Compositional Effects on Solidification of Congruently Melting InSb

In vertical Bridgman and Czochralski growth of stoichiometric electronic materials such as InSb, GaSb, and GaAs, growth from stoichiometric melts is commonly desired to achieve high quality. Off-stoichiometric growth is considered significant in the quest to understand transport phenomena leading to the observed sporadic inclusions. Here we apply radiographic interface visualization and calibrated interface temperature measurements to study growth of InSb from off-stoichiometric melts. The crystals are analyzed for structure and chemical segregation. Results indicate concentration boundary layer formation in the melt ahead of the interface. Evidence is presented for heterogeneous nucleation sites within αInSb. Analysis indicates that these nucleation sites develop ahead of the interface in the off-stoichiometric melt phase as the melt temperature at the interface drops below the congruent melting temperature of αInSb.     

熔体法生长大尺寸有机晶体

大尺寸有机晶体在太赫兹波产生、中子探测、微波激射等多个关系国计民生、涉及国家安全的领域具有重要应用前景.但大尺寸有机单晶生长一直是国际公认的难题,无论是在生长理论、生长方法还是生长设备方面都远远落后,在整个人工晶体领域相对小众;而且有机晶体硬度低、脆性高、易解理等本征特性为加工和后期应用带来了很多困难,制约了相关领域的...     

Dendritic growth with interfacial energy anisotropy

A theory for dendritic growth of needle shaped crystals growing in supercooled pure melts and dilute alloys is proposed. This theory predicts the growth velocity and tip radii as functions of supercooling and alloy concentrations without introduction of additional conditions such as marginal stability. A key ingredient of the theory is introducing the effect of the interfacial energy anisotropy. Deviation of the shape of the dendrite from a paraboloid of revolution is permitted, consistent with a small interfacial energy anisotropy. The radius of curvature and the growth rate as functions of melt supercooling and alloy concentrations are determined in terms of the anisotropy, and are compared with experimental results. The predictions are in agreement with the experimental results, especially at large supercoolings. The deviation at lower supercoolings can be attributed to the neglect of natural convection in the present theory.     

Marangoni Convective Effect during Crystal Growth in Space

GaSb:Te and GaInSb samples have been solidified under microgravity conditions during the D2 Spacelab mission. Experimental design and parameters are described. Analysis of the thermal data taken during the flight, associated to numerical simulations of heat transfer in the experiment, with the help of FIDAP, gave the experimental conditions (thermal gradients and growth rate). Quantitative chemical analyses of the samples show a chemical segregation characteristic of strong mixing in the melt during crystal growth. Silica crucibles with an internal screw thread groove on the inner wall were used in order to get dewetting of samples from the crucible. It was therefore supposed that Marangoni convection on the free surface associated to the groove might have been the source of convection. This hypothesis has been studied by numerical simulation using FIDAP and the velocity field obtained is in agreement with a strong perturbation of the solutal boundary layer ahead the solid-liquid interface. This can explain the observed chemical segregation.     

Interface Dynamics during Indium Antimonide Crystal Growth

Experiments with a stoichiometric InSb compound were first performed at small temperature gradient across the crystal/melt interface of 3 °C/cm and furnace translation velocity, V_frn, of 2 μ/sec. Known growth requirements for quality crystals were confirmed. They are, (1) the interface temperature must be close to the congruent melting temperature and, (2) the interface must be located within the adiabatic zone. These requirements can be obtained only through specific settings of the heater temperatures. An X-ray radioscopic system has been modified to accommodate real-time visualization of the crystal/melt interface during vertical Bridgman-Stockbarger growth of InSb. It is shown that asymmetric temperature settings of the heaters can be advantageously used to minimize defect formation. The interface temperature was assessed indirectly with calibrated outside thermocouples. Optical microscopy and electron microprobe analyses provided feedback on crystalline homogeneity.     

Thermodynamic and lamella models relationship for the eutectic system benzoic acid – cinnamic acid

The present investigation reveals the relationship between excess thermodynamic functions and the growth habits of the eutectic phases from the melt by continuous melt‐growth technique. Excess thermodynamic functions computed for different compositions of the benzoic acid – cinnamic acid eutectic system have been found consistent with the criteria of spontaneity and Planck formulation, and their reliability has been ascertained by the application of Guggenheim lattice theory. The results on the kinetics of anisotropic growth of the eutectic phases from the melt, evidentially evince the dislocation mechanism. Evidences have been obtained for a parabolic variation of mechanical strength with growth velocity of the eutectic material grown anisotropically from the melt at different intervals, which offer supporting complement to the dislocation mechanism governing the dependence of growth velocity on supercooling ΔT in the solidus – liquidus interface in a form : V = k(ΔT)². A moderate anisotropic growth region has been explored by unique results of strength properties and microscopic results as well, to growing a layer of lamellae in a unidirectional lamina. An anisotropic eutectic composite lamellae lamina developed by moderate growth velocity (7.3 × 10^‐8m³s^‐1), is of greater interest offering optimum hardness, approximately varying between three‐and eight fold average increase in different modes of the mechanical strength in comparison to its isotropic growth carried out in an ice‐bath (∼273K), and manifold superior to its constituent phases irrespective of the growth mode. The directional lamina of uniform microstructural parameter lamellae, indicates that there is a perfect lamella‐ matrix equilibrium for which excess thermodynamic functions do vanish. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth rate from the AgNO3-Dimethylsulfoxide melt

