移动加热器法生长碲锌镉晶体的组分输运与界面形貌研究

移动加热器法(THM)生长碲锌镉晶体时,界面稳定性对晶体生长的质量有很大影响。本文基于多物理场有限元仿真软件Comsol建立了THM生长碲锌镉晶体的数值模拟模型,讨论了Te边界层与组分过冷区之间的关系,对不同生长阶段的物理场、Te边界层与组分过冷区进行仿真研究,最后讨论了微重力对物理场分布的影响,并对比了微重力与正常重力下的生长界面形貌。模拟结果表明,Te边界层与组分过冷区的分布趋势是一致的,在不同生长阶段,流场中次生涡旋的位置会发生移动,从而导致生长界面的形貌随着生长的进行发生变化,同时微重力条件下形成的生长界面形貌最有利于单晶生长。因此,在晶体生长的中前期,对次生涡旋位置的控制和对组分过冷的削弱,是THM生长高质量晶体的有效方案。     

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.     

Measurement of two‐dimensional distribution of surface supersaturation over a sodium chlorate crystal surface using multidirectional interferometry

The two‐dimensional (2D) distributions of surface supersaturation of sodium chlorate crystals with and without solutal convection have been measured by means of a multidirectional interferometry (MDI) technique coupled with the principles of three‐dimensional (3D) computer tomography. When solutal convection was present over a top face, the supersaturation at the center of the face was depleted by a factor of >0.9 with reference to the value at the edges of the crystal. When the convection was suppressed using an upside‐down geometry, the depletion of supersaturation at the center of the face was much smaller, <0.4. Therefore, the supersaturation difference between the edges and the face center, which is responsible for the morphological stability due to volume diffusion for the solute, becomes less important compared to the effect of convection due to hydrodynamic reasons. This result should give us a key to solve why the crystal quality is sometimes better in convection‐free microgravity conditions because of improved stability of a crystal face caused by more homogeneous distribution of supersaturation over the crystal surface.     

Numerical study to investigate the effect of partition block and ambient air temperature on interfacial heat transfer in liquid bridges of high Prandtl number fluid

Surface heat transfer at the liquid–air interface in liquid bridges of high Prandtl number fluid is known to affect the transitional characteristics appreciably. The heat transfer characteristics under microgravity conditions become much different from those of normal gravity mainly due to the absence of natural convection. The present study deals with numerical computations of flow and heat transfer characteristics in the liquid and surrounding air and also at the liquid–air interface of thermocapillary flow in liquid bridges of high Prandtl number fluid. The governing equations are solved in the coupled domain of the liquid bridge and the surrounding air with the help of available commercial CFD software. The results obtained for a range of Marangoni numbers indicate that by placing a partition block in the air region under normal gravity conditions, the surface heat transfer characteristics of microgravity conditions could be effectively mimicked. The effect of ambient temperature on the surface heat transfer has also been investigated and it has been found that the behavior of heat transfer at the interface changes from heat loss to heat gain when the ambient temperature is increased. Moreover, the presence of partition block under normal gravity suppresses surface heat loss as well as surface heat gain similar to microgravity conditions. Streamlines and temperature contours have been presented for various conditions in order to clarify the underlying physics more meaningfully. The computed profiles for velocity and temperature at the liquid–air interface have been validated against established experimental results.     

Cooling crystallization experiments observed by in situ scanning force microscopy

The change in surface morphology of potassium nitrate and potassium alum has been studied in situ by means of scanning force microscopy. The supersaturation and undersaturation were varied in a cooling crystallizer under flow conditions. To keep the crystal growth rate of potassium nitrate low, the specific additive DOW FAX 3B2 had been used in different concentrations. The crystal growth rate of both systems could be determined and the growth and dissolution surface morphologies of potassium alum exhibited structures similar to those of microscopic measurements.     

