Computational studies of the transient behavior of horizontal MOVPE reactors

Dynamic models of the mass transfer in horizontal reactors used for metalorganic vapor phase epitaxy (MOVPE) of compound semiconductors have been developed and used to study the duration of transients on the substrate during the growth of heterostructures. Dispersion of reactants during gas switching can be detrimental to the abruptness of the interfaces. A solution to this problem is the operation of MOVPE reactors at very high flow rates and low pressures, but this leads to low conversions of the expensive precursors. Our simulations indicate that critical Péclet numbers can be identified, beyond which no significant reduction in the duration of transients on the substrate occurs when increasing the gas velocity. The substrate always reached a new steady state much faster than the entire reactor. Symmetry of filling and purging with respect to transients was also observed. Performance diagrams connecting optimal operating conditions with reactor geometry have been constructed. Time-dependent models of the MOVPE process can help identify optimal operating conditions and reactor shapes leading to abrupt interfaces with maximum precursor utilization.     

Influence of internal radiation on the heat transfer during growth of YAG single crystals by the Czochralski method

Heat and mass transfer taking place during growth of Y₃Al₅O₁₂ (YAG) crystals by the Czochralski method, including inner radiation, is analyzed numerically using a Finite Element Method. For inner radiative heat transfer through the crystal the band approximation model and real transmission characteristics, measured from obtained crystals, are used. The results reveal significant differences in temperature and melt flow for YAG crystals doped with different dopands influencing the optical properties of the crystals. When radiative heat transport through the crystal is taken into account the melt‐crystal interface shape is different from that when the radiative transport is not included. Its deflection remains constant over a wide range of crystal rotation rates until it finally rapidly changes in a narrow range of rotation rates. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The role of inner and internal radiation on the melt growth of sapphire crystal

In this paper, for an inductively heated Czochralski furnace used to grow sapphire single crystal, influence of the inner (wall‐to‐wall) and crystal internal (bulk) radiation on the characteristics of the growth process such as temperature and flow fields, structure of heat transfer and crystal‐melt interface has been studied numerically using the 2D quasi‐steady state finite element method. The obtained results of global analysis demonstrate a strong dependence of thermal field, heat transport structure and crystal‐melt interface on both types of radiative heat transfer within the growth furnace.     

In situ surface passivation of III–V semiconductors in MOVPE by amorphous As and P layers

A new process for chemical passivation of III–V semiconductor surfaces in metalorganic vapour phase epitaxy (MOVPE) is developed. A passivation layer is deposited directly after growth in the reactor. It consists of amorphous arsenic or a double-layer package of amorphous phosphorus and arsenic, which are grown by photo-decomposition of the group-V hydrides. These layers (caps) serve to protect the surfaces against contamination in air after removing the samples from the MOVPE growth reactor. Such passivation is applicable e.g. for a two-step epitaxy or for further surface characterizations.     

Simulation of temperature and flow fields in an inductively heated melt growth system

The goal of the research presented here is to apply a global analysis of an inductively heated Czochralski furnace for a real sapphire crystal growth system and predict the characteristics of the temperature and flow fields in the system. To do it, for the beginning stage of a sapphire growth process, influence of melt and gas convection combined with radiative heat transfer on the temperature field of the system and the crystal‐melt interface have been studied numerically using the steady state two‐dimensional finite element method. For radiative heat transfer, internal radiation through the grown crystal and surface to surface radiation for the exposed surfaces have been taken into account. The numerical results demonstrate that there are a powerful vortex which arises from the natural convection in the melt and a strong and large vortex that flows upwards along the afterheater side wall and downwards along the seed and crystal sides in the gas part. In addition, a wavy shape has been observed for the crystal‐melt interface with a deflection towards the melt. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth monitoring by reflectance anisotropy spectroscopy in MOVPE reactors for device fabrication

Reflectance anisotropy spectroscopy (RAS) has proved its capability to study surface processes during metalorganic vapour phase epitaxy (MOVPE) growth of a variety of III–V compounds. However, these investigations up to now have been mostly restricted to specialized research reactors. Therefore, we studied the feasibility of in-situ monitoring by RAS during growth on two production-type MOVPE reactors: horizontal 2 inch single wafer reactor AIX 200 and Planetary Reactor™ AIX 2000 for 5 × 3 inch. The slight modifications of the reactors necessary to gain normal incidence optical access to the sample do not alter the properties of the grown materials. While in the horizontal reactor the strain-free optical window allows one to obtain well-resolved RAS spectra the signals in the multiwafer reactor are affected by the anisotropy of the ceiling plate. Even in this case RAS spectra can be extracted. First measurements on rotating samples in the horizontal reactor demonstrate the possibility to obtain RAS spectra by multitransient spectroscopy. As an application monitoring of the growth of p-type layers for the base of GaInP/GaAs hetero-bipolar-transistors (HBTs) is discussed. The linear electro-optic effect (LEO) gives information on doping type and doping level. Time-resolved transients at specific energies are used to study the impact of different switching schemes on the properties of the base-emitter interface.     

