Chemical Segregation in Vertical Bridgman Growth of GaInSb Alloys

A set of experiments on the solidification of Ga _1-x In _x Sb alloys with a large variation of the sample diameter (from 1mm to 10mm), of the growth rate (from 0.7 to 7 μm/s) and of the concentration (from x=0.01 to x= 0.1) is described. The associated radial and longitudinal segregation of the In have been analysed by SIMS or electron microprobe. Numerical simulation of the experiments, taking into account thermal, hydrodynamic and chemical behaviour has been carried out with the help of FIDAP. It is shown from these numerical results that a plateau of concentration can be reached even if a convective loop is present close to the interface, provided that the convection does not extend into the bulk of the liquid. This is in full agreement with the experimental results obtained. Supporting this analysis, in some experiments, a defect in term of verticality of the crucible led to complex 3-D convection involving the whole liquid, and in that case no plateau was obtained. For the radial segregation ΔC_R, three regimes of transport are found, characterised by the convective level: - A diffusive one, with a low, constant, ΔC_R related to the interface curvature. - A quasi-diffusive one (weak convection) in which ΔC_R increases with convection. - A convective one in which it decreases. Measured radial segregations are in good agreement with predictions from the numerical simulations.     

Shape evolution of detached Bridgman crystals grown in microgravity

Detached (or dewetted) Bridgman crystal growth defines that process in which a gap exists between a growing crystal and the crucible wall. In microgravity, the parameters that influence the existence of a stable gap are the growth angle of the solidifying crystal, the contact angle between the melt and the crucible wall, and the pressure difference across the meniscus. During actual crystal growth, the initial crystal radius will not have the precise value required for stable detached growth. Beginning with a crystal diameter that differs from stable conditions, numerical calculations are used to analyze the transient crystal growth process. Depending on the initial conditions and growth parameters, the crystal shape will either evolve towards attachment at the crucible wall, towards a stable gap width, or inwards towards eventual collapse of the meniscus. Dynamic growth stability is observed only when the sum of the growth and contact angles exceeds 180°.     

Bridgman法晶体生长的瞬态数值模拟

采用变形有限元法对坩埚下降法晶体生长过程进行了瞬态数值模拟.对随下降距离生长位置、生长速度、界面位置处的法线方向温度梯度和凹度的变化进行了分析说明,将生长过程划分为三个阶段.结果表明在整个生长过程中,晶体生长条件一直处于变化之中,因而晶体的质量也在整块晶体中呈现一定的波动性.     

Optimization of thermal conditions during crystal growth in a multi‐zone resistance furnace

The thermal condition is one the of most important control parameters for crystal growth. In this paper we present an effective numerical method in detail for optimizing thermal conditions in multi‐zone crystal growth facilities, especially for crystal growth by the float zone (FZ) technique. A furnace function Ω is introduced to integrate the character of a growth furnace into a linear equation system. The desired power distribution can be therefore approached by solving the linear equation system iteratively. An expert systemlike algorithm has been developed in order to obtain a more suitable solution for practical applications. This method was used to investigate thermal parameters for experiments of SiGe/GeSi single crystal growth by the FZ technique. It is an individual program which can be combined with any commercial finite element/finite volume (FE/FV) program such as FIDAP^TM.     

Heat and Momentum Transfer Numerical Analysis in a Vertical Bridgman Growth System

In this work the momentum and heat transfer on a Bridgman system for the growth of GaSb has been studied. The main objective was to obtain some information about the role of the different processes like conduction, radiation and convective effects both in the melted material and the surrounding environment. These simulations are based on a 2D axi‐symmetrical model using a finite element method based code. The simulations have been carried out both in steady and transient states. It has been demonstrated that the consideration of a moving environment is important in the distribution of temperatures. The effects of the variations of thermal conductivities and emisivities on the thermal and velocity fields have been investigated. The results show that the key parameters are the thermal conductivities of the different materials present in the system, which produce significant changes in the convective flows inside the melt.     

Use of Labels and Loops for the FIDAP Mesh Generation

The use of do-loops in connection with variables for the FIDAP mesh generation is demonstrated. Special focus is drawn on the advantage of labeling objects explicitly especially for more complicated meshes. These concepts are illustrated with the mesh generation for a three zone resistance furnace.     