The growth rate of AgNO₃·DMSO crystals from its melt and concentrated aqueous solutions was studied in the dependence on supercooling (ΔT = 0.5–65°C) by microscopic technique. The experimental results were analyzed according to the formalism proposed for describing growth kinetics from melts.     

熔体温度对负离子配位多面体生长基元聚集体结构的影响

据Na2SiO3与BaB2O4晶体和熔体的高温拉曼光谱测试结果综合分析后提出:熔体的温度对负离子配位多面体生长基元相互联结的聚集体结构有影响.在高温熔体中,高电价、离子半径小的阳离子配位多面体往往孤立存在.当熔体过冷度大时,孤立的负离子配位多面体顶角上的氧与低电价、离子半径大的阳离子配位构成大维度的聚集体.同质异构晶体的熔体拉曼谱都显示出相同的孤立负离子配位多面体振动峰.     

Calculation of Diffusion-limited Growth of Hg1−x Cdx Te Epilayers on CdTe from Te-rich Melts by Step-Cooling LPE

Calculations of layer thicknesses and composition profiles in Hg_1−xCd_xTe layers on CdTe substrates for the growth from Te-rich melts have been carried out for liquidus temperatures of 460 °C, 480 °C, and 500 °C. This has been made on the basis of the multicomponent diffusion model of SMALL and GHEZ and the solid-liquid phase relation of BRICE . It could be shown that growth velocity increases only slightly with rising liquidus temperature. On the other hand, the interdiffusion velocity of Hg and Cd in the solid increases remarkably at a higher temperature. Therefore, to get layers with a constant x-value a higher supersaturation of the melt is necessary. The x-value decreases with rising supercooling by about 0.003 K⁻¹. To demonstrate the thermodynamically and kinetically advantageous properties of CdTe as substrate material, comparative calculations for a “hypothetical” HgTe substrate have been involved.     

Growth of equiaxed dendritic crystals settling in an undercooled melt,Part 1: Tip kinetics

Experiments are conducted to measure the dendrite tip growth velocities of equiaxed crystals of the transparent model alloy succinonitrile–acetone that are settling in an undercooled melt. The tip velocities are measured as a function of the crystal settling speed and the Eulerian angle between the dendrite arms and the flow direction relative to the crystal. The ratio of the settling speed (or flow velocity) to the tip growth velocity ranges from 62 to 572. The ratio of the measured tip velocity to that predicted from a standard diffusion theory for free dendritic growth ranges from almost zero for dendrite tips growing in the wake of the crystal, about unity for dendrite tips with an orientation close to normal to the flow direction, and up to two for dendrite tips growing into the flow. Despite the relatively strong flow relative to the crystal, the average tip growth velocity of the six primary dendrite arms of an equiaxed crystal is found to be in excellent agreement with the standard diffusion theory result. The individual tip velocities are correlated using a boundary layer model of free dendritic growth in the presence of melt flow that is modified to account for the flow angle dependence. Using the same dendrite tip selection parameter, σ^*, as established previously under purely diffusive conditions (0.02), good agreement is achieved between the measured and predicted tip velocities. The model is also found to predict well the variations in the tip velocity that occur during settling due to crystal rotation and settling speed changes.     

Morphological stability of sapphire crystallization front

The main factors and specificity of growth conditions for sapphire and Ti:sapphire crystals, which affect the morphological stability of the crystal–melt interface, have been investigated with allowance for the concentration and radiative melt supercooling. It is shown that the critical sapphire growth rate is determined to a great extent by the optical transparency of the melt and the mixing conditions near the crystallization front.     

Fluctuation mechanism of normal crystal growth during solidification of binary metallic melts

A recently published theory on the solidification of a one-component melt has been extended to the more complex case of binary systems. The theory is based on the model of a two-phase transitional zone existing between the crystalline phase and the melt. The concentration of solid state atoms within each mono-atomic layer of the transitional zone are assumed to fluctuate due to thermal fluctuations. A crystal growth law has been derived expressing the crystallization velocity in terms of probability functions describing these concentrations fluctuations. When certain restricting conditions concerning the atomic interaction energies within the transitional zone and the distribution of the atoms among the solid and liquid phases at supercooling are fulfilled the crystal growth law attains a simple form predicting for small supercoolings a growth rate proportional to supercooling (linear growth law), roughly proportional to physical parameter θ_AA, and with a weak dependence on another parameter Δ.     