New approach to simulation of radiative-conductive heat transfer in semi-transparent crystals being pulled from a melt

A method is suggested for the solution of multi-dimensional radiative heat transfer problems arising in growing crystals. The basic idea of the approach lies in the construction of a special division of the unit sphere into a set of solid angles (cells) and in the approximation of the radiation intensity in each solid angle by the P₁ approximation. The radiant transport equation is satisfied in the mean over each elementary cell and the system of partial differential equations of the second order relative to the local zeroth-moments of radiation intensity are obtained. It is shown that the solid angle subdivision can be carried out in different ways with respect to specific features of the heat transfer problem under consideration. As a result even a very rough partition permits satisfactory accuracy of the numerical solutions. One of the main advantages of the method consists in using solid angle subdivisions which can be varied from point to point of the spatial domain. The latter gave possibility to simulate the radiative heat transfer in a circular cylinder of finite length with specular side surface. On this basis the calculation of the temperature field in a cylindrical sapphire crystal being pulled from the melt has been carried out without any restriction on the size of the crystal     

Investigation of the heat exchange processes during growth of basal-plane-faceted sapphire ribbons by the Stepanov method

A three-dimensional model is proposed for the global heat exchange during growth of basal-plane-faceted sapphire ribbons. The model is based on the method for solving three-dimensional problems of radiative heat transfer in complex regions with diffusely and specularly reflecting boundaries. The temperature distributions in the ribbon and elements of the thermal zone are investigated. It is shown that the developed model correctly reflects the main features of the processes of heat exchange in the crystallization setup and makes it possible to purposefully modify the thermal zone.     

The chemistry and transport phenomena of chemical vapor deposition of silicon from SiCl4

The chemical vapor deposition (CVD) of silicon is among the most important synthesis methods in electronic industry. We developed and applied novel methods of characterization to studies of CVD of Si from SiCl₄. In particular, we studied the chemistry of the Si-Cl-H system as well as transport phenomena, such as the momentum, heat, and mass transport in a horizontal CVD reactor. A flow visualization was used to study the flow dynamics, i.e., the momentum transport in the reactor. The heat transport was studied by measuring temperatures at various points in the reactor as a function of flow-rates and susceptor temperatures. A specially designed movable probe was used for a mass spectrometric sampling in the reactor. In these experiments, we were able to determine quantitatively partial pressures of reactants and products at some desired location in the reactor, thus studying the mass transport during the CVD of Si. The conducted studies of transport phenomena were used to establish a model which can be used to predict the efficiency and uniformity of the deposition.     

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.     

Progress in Modeling of III-Nitride MOVPE

This review provides an introduction to III-Nitrides MOVPE process modeling and its application to the design and optimization of MOVPE processes. Fundamentals of the MOVPE process with emphasis on transport phenomena are covered. Numerical techniques to obtain solutions for the underlying governing equations are discussed, as well as approaches to describe multi-component diffusion for typical regimes during MOVPE. Properties of common industrial MOVPE reactor types like close spaced showerhead reactors, rotating disk reactors and Planetary Reactors are compared in terms of underlying working principles and generic process parameter dependencies.The main part of the paper is devoted to reviewing gas phase and surface reaction mechanisms during MOVPE. The process design in particular for MOVPE of III-Nitrides is determined by complex gas phase reaction kinetics. Advances in the modeling and predicting of these processes have contributed to understanding and controlling these phenomena in industrial scale MOVPE reactors. Detailed kinetics and simplified surface kinetic approaches describing the incorporation of constituents into multinary solid alloys are compared and a few application cases are presented. Differences in thermodynamic and kinetic properties of multi-layered structures of different compositions such as InGaN, AlGaN can cause enrichment of the adsorbed layer by certain group III atoms (indium in case of InGaN and gallium in case of AlGaN) that translate into specific features of composition profiles along the growth direction.An intrinsic feature of III-nitride materials is epitaxial strain that shows up in different forms during growth and affects both deposition kinetics and material quality. In case of InGaN MOVPE there is a strong interplay between indium content and strain that has direct influence on distribution of material composition in the epitaxial layers and multi-layered structures. Epitaxial strain can relax via different routes such as nucleation and evolution of the extended defects (dislocations), layer cracking and roughening of the surface morphology. Simulation approaches that address coupling of growth kinetics with strain and defect dynamics are discussed and exemplified.     