In situ AFM investigation of 2D nucleation on the (100) face of KDP

Surface morphology of the (100) face of potassium dihydrogen phosphate (KDP) crystals which were grown at different supersaturations at 25 °C was investigated by in situ atomic force microscopy (AFM). Various AFM images of 2D nucleation under different growth conditions were presented. It is found that the growth of KDP is controlled by polynuclear nucleation mechanism at the high supersaturation. With reduction of the supersaturation, the growth velocity of 2D nuclei becomes very slow and shows typical anisotropy. It is found that the process of coalescence of 2D nuclei does not lead to defect. The experiments show that the growth mechanism for KDP at 25 °C changes between step flow and 2D nucleation in the supersaturation range of 4.5‐5%. The triangular nuclei which are close to equilateral triangle are observed in the experiment at the supersaturation σ = 6% for the first time, showing typical anisotropic growth. Through observing the dissolution of 2D nuclei, the dissolving process can be regarded as the reverse process of growth. We also find that the microcrystals landing on the surface at σ = 9% would grow and coalesce with each other and there is no observable defect in the coalescence. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

一水甲酸锂晶体生长界面过饱和度的测量

本文采用激光全息相衬干涉显微术研究了有机非线性光学晶体一水甲酸锂晶体的生长,计算了晶体生长的界面过饱和度.我们的研究结果表明,晶体生长的界面过饱和度随体过饱和度的增加而非线性增加;不同晶面的界面过饱和度不同;当体过饱和度增加到一定程度时,不同晶面的界面过饱和度趋于相同.     

Understanding supersaturation‐dependent crystal growth of L‐alanine in aqueous solution

The dependence of crystal growth rate of L‐alanine on solution supersaturation was investigated by combining experiments and molecular dynamics (MD) simulations. The experimental results show that lower supersaturated solution yields more elongated L‐alanine crystals along the c‐axis, i.e., the aspect ratio (c/b) of the crystal decreases with the increase of solution supersaturation, which is due to the higher supersaturation inducing a rise in the relative growth rate between the main side surface (the (120) surface) and the main end surface (the (011) surface). MD simulations on the two surfaces in contact with different supersaturated solutions revealed that the solute molecules tend to be more efficiently attached to the (011) surface than to the (120) surface at both supersaturations studied, as the interaction between the solute molecules and the L‐alanine molecules in the first layer of the (011) surface is stronger than that of the (120) surface. However, higher supersaturation leads to larger relative interaction energy between the (120) and (011) surfaces, suggesting an increase in the relative growth rate of the two surfaces (R₍₁₂₀₎/R₍₀₁₁₎) with supersaturation, which is in agreement with the experimental results.     

Unsteady-state transfer of impurities during crystal growth of sucrose in sugarcane solutions

In this work, we present growth rate data of sucrose crystals in the presence of impurities that can be used by both sugar technologists and crystal growth scientists. Growth rate curves measured in a pilot-scale evaporative crystallizer suggest a period of slow growth that follows the seeding of crystals into supersaturated technical solutions. The observed trend was enhanced by adding typical sugarcane impurities such as starch, fructose or dextran to the industrial syrups. Maximum growth rates of sucrose resulted at intermediate rather than high supersaturation levels in the presence of the additives. The effects of the additives on the sucrose solubility and sucrose mass transfer in solution were taken into account to explain the observed crystal growth kinetics. A novel mechanism was identified of unsteady-state adsorption of impurities at the crystal surface and their gradual replacement by the crystallizing solute towards the equilibrium occupation of the active sites for growth. Specifically designed crystallization experiments at controlled supersaturation confirmed this mechanism by showing increasing crystal growth rates with time until reaching a steady-state value for a given supersaturation level and impurity content.     

Radial segregation due to weak convection in a floating zone

The influence of weak convection, caused by surface tension forces, on radial dopant segregation occurring in crystals grown under microgravity conditions is studied numerically. The geometry considered corresponds to a floating-zone configuration with partially coated melt surfaces consisting of small evenly distributed spots of free surfaces. In order to distinguish dopant distribution due to weak convection clearly from distribution due to diffusion the spots only cover one quarter of the periphery. Thus, surface tension-driven convection is allowed only over one quarter of the floating-zone configuration resulting in an asymmetric dopant distribution. The percentage of free surfaces present is varied in order to alter the Marangoni flow rates. The maximum dopant concentration due to radial segregation is plotted as a function of a certain convection level. The results of the present numerical study are supposed to be used to design corresponding space experiments launched at the end of the year 2000.     