Cr3+‐doped LiNbO3 crystals grown by the Bridgman method

The growth of LiNbO₃ crystals doped with Cr³⁺ ions in 0.1, 0.2, and 0.5 mol % concentrations by Bridgman method were reported. The Cr³⁺ ion concentrations in crystals were measured by inductively coupled plasma spectrometry. Electron paramagnetic resonance had been used to investigate the sites occupied by the Cr³⁺ ions. Two Cr³⁺ ion centers located at Li⁺ and Nb⁵⁺ sites (Cr_Li³⁺ and Cr_Nb³⁺ centers, respectively) were observed. Optical absorption and temperature‐dependence emission spectra of the Cr³⁺ ions were reported. The crystal‐field parameters and Racah parameters of the Cr³⁺ ion defect sites were reported and compared with those grown by Czochralski technique. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bridgman growth of langasite‐type piezoelectric crystals

Three langasite family crystals of Sr₃Ga₂Ge₄O₁₄ (SGG), Ca₃NbGa₃Si₂O₁₄ (CNGS), and Sr₃NbGa₃Si₂O₁₄ (SNGS) were successfully grown by the modified Bridgman method. Among them, SGG crystals up to 2 inches were obtained with the multi‐crucible industrial Bridgman furnace; SNGS crystal grown in any orientation direction other than along a‐axis was realized. Commercially availability SGG boules and the advantage in SNGS crystal indicated that the modified Bridgman technique is a prospective method to realize the mass‐production of the langasite‐type crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

LiNbO3晶体的坩埚下降法生长

通过选择合适的原料配比(Li2O 48.6mol;,Nb2O5 51.4mol;),控制固液界面处的温度梯度为20～40℃/cm,晶体生长速度为0.6～1.5mm/h,采用密闭条件下的坩埚下降法工艺成功地生长出了具有良好光学均匀性的完整LiNbO3单晶.用X射线粉末衍射表征获得的LiNbO3晶相,讨论了若干工艺条件对晶体组分与质量的影响.测定了未密闭条件下生长的LiNbO3晶体不同部位样品的紫外可见光谱,发现其吸收边沿生长方向发生红移,并讨论了产生此现象的原因.     

四方晶系晶体的Bridgman法生长的稳态数值模拟

本文对四方晶系晶体的Bridgman法生长进行了稳态数值模拟.当熔体的导热系数位于晶体横向导热系数和纵向导热系数中间的一小段时,将产生"W"形固液界面.通过比较,指出不同导热系数组合时晶体生长的难易.当熔体的导热系数位于晶体横向导热系数和纵向导热系数中间的一小段时,界面平坦,容易长出较好质量的晶体.对中、低级晶系的生长,晶体横向导热系数应大于纵向导热系数.     

Bridgman法晶体生长的热物性各向同性坩埚的选择

本文对不同坩埚热物性组合时计算得到的结果进行了比较.对各向同性坩埚而言,应该优先选择具有与晶体和熔体的导热系数相当导热系数的材料,也可选择导热系数较大的材料.在强度允许的情况下,减小坩埚壁厚对晶体生长有利.     

Contribution to the stability analysis of the dewetted Bridgman growth under microgravity conditions

Experimental observations show that the gap between the sample and the crucible, commonly obtained after solidification in microgravity, is remarkably stable. With the aim to understand the reason of this stability, the dewetting phenomenon is studied by Lyapunov's method. After a short review of the existing mechanisms leading to dewetting, the open smooth crucible configuration is chosen as the most representative. The analytical stability analysis, taking into account geometrical and thermal effects, performed under some boundary heat transfer approximations, shows that, in most cases, the dewetting process is intrinsically stable. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

环境条件对Bridgman法晶体生长过程的影响

本文对不同环境条件时Bridgman法晶体生长过程进行计算,并对不同条件对生长过程的影响加以讨论.较大的温度梯度、较大的换热系数和适量的底部冷却是Bridgman法晶体生长的必备条件,也是工艺优化的重要方向.     

