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.     

Kinetics of a Single Crystal Growth from Supersaturated Liquid Solution. An Attempt on the Analytical Description of the State of Solution

The attempt was made at formulating a mathematical model describing the state of the supersaturated liquid solution circumfluenting a single crystal, as well as the transport processes occurring in that solution. As the result of a suitable computation procedure, numerical values of velocity components, concentrations, temperatures and the normal components of the mass flux in the vicinity of the crystal surface have been obtained.     

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.     

Low-temperature growth of epitaxial (1 0 0) silicon based on silane and disilane in a 300 mm UHV/CVD cold-wall reactor

Epitaxial (1 0 0) silicon layers were grown at temperatures ranging from 500 to 800 °C in a commercial cold-wall type UHV/CVD reactor at pressures less than 7×10⁻⁵ Torr. The substrates were 300 mm SIMOX SOI wafers and spectroscopic ellipsometry was used to assess growth rates and deposition uniformities. High-resolution atomic force microscopy (AFM) was employed to verify the atomic terrace configuration that resulted from epitaxial step-flow growth. Deposition from disilane exhibited a nearly perfect reaction limit for low temperatures and high precursor flow rates (partial pressures) with measured activation energies of ≈2.0 eV, while a linear dependence of growth rate on precursor gas flow was found for the massflow-controlled regime. A similar behavior was observed in the case of silane with substantially reduced deposition rates in the massflow-limited regime and nearly a factor of 2 reduced growth rates deep in the reaction limited regime. High growth rates of up to 50 μm/h and non-uniformities as low as 1σ=1.45% were obtained in the massflow-limited deposition regime. Silicon layers as thin as 0.6 nm (4.5 atomic layers ) were deposited continuously as determined using a unique wet chemical etching technique as well as cross-sectional high-resolution transmission electron microscopy (HRTEM). In contrast, epitaxial silicon deposited in RPCVD at 10 Torr using disilane within the same temperature range showed imperfect reaction limitation. While activation energies similar to that of UHV/CVD were found, no partial pressure limitation could be observed. Furthermore, layers deposited using disilane in RPCVD exhibited a large number of defects that appeared to form randomly during growth. We attribute this effect to gas phase reactions that create precursor fragments and radicals—an effect that is negligible in UHV/CVD.     

Hg-rich liquid-phase epitaxy of Hg1−xCdxTe

Over the past decade, liquid-phase epitaxy (LPE) has become an established technique for the growth of HgCdTe. This article reviews one of the successful LPE technologies developed for HgCdTe, specifically, “infinite-melt” vertical LPE (VLPE) from Hg-rich solutions.

In spite of the relatively low solubility of Cd in Hg-rich solutions and the relatively high Hg pressure at the usual growth temperatures, this approach has been found to offer superior results for growth of HgCdTe suitable for various compositions and layer structures.

An historical perspective and the current status of VLPE technology are presented. Particular emphasis is placed on the important role of the thermodynamic parameters (phase diagram), on control of stoichiometry (defect chemistry) and on impurity doping (distribution coefficient) for growth of HgCdTe layers from Hg solutions. Critical material characteristics, such as transport properties, minority-carrier lifetime, morphology and crystal structure, are also discussed.     

RHEED studies of the growth of Si(001) by gas source MBE from disilane

The growth of Si(001) from a gas source molecular beam epitaxy system (Si-GSMBE) using disilane (Si₂H₆) was investigated using reflection high-energy electron diffraction (RHEED). The surface reconstructions occurring between 100 and 775°C were studied as a function of both substrate temperature and surface coverage. We report the first observation of (2x2) and c(4x4) reconstructions during growth at substrate temperatures near 645°C using Si₂H₆. All growth was found to be initiated by the formation of three-dimensional (3D) islands which coalesced at substrate temperatures above 600°C. The surface reconstruction was found to change from a disordered to an ordered (2x1)+(1x2) structure at 775°C via intermediate (2x2) and c(4x4) phases. Thereafter, growth was found to proceed in a 2D layer-by-layer fashion, as evidenced by the observation of RHEED intensity oscillations. This technique has been used, for the first time, to calibrate growth rates during Si-GSMBE. The intensity oscillations were measured as a function of both substrate temperature and incident beam flux. Strong and damped oscillations were observed between 610 and 680°C, in the two-dimensional growth regime. At higher temperatures, growth by step propagation dominated while at lower temperatures, growth became increasingly three-dimensional and consequently oscillations were weak or absent. Similarly, there was a minimum flux limit ( <0.16 SCCM), below which no oscillations were recorded.     