Growth and dissolution kinetics of potassium sulfate in pure solutions and in the presence of Cr3+ ions

The growth and dissolution kinetics of potassium sulfate was studied based on single crystal measurements. The growth rate is correlated to the supersaturation with power low equation. At all the temperatures studied, the growth rate order lies in the range of 1‐1.5 with the surface integration process as the controlling step. The estimated value of the activation energy of growth is 39.4 kJ/mol. The dissolution rate order decreases with increasing the temperature. The diffusion step is controlling the dissolution process. The addition of 5 ppm Cr³⁺ ions reduces the growth rate. Both growth rate dispersion and dissolution rate dispersion occur in the growth and dissolution processes of potassium sulfate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of electrical field on dendritic growth of boric acid

Growth rates of boric acid crystals have been measured both in pure aqueous solution and under the influence of electrical field as a function of supersaturation and electrical field intensity in a laboratory scale fluidized bed crystallizer at the temperature of 30°C. The effect of electrical field was estimated from the growth rate data to evaluate the relative magnitude of two resistances, diffusion and integration. In absence of electrical field, the obtained results indicate that the controlling mechanism is mainly integration. However, in presence of electrical field, growth rate of boric acid were controlled by diffusion and reaction steps. In the absence of electrical field, boric acid crystals grow dendritically at any level of supersaturation from pure boric acid solution. In case of electrical field, the dendritic structure was depressed.     

Metastability and crystal growth kinetics on L‐arginine phosphate

Stability of saturated L‐Arginine Phosphate (LAP) solution studied as a function of supercooling rate and crystal growth kinetics investigated as a function of supersaturation are reported in this communication. Solution stability was studied by observing the metastable zone width at different cooling rates employing a polythermal method. Analysis of the experimental data yielded the kinetic constant of nucleation and the order of nucleation. Crystal growth rates studied on small seed crystals with regular morphology, under normal growth conditions and at different supersaturation levels were found to satisfy BCF surface diffusion model. Crystal growth rates were investigated normal to the (100), (010) and (00 ) faces. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of potassium titanyl phosphate (KTP) flux growth by holographic phase-contrast interferometric microphotography

This paper describes a special set of equipment we designed, which is suitable to be used to study the high temperature solution growth process by optical method. The variation regularities of the solid-liquid interface boundary layer in the potassium titanyl phosphate (KTP) crystal growth and dissolution process have been investigated by holographic phase-contrast interferometric microphotography. It has been found that under the condition of free convection, the relation between the thickness of the boundary layer and supersaturation is linear. Moreover, the variation of refractive index caused by the change of solute concentration in the boundary layer will form an exponential function of the distance from the crystal face.     

The induction time,interfacial energy and growth mechanism of maltitol in batch cooling crystallization

Maltitol is crystallized with seeds by cooling mode in industry, often with large amount of fine crystals and wide crystal size distribution. To eliminate the fine nucleation, it's necessary to understand the nucleation kinetics. In this work, the solubility of maltitol in water was measured by the gravimetric method, the nucleation kinetics of maltitol in batch cooling crystallization was investigated using focus beam reflectance measurement (FBRM), and a novel method was proposed to determine the induction time from the trend of the crystal median chord given by FBRM. Based on the relationship between the induction time and the supersaturation, the nucleation mechanism was obtained, including homogenous nucleation at high supersaturation and heterogenous nucleation at low supersaturation. Additionally, combining the classical nucleation theory (CNT) and Arrhenius’ principle, the crystal‐solution interfacial energy and the energy barrier of homogenous nucleation were calculated. From the scanning electron microscope (SEM) images, the growth mechanism of maltitol was identified as surface nucleation growth and the surface entropy factor calculated from the kinetic analyses of t_ind data corroborated this growth mechanism.     