Reactor problems in modified chemical vapour deposition (i). the collapse of quartz glass tubes

In the case of the so-called “Modified Chemical Vapour Deposition” for the preparation of optical fiber preforms, the quartz glass reactor is identical with the substrate. Therefore, the knowledge of reactor properties such as the viscous flow of the tubes (collapse) and the heat transport through the wall are especially important for a successful control of the process. As a first step, an analysis is presented for the calculation of the viscous flow of the tubes under the real conditions of dynamic heating by a traversing flame. The experimental determination of the material parameters surface tension and viscosity by collapsing experiments yields an approach to the problem of the temperature distribution in the tube wall.     

In situ reflectance difference spectroscopy of ZnSe-based semiconductor surfaces

We will give a brief report on applications of reflectance difference spectroscopy (RDS) for in situ growth monitoring during MOVPE. The experiments were made on GaAs(001) substrates using dimethylzinc-triethylamine, ditbutylselenide and as metalorganic precursors in a laminar flow reactor. We analyzed the influence of the in situ GaAs-substrate preparation on the optical response of the surface. The growth of ZnSe was investigated and compared to data obtained in an MBE process. Spectra at various stages of growth and time-dependent kinetic RDS records were measured during deposition and fitted with a three-layer growth model. Furthermore we utilized the surface sensitivity of the RDS technique to demonstrate surface kinetic processes during p-doping with tbutylamine.     

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.     

MOVPE of GaN using a specially designed two-flow horizontal reactor

GaN epilayers have been grown on (0001) sapphire substrates with a specially designed two-flow horizontal metalorganic vapor phase epitaxy (MOVPE) reactor. Epilayers with flat and smooth surfaces were obtained at the growth temperature of 950°C with relatively low source supply rates. This indicates a relatively high growth efficiency of the reactor. Characterization by photoluminescence, X-ray diffraction and Hall measurements reveal that the epilayers are of reasonably high quality.     

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.     

Radiative Heat Transfer in a Resistance Heated Floating Zone Furnace: A Numerical Study with FIDAPTM

This paper presents a numerical study of radiative heat transfer in a floating zone (FZ) furnace which was performed by using the commercial finite element program FIDAP^TM. This resistance furnace should provide a temperature higher than the melting temperature of silicon (i.e. T_max ≈ 1500 °C) and a variable temperature gradient at the liquid/solid interface (≥ 25 K/cm). Due to the high working temperatures, heat radiation plays the dominant role for the heat transfer in the furnace. For this reason, the quality of view factors used in the wall‐to‐wall model was carefully inspected with energy‐balance checks. A numerical model with two control parameters is applied to study the influence of material and geometrical parameters on the temperature field. In addition, this model allows us to estimate the internal thermal conditions which were used as thermal boundary conditions for partial 3D simulations. The influences of an optical lens system on the radial symmetry of the temperature field were examined with these partial 3D simulations. Furthermore, we used the inverse modeling method to achieve maximum possible temperature gradients at the liquid/solid interface according to the limitation of maximum available power and the maximum stable height of a melt zone.     

Enhanced two-dimensional growth of MOVPE InN films on sapphire (0 0 0 1) substrates

MOVPE growth of InN on sapphire substrates is compared using two different designs of horizontal reactor. The major difference between the two designs is a variation in the reactant-gas flow-spacing between the substrate and the ceiling of the quartz chamber: 33 mm for the Type A reactor and 14 mm for Type B. Compared with the Type A reactor, the Type B reactor brings about InN films with a larger grain size. This is especially true when InN is grown at 600°C using the Type B reactor, in which case the two-dimensional (2D) growth of InN is found to be extremely enhanced. An investigation of the NH₃/TMIn molar ratio dependence of the surface morphology of grown InN films using the two reactors suggests that the enhanced 2D growth is attributed to the decrease in the effective NH₃/TMIn ratio in the growth atmosphere. Even using the Type A reactor, a film with enhanced 2D growth can be obtained when the NH₃/TMIn ratio is considerably low (1.8×10⁴). The enhanced 2D growth results in a smaller XRC-FWHM (full-width at half maximum of the X-ray rocking curve) (1500 arcsec), than that for a 3D-grown film (5000 arcsec).     

SiC晶体PVT生长系统的流体力学模型及其有限元分析

本文根据SiC晶体PVT生长炉的实际提出了生长系统温度场计算的流体力学模型,采用有限元法分析了生长腔内的热传导、辐射和对流对生长腔内和生长晶体中温度空间分布的影响.通过对生长腔内及生长晶体中温度瞬态和稳态分布的分析,得出在加热的初始阶段腔内气体对流对坩埚内的温度分布有较大影响,在系统热平衡后辐射对腔内温度分布起决定作用的结论.     

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.