Bubble transport in three-dimensional laminar gravity-driven flow - mathematical formulation

This paper presents a complete set of coupled equations that govern the bubble transport in three-dimensional gravity-driven flow. The model accounts for bubble growth or shrinkage due to pressure and temperature changes as well as for multiple gas diffusion in and out of the bubbles but neglects bubble coalescence, break-up, and nucleation. The model applies to glass melting furnaces but it could be extended to other two-phase flow applications such as metal and polymer processing, passive cooling systems, and two-phase flow around naval surface ships. Governing equations are given for the key variables which are, in the present case, (1) the refining agent concentration, (2) the gas species dissolved in the liquid phase, and (3) the bubble radius, gas molar fraction, and density function. The method of solution based on the backward method of characteristics is briefly discussed.     

An analysis of flow and mass transfer during the solution growth of potassium titanyl phosphate

The first fully three-dimensional solution flow and solute transport simulations are performed to model the potassium titanyl phosphate (KTP) growth system of Bordui et al. Steady flows and supersaturation fields for two crystal mounting geometries are computed using a stabilized finite element method implemented on a data-parallel supercomputer. Our results present a mechanistic picture of solute transport which is consistent with inclusion formation patterns obtained in experiments. The simulations also explain beneficial outcomes, in terms of better global mixing and more uniform surface supersaturation, observed for a crystal mounting geometry which strongly breaks cylindrical symmetry in the system.     

Solutal convection around growing protein crystals and diffusional purification in Space

Convective and diffusional mass transport to an isolated crystal growing from solution, with slow linear interface kinetics, is considered analytically as a generic scaling model. We focus on the interface kinetics which is slow as compared to the diffusion mass transport which is typical of protein crystal growth. Independently, full-scale numerical solutions of transport equations around a cylindrical crystal, at the center of the bottom of a cylindrical cell filled with the solution, are found. The two approaches give results that agree over a wide range of parameters, providing dimensionless relationships that allow predictions of the contribution of convection and diffusion to mass transport. Requirements for microgravity level in Space experiments to achieve diffusional mass transport are estimated on the basis of these relationships. Coefficients of impurity distribution between a growing crystal and its solution, under the influences of convection and diffusion around the crystal, were numerically evaluated as functions of time. The results provide further support for the hypothesis concerning the role of the impurity depletion zone in the purification of a growing crystal. They also reveal that in general, the impurity distribution within the crystal is not homogeneous due to convection. The effects of various factors on growth kinetics and crystal purity are considered.     

Purification of ZnSiP2 and ZnSiAs2 by sublimation in a hermetically sealed system

In many cases the ternary compounds of the type ZnSiC₂^v are produced by gas phase transport or growth from solution. In this way prepared ternary substances contain binary compounds as a rule which are mixed or intergrown with the ternary compound. By sublimation of binary accompanying components in closed ampoules may be purified these ternary compounds. The separation of contaminants is complete and the loss of ternary substance is negligible. The inhibited decomposition of the ternary compounds during sublimation compared with binary compounds is probably caused by formation of an Si surface layer hindering diffusion of the highly-volatile elements of group II and V to the surface and their sublimation.     