Thermosolutal Convection during Vertical BRIDGMAN Growth of Semiconductor Melts

An attempt is made to investigate the influence of the solutal effect on convection in BiSbTe₃ melts as a representative for semiconductor melts of low PRANDTL number. Calculations have been performed for a 3D BRIDGMAN configuration applying an experimentally measured temperature profile at the outer surface of the ampoule. The FIDAP^TM FEM code was used to solve the transient hydrodynamic moving-boundary problem. Results are presented for the excessive tellurium as a melt component as well as for an additive lead doping. It is shown that, according to the growth conditions, the melt components differently contribute to the thermosolutal convection. For Bridgman growth experiments in space, arbitrary orientations of the ampoule axis with respect to the residual gravity vector can occur. Calculations have been performed for certain orientations (angles) at a constant microgravity level. They show an influence of the solutal effect only for large deviations of the ampoule axis from the direction of the residual gravity vector.     

Results of crystal growth of bismuth-antimony alloys (Bi100–xSbx) in a microgravity environment

Results of two experiments are presented for growth of crystals from (Bi_100–xSb_x) alloys in a microgravity environment. In the growth experiments different variants of the Bridgman technique were used. It was shown that in crystal growth from the melt in closed ampoules under microgravity conditions convection can be prevented completely. Therefore it is possible to grow crystals from melts of some components under diffusion controlled conditions of mass transfer. In microgravity a reduced interaction between the melt and the confining walls was observed even if they have large contact with each other. The investigation of surface morphology corroborated the importance of surface effects for crystal growth from the melt under microgravity conditions. Measurements of electronic properties of crystals grown in microgravity showed a good quality in comparison to earth grown crystals. Because under microgravity conditions in closed ampoules the diffusion controlled mass transfer can be realized and the interaction between the melt and confining wall is reduced, homogeneous crystals with high perfection can be grown melts of some components.     

Study on the Growth of Triglycinsulphate Single Crystals

Crystallization of TGS at 52.0°C - above the transition point - has been studied in a wide range of supersaturation of the solution (σ = 0 to 10⁻²). The rates of growth of {110} and {001} faces were measured as a function of supersaturation at constant hydrodynamical conditions (Re = 3.4 · 10⁻³). Further, the influence of hydrodynamical conditions on the growth of {110} faces at constant supersaturation (σ = 4.2 · 10⁻³) was established. The parameters of the experimentally found dependences are determined on the basis of the surface-diffusion model of BURTON . CABRERA and FRANK . From these dependences follows that the growth rate of the {110} faces is already almost limited by the volume diffusion of TGS molecules towards the crystal surface, while in the case of {001} faces the surface diffusion mechanism of crystallization is clearly manifested. Dislocation densities in the crystals have been determined by means of etching technique. The number of dislocations increases with increasing supersaturation; hence, supersaturation of the solution together with the processes taking place in the regeneration zone surrounding the seed determine the number of dislocations in the crystal volume and thus the resulting structural perfection of single crystals. Investigation of the spontaneous redistribution of domains showed that the growth rate of TGS crystals influences the dielectric properties to much smaller extent than does chemical purity.     

Effect of supersaturation on deuteration distribution in K(H1‐xDx)2PO4 crystals

The homogeneity of deuterium distribution in potassium dideuterium phosphate single crystals was studied by Raman and infrared spectroscopy analyses. Results indicated that the pyramidal section exhibited more homogeneous deuterium distribution than the prismatic section. Supersaturation slightly affected the deuterium homogeneity in the pyramidal section of crystals grown rapidly from 80% deuterated solution. Deuterium homogeneity in the prismatic section decreased with increasing supersaturation level of the growth solution.     

Growth of Zn‐doped Germanium under Microgravity

The doping of germanium with zinc from a remote, temperature‐stabilized source was studied under microgravity. A nominally undoped Ge‐crystal was grown by the Gradient‐Freeze technique with the melt surface being in permanent contact with a gaseous atmosphere of zinc. The dopant and carrier concentrations in the solidified Germanium were measured by SIMS, Hall and resistance measurements and compared with the results of a terrestrial reference experiment as well as with concentration profiles calculated on the basis of the thermodynamics of the growth system. The results prove the possibility of vapour phase doping under microgravity. Moreover, the Zn‐concentration at the initial phase boundary even agrees well with the equilibrium value, strongly indicating a nearly homogeneous distribution of the dopant within the melt before the crystallization.