that the size distribution of depositing particles at the wall is in general different from that of the bulk, which normally is the measured one. The effects of important operating parameters such as temperature, pressure, inlet TiCl₄ concentration, and inlet stream velocity on various system performance indicators are also investigated.     

西门子CVD还原炉内硅棒生长环境的数值模拟

考虑包括热辐射在内的质量传递、动量传递、热量传递三维模型,利用流体力学计算软件,对18对棒西门子多晶硅CVD还原炉实际情况进行数值模拟.考察了两种进气方式下还原炉内的流场和温度场分布.计算结果表明,为了实现硅棒均匀沉积,与底盘上分散进气、中心集中出气的还原炉结构相比,中心集中进气、中环与外环之间分散出气的流场及温度场分布更为合理.后者可能有效避免气体在进出口间的“短路”现象,又使炉内各处温度分布更为均匀,减小硅棒不均匀生长现象.模拟结果还表明,采用典型工况的数据,还原炉中总能量损失占能量输入的78.9;,辐射热损失占总能量损失的70.9;,产品单位质量能耗为72.8 kWh/·kg-1,与很多其他研究结果及实际相一致.     

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.     

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.     

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.     

Numerical simulation of thermoconvective flows and more uniform depositions in a cold wall rectangular APCVD reactor

At atmospheric pressure, the usual flow conditions in the cold wall horizontal rectangular thermal CVD reactors correspond to steady longitudinal thermoconvective rolls that make non-uniform vapour depositions, in shape of longitudinal parallel ridges. In order to get more uniform depositions, the pressure is generally lowered under the atmospheric pressure to promote forced convection flows, instead of mixed convection ones. In the present paper, using three-dimensional direct numerical simulations, we propose and analyse a method to get uniform deposition without lowering the pressure in the reactor. It consists in adequately exciting the parallel thermoconvective rolls at channel inlet to make them unsteady, periodic and sinuous in order to get a uniform time average of the deposition. This method is shown to be adapted for the horizontal and rectangular APCVD reactors with large longitudinal and transversal aspect ratios, when the Reynolds number of the gas flow is O(100), whatever the value of the surface Damköhler number. This situation is encountered in the online or scrolling APCVD reactors used to deposit coatings on float glass in the flat glass industry for instance. The simulations are based on simplified models for the transport equations (Boussinesq model) and the kinetics of the heterogeneous reactions (deposition model of silicon from hydrogen and silane: SiH₄→Si+2H₂).     

Der Einfluß der Reaktorgeometrie auf die Si3N4-Abscheidung

To explain the different efficience and kinetics as they were found in reactors with various geometry the model of thermal diffusion was attracted. The factor of separating, derived from the diffusion equation containing a term of thermal diffusion permits statements on comparability and transferability of reactors. Further it is possible to discuss the influence of temperature on deposition rate different in the various reactors. It is suggested that the wide spectrum of deposition conditions reviewed in literature for similar physical film properties is based on the different reactor geometry used by investigators.     

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.     

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...     

径向流动MOCVD输运过程的数值模拟和反应器优化

针对三重进口径向流动行星式MOCVD反应器的输运过程进行二维数值模拟研究,探讨有关行星式反应器流道高度和托盘直径能否继续扩大,如何控制基片上方温场和浓度场为最佳分布这样一些本质问题,同时寻找反应器的优化条件.模拟结果发现:(1)通过对反应器形状进行优化,使进口处流道趋向于流线的形状,可以大大地削弱甚至消除由流道扩张引起的涡旋;(2)在影响对流涡旋的几何参数中,反应腔高度起主要作用,而反应腔直径影响较小.对于优化后的反应器,发生对流涡旋的临界高度提高到2～2.5cm,对应的反应器直径增加到40cm;(3)在相同温差、不同衬底温度的条件下,反应器内的流动形态不同.衬底温度高,对流涡旋较弱;衬底温度低,对流涡旋较强.其原因在于气体的粘滞力随温度升高从而抑制了浮升力的作用;(4)衬底上方均匀的流场对应均匀的温场和较高的反应物浓度,热扩散则使TMGa在衬底处的浓度降低.     