Effects of ultraviolet irradiation during growth of ZnSe epilayers by atmospheric pressure metalorganic vapor-phase epitaxy using dimethyl zinc and H2Se

This work has investigated the effects of ultraviolet irradiation on the epitaxial growth process of undoped ZnSe by atmospheric-pressure metalorganic vapor phase epitaxy. Dimethyl zinc and H₂Se at a [VI]/[II] mole ratio of 20 were the source gases used for growth onto (100)-just oriented semi-insulating GaAs substrates. Hydrogen was used as the carrier gas. A 500 W Hg-Xe lamp irradiated the substrate at 300 nm wavelength during growth. Growth temperature was varied from 210 to 450°C. Epilayers grown in the presence of irradiation experienced a prominent decrease in growth rate, which occurred even at high temperatures. Through a combination of surface and vapor-phase reactions, UV irradiation also affected the photoluminescence properties, crystalline quality, and surface morphology of the epilayers.     

Dynamic crystallization of II–VI compounds from vapours of the component elements

Dynamic crystallization in II–VI compounds synthesis from the vapour phase has been discussed. The method consists in the displacement of the growth zone by the predetermined change of the evaporation temperatures of the initial elements at constant flows of the transport gas. It leads to uniform distribution of grown crystals in the crystallization region and to the increase of the size and of the yield of crystals. Dynamic crystallization makes it possible to control the photoelectrical properties of the crystals and to increase the yield of the crystals with the required photosensitivity by changing the rate and the direction of the displacement of the growth zone.     

Micro/macro modeling of CVD synthesis

We propose a CVD reaction scheme in which a source material undergoes a gas-phase reaction to produce an intermediate, and then the intermediate diffuses to the solid surface and changes into a solid film through a surface reaction. A series of simple Monte Carlo (SMC) codes has been developed to simulate the observed film shape on micro-trenches and holes. By using these codes, surface reaction rate constants were determined so as to reproduce the experimentally observed film shape. By means of a macro-scale reactive transport analysis of a hot wall tubular reactor, gas-phase reaction rate constants for single component systems were determined to simulate the experimental growth rate distributions. The composition and growth rate of Yttria stabilized Zirconia (YSZ) film, a solid solution of Yttria and Zirconia, were qualitatively explained by a sum of single component's growth rates. As an application of these reaction models, we simulated a rotating-disk CVD reactor under low pressure. The simulations based on a quasi three-dimensional model revealed that the susceptor rotation suppresses the buoyancy convection and forms steeper gradients in temperature and concentration near the susceptor uniformly over wide area. At higher temperatures, the growth rate increased with rotation speed, but at lower temperatures the growth rate decreased with increasing rotation speed because the reduced retention time in the high-temperature region suppressed the gas-phase reaction.     

籽晶台形状对PVT法同质外延生长氮化铝单晶初始生长的影响

借助专业晶体生长模拟软件FEMAG和自主开发的对流、传质、过饱和度及生长速率预测等有限元模块研究了物理气相传输法(PVT)同质外延生长氮化铝(AlN)单晶工艺时的初始传热及传质过程,并分析了不同形状籽晶台对生长室内的温度场、流场、过饱和度及生长速率的影响。温度场模拟结果表明籽晶台侧部角度改变可影响籽晶表面轴向及径向温度梯度,流场及传质模拟表明籽晶台侧部角度变化对籽晶台周边的传质有巨大影响。传质及过饱和度模拟结果表明,当籽晶台侧部角度为130°时,籽晶表面温度梯度较小且可以完全抑制籽晶台侧部多晶沉积,有利于通过同质外延工艺生长出无寄生、无裂纹的高质量氮化铝单晶锭。     

Validation of strong magnetic field asymptotic models for dopant transport during semiconductor crystal growth

This paper presents a numerical solution for the unsteady transport of a dopant during the growth of a semiconductor crystal from a melt with an externally applied magnetic field. This solution confirms the results of an asymptotic model. Both solutions show that at every time during the growth of the crystal, the dopant distribution (1) is very nonuniform throughout the melt, and (2) is far from the instantaneous steady state. The present numerical solution for an arbitrary mass Péclet number Pe_m and an arbitrary Hartmann number Ha predicts a dopant distribution in the crystal, which agrees remarkably well with the dopant distribution predicted by the asymptotic solution for Pe_m 1 and Ha 1. The maximum difference between the crystal compositions predicted by these two different approaches is less than 4% for the range of magnetic field strengths considered.     