Properties of AgGa1‐xInxSe2 single crystals grown by Bridgman method

High‐pure and single‐phase AgGa_1‐xIn_xSe₂ (x=0.2) polycrystalline was synthesized by the mechanical and temperature oscillation method. Adopting the modified Bridgman method an integral AgGa_1‐xIn_xSe₂ single crystal with diameter of 14 mm and length of 35 mm has been obtained at the rate of 6 mm/day. It was found that there is a new cleavage face which was (101), and observed the four order X‐ray spectrum of the {101} faces. By the method of DSC analysis the melting and freezing points of the AgGa_1‐xIn_xSe₂ (x=0.2) single crystal were about 828°C and 790°C. The transmission spectra of the AgGa_1‐xIn_xSe₂ (x=0.2) sample of 5×6×2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting frequency was 774.316nm and the band gap was 1.6eV. It can be found in the infrared spectrum that the infrared transmission was above 60% from 4000cm^‐1 to 600cm^‐1. The value of α in 5.3µm and 10.6µm were 0.022cm^‐1 and 0.1cm^‐1 respectively. All results showed that the crystal was of good quality. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On favorable thermal fields for detached Bridgman growth

The thermal fields of two Bridgman-like configurations, representative of real systems used in prior experiments for the detached growth of CdTe and Ge crystals, are studied. These detailed heat transfer computations are performed using the CrysMAS code and expand upon our previous analysis [C. Stelian, A. Yeckel, J.J. Derby, Influence of thermal phenomena on crystal reattachment during the dewetted Bridgman growth, J. Cryst. Growth, in press] that posited a new mechanism involving the thermal field and meniscus position to explain stable conditions for dewetted Bridgman growth. Computational results indicate that heat transfer conditions that led to successful detached growth in both of these systems are in accordance with our prior assertion, namely that the prevention of crystal reattachment to the crucible wall requires the avoidance of any undercooling of the melt meniscus during the growth run. Significantly, relatively simple process modifications that promote favorable thermal conditions for detached growth may overcome detrimental factors associated with meniscus shape and crucible wetting. Thus, these ideas may be important to advance the practice of detached growth for many materials.     

Bridgman growth and characterization of birefringent crystal NaNO3

With a bigger birefringence than calcite, sodium nitrate (NaNO₃) single crystal might have potential applications in fiber‐optic polarizer, opto‐isolators and polarizing prisms. However, it is difficult to grow large‐size NaNO₃ crystals for their thermal conductivity anisotropy and phase transition at 275°C. In this paper, crack‐free NaNO₃ crystals with size of Φ20×100 mm³ were prepared by Bridgman method with lower growth rate and lower interface temperature gradient. The dependence of the transmittance on the sample exposure time was measured and studied. The principal refractive indices of NaNO₃ crystal at the wavelengths 0.4730, 0.5320, 0.6328, 1.064 and 1.338 μm were measured by auto‐collimation method. From which, we calculated and obtained the Sellmeier's equation of NaNO₃ crystal. Moreover, the photoluminescence spectra were detected under the excitation at 240 nm, and NaNO₃ crystal presented its fluorescence around 416 nm.     

坩埚下降法中各向热异性坩埚热场的数值模拟

本文对不同坩埚热物性组合时计算得到的结果进行了比较.对各向异性坩埚而言,纵向导热系数应该优先选择较小的材料;也可选择具有与晶体和熔体的导热系数相当导热系数的材料.横向导热系数则越大越有利于晶体生长.复合坩埚两种坩埚材料的导热系数最好不要相差太大.     

分离结晶垂直Bridgman法生长CdZnTe晶体的全局数值模拟

采用FLUENT软件对分离结晶Bridgman法生长CdZnTe晶体进行了全局数值模拟.模拟对象为:熔体上部边界条件分别为固壁和自由表面时两种晶体生长系统.重点考虑坩埚和晶体之间狭缝宽度e和重力对分离结晶过程的影响.在计算中分别取e=0 mm、0.5 mm和1 mm三种狭缝宽度,得到了在微重力和常重力条件下的温度分布、结晶界面形状以及流函数分布图.结果表明:在微重力条件下,当熔体上部为固壁时,随着狭缝宽度的增大,热毛细力作用增强,流动强度增强;当熔体上部为自由表面时,则与之相反.在常重力条件下,由于浮力-热毛细对流的共同作用,随着狭缝宽度的增加,流动强度逐渐减弱,有助于提高晶体生长质量.