径向三重流MOCVD反应器生长GaN的数值模拟

采用计算流体力学方法对生长半导体材料GaN的重要设备三重进口行星式MOCVD (金属有机物化学气相沉积) 反应室中的输运过程进行了二维数值模拟.从浓度场的角度分析反应器内衬底上方NH3和TMGa的浓度影响因素.根据对模拟结果的分析,发现较均匀的流场对应衬底上方的反应物浓度较高,降低反应器内压强,也可获得衬底上方较高的反应物浓度,由于MOCVD反应器内有较大的温差,因此热扩散效应不能忽视.     

Design and operating considerations for a water-cooled close-spaced reactant injector in a production scale MOCVD reactor

In a previous paper, we described experimental results of the growth of a wide range of III–V materials using a water-cooled close-spaced injector that permits organometallic and hydride reactants to be injected 1 cm above the hot wafer. In this paper, we describe important design and operating considerations for this new metalorganic chemical vapor deposition (MOCVD) injector, including construction details, deposition efficiency and process window considerations. Our theoretical modeling indicates that the gas flow patterns are very different from those in a typical rotating disk reactor. By making analytical approximations for the velocity and temperature profiles, we have developed a flow stability parameter and find that the thermal stability depends on the square of the injector-to-substrate gap.     

Simulation of particle transport and deposition in the modified chemical vapor deposition process

The many complex interactions between system variables means that the experimental understanding of the mechanisms of soot generation, transport and deposition in the modified chemical vapor deposition process used to fabricate silica-based optical fibers is limited. This paper presents a computational fluid dynamics study of the process, in which the particle formation zone and flow field are calculated and silica particles are ‘launched’ at the reaction front and tracked until they either deposit on the substrate tube or exit the system. Variables which can affect this process are tube rotation rate, wall temperature profile, inlet feed composition and gas flow rate. It is shown that buoyancy alone and a combination of buoyancy and tube rotation are ‘symmetry breakers’ in terms of particle generation-deposition and that the most important factors affecting deposition are the gas flow rate and the shape of the wall temperature profile. This sensitivity arises from the competing forces of fluid drag and thermophoresis acting on the particles. It is suggested that altering the wall temperature profile by use of different size burners or changing the substrate tube cooling conditions could achieve significantly different soot deposition layer quality, which would be reflected in the final optical fiber performance.     

On batch homogeneity in horizontal CVD reactors (I). Model of heating the process gas

A model of heating of the process gas during its flow along the heater is given as a supposition for a modelling of the batch homogeneity with layer deposition and gas phase etching processes in horizontal CVD-reactors. An analytical expression is derived for the resulting longitudinal temperature profile T(x) in dependence of gas properties, suszeptor temperature, geometric parameters of the reactor, and gas flow rate.     

Copper Incorporation in ZnO during LP-MOCVD

The MOCVD of ZnO layers, at a reduced reactor pressure and using DMZ.2THF and tertiary butanol as zinc and oxygen sources, resp., presents a number of advantages compared with the deposition at normal pressure. This also applies to the copper incorporation by means of cyclopentadienyl-copper(I)-triethyl phosphine. For the copper concentration in the ZnO layers, which linearly increases with the flow rate of the organocopper compound, values > 10²⁰ cm⁻³ can be achieved. Even in case of high concentrations, the desired compensating effect of the copper is, for the time being, comparatively little, but increases considerably after a thermal retreatment of the layers. Some chemical-defect aspects of ZnO will be discussed for the purpose of interpretation.     

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.     

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.     

Transport phenomena analysis for boron CVD in a horizontal cold-wall reactor

The transport phenomena in a horizontal cold-walled semicircular reactor are analyzed for the CVD of boron from BCl₃ and H₂. The mixed problem of energy, momentum, and mass conservations is solved by a simple finite difference method. The concentration of the B-reactant on the deposition surface is substituted by the sum of equilibrium mole fractions of the B-containing gas species. The profiles of temperature, velocity, and reactant concentrations in the CVD reactor are illustrated, and the boron deposition rate profile along the substrate is predicted. The effect of the reactant input composition on the deposition rate is calculated, and compared with the experimental data.