Melt Flow and Species Transport in μg‐Gradient‐Freeze Growth of Germanium

The result of a μg‐experiment on the Gradient‐Freeze growth of Ge:Zn with doping from the vapour phase shows a homogeneous distribution of the zinc in the melt, indicating the dominating role of a gravity‐independent transport mechanism. This effect is investigated numerically on the basis of a global model of the growth setup. The numerical simulation includes the melt flow and the transport of the dopant taking into account buoyant and thermocapillary forces. The results confirm the minor influence of gravity on the species transport. The complete mixing of the melt can be explained by thermocapillary (Marangoni) convection only.     

Surface morphology and growth mechanisms of argyrodite-type Cu6PS5 hal crystals

Single crystals of Cu₆PS₅Hal (Hal = Cl, Br, I) have been grown by dissociative sublimation and by chemical vapour transport with P, S, Hal, CuHal and combinations thereof as transporting agents in the temperature range 800 to 1000 K. Microscopic observation of the tetrahedral faces revealed several growth features. Macrosteps, closed loop steps and surface protuberances are always accompanied with the presence of liquid CuHal/Cu₂S droplets on the growing crystal surface. The phenomena are characteristic for a two-dimensional Vapour-Liquid-Solid growth mechanism. In the absence of CuHal/Cu₂S liquid phase, direct growth from the gas phase (VS growth) takes place leading to hillocks and growth spirals with low step heights (∼ 5–10 Å).     

Metal organic vapour phase epitaxy of MgO films grown on c-plane Sapphire

Metal organic vapour phase epitaxy (MOVPE) has been used to epitaxially grow MgO films on c-plane sapphire substrates. Bismethylcyclopentadienyl magnesium (MCP₂Mg) and nitrous oxide (N₂O) were used as the magnesium and the oxygen source, respectively, with nitrogen (N₂) as the carrier gas. The dependence of the growth rate on the partial pressure of magnesium and on the growth temperature was investigated. The growth rate increases with the magnesium partial pressure. The morphological and structural properties of MgO films were investigated using atomic force microscopy and X-ray diffraction. The structural properties are strongly dependent on the growth temperature in the range 400–800 °C. (1 1 1)-oriented MgO layers are observed at growth temperatures above 600 °C whereas no diffraction peak is found at lower growth temperatures. The atomic force microscopy (AFM) images reveal a smooth surface morphology.     

Concentration distribution in crystallization from solution under microgravity

Concentration distribution in crystallization from solution under microgravity is numerically studied. A quasi-steady state growth and dissolution in a 2D rectangular enclosure filled with sodium chlorate (NaClO₃) aqueous solution, in which one wall is the growth surface of the crystal and the opposite one is the dissolution surface, is considered. The solute transport process at the growth surface is described by the diffusion-reaction theory with finite interface kinetics coefficient. The results show that the concentration at the growth surface is supersaturated and the supersaturation distribution is of non-uniformity, i.e. the supersaturation in a region facing an incoming flow is high. On the other hand, the non-uniformity of supersaturation at the growth surface is closely related to the gravity level even under microgravity, it exponentially increases as the thermal Rayleigh number on behalf of the gravity level rises.     

The growth kinetics of (SmY)3(FeGa)5O12 epitaxial layers in the 920–980°C range

The growth kinetics of (SmY)₃(FeGa)₅O₁₂ garnets obtained by liquid phase epitaxy on Gd₃Ga₅O₁₂ substrates are discussed in the 920 to 980°C. range. The experiments have been carried out with the substrates in a horizontal plane and with unidirectional rotation ranging from 30 to 300 rotations per minute (rpm). A sharp increase in the growth velocity at temperatures higher than 960°C is interpreted on the basis of a diffusion-reaction theory. It is found that the diffusion constant increases steeper at higher temperatures and that the linear law of the growth rate as a function of the square root of the rotation rate holds to much higher rotation rates at these temperatures. The influence of the surface incorporation is too small to be detectable. The results are compared with published data concerning other compositions.