溶液、熔体中负离子配位多面体生长基元的分布与缔合

根据对晶体生长溶液、熔体拉曼光谱的测试结果,剖析了溶液和熔体中负离子配位多面体的分布及其缔合过程,总结出了不同过饱和溶液和不同过冷度熔体中负离子配位多面体生长基元的缔合形式和维度的规律.在靠近晶体的边界层处已出现与晶体结构相同或相似的大维度生长基元.实验表明,生长基元的分布和缔合与溶液过饱和度和熔体过冷度密切相关,从而提出用拉曼光谱进行实时监控,寻找最佳生长物化条件,优化晶体生长边界层的厚度和大维度生长基元的数量,为选择最佳工艺条件提出理论依据.     

Study on phase diagram of Bi2O3---SiO2 system for Bridgman growth of Bi4Si3O12 single crystal

Phase relation of Bi₂O₃---SiO₂ system was evaluated experimentally from DTA and XRD measurements and its stable and metastable phase diagrams were proposed. Although BSO melts near-congruently at 1025°C in the stable phase equilibrium, its melt crystallizes to form metastable phase Bi₂SiO₅ in accordance with the metastable phase diagram while cooling. Therefore, BSO couldn't nucleate and crystallize spontaneously without crystal seed and only Bi₂SiO₅ crystallized at about 850°C with significant supercooling during Bridgman growth. BSO single crystal with 20×20×100mm³ was grown in a vertical Bridgman furnace with a BSO seed according to its phase diagram. The measuring results of scintillation properties of BSO specimen show that its decay constant is 91 ns (about 1/3 of BGO) and light output is 23% of BGO.     

Crystal growth from a calcium nitrate tetrahydrate melt

The kinetics of growth of calcium nitrate tetrahydrate crystals from its melt were studied in the supercooling region ΔT = 0 — 65 K. The experimental results were compared with the theoretical equations, and it was found that the growth proceeds according to a dislocation mechanism at low supercooling values and changes to continuous growth governed by the melt viscosity at higher values of supercooling.     

Concept of specific supersaturation (specific supercooling) and practical aspects of its application

It is demonstrated that the normal growth rate of crystals from solutions and melts depends on the area of the crystallization front. New growth parameters, namely, the specific supersaturation and the specific supercooling, are introduced, and the quantitative dependence of the normal growth rate on these parameters is determined. It is noted that the normal growth rate affects the formation of defects. The criteria and the range of the possible use of the specific supersaturation (specific supercooling) for optimizing the conditions of crystal growth from solutions and melts are revealed.     

Numerical simulation of thermal and mass transport during Czochralski crystal growth of sapphire

The thermal and flow transport in an inductively heated Czochralski crystal growth furnace during a crystal growth process is investigated numerically. The temperature and flow fields inside the furnace, coupled with the heat generation in the iridium crucible induced by the electromagnetic field generated by the RF coil, are computed. The results indicate that for an RF coil fixed in position during the growth process, although the maximum value of the magnetic, temperature and velocity fields decrease, the convexity of the crystal‐melt interface increases for longer crystal growth lengths. The convexity of the crystal‐melt interface and the power consumption can be reduced by adjusting the relative position between the crucible and the induction coil during growth. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of the Temperature Fluctuation of the Melt on β‐BaB2O4 (BBO) Crystal Growth

In this paper the effect of the growth temperature fluctuation, for instance, the transient furnace temperature variation due to a short‐term electric power supply interruption on BBO crystal growth was investigated based on the theory of temperature wave transmitting in melt and the boundary layer theory of melt. It was found that the critical width of the temperature pulse to avoid the temperature wave penetrating through the boundary layer and reaching to the growth interface at a constant rotation speed (9∼4 r/min) is 69∼150 s and the corresponding amplitude of the temperature pulse is high more than 60 °C due to the large thickness of the velocity boundary layer of the melt. This result indicates that a small transient temperature fluctuation has no significant effect on the crystal quality, and therefore implies that not only transport processes but interface growth kinetics, a two‐dimensional nucleation growth mode at the interface may also dominate the crystal growth.     

Growth of SiGe bulk crystals with uniform composition by utilizing feedback control system of the crystal–melt interface position for precise control of the growth temperature

We developed an automatic feedback control system of the crystal–melt interface position to keep the temperature at the interface constant during growth, and demonstrate its successful application to grow Ge-rich SiGe bulk crystals with uniform composition. In this system, the position of the crystal–melt interface was automatically detected by analyzing the images captured using in situ monitoring system based on charge-coupled-devices camera, and the pulling rate of the crucible was corrected at every 1 min. The system was found to be effective to keep the crystal–melt interface position during growth even when the variation of the growth rate is quite large. Especially, the interface position was kept for 470 h during growth of Ge-rich SiGe bulk crystal when we started with a long growth melt of 80 mm. As a result, a 23 mm-long Si_0.22Ge_0.78 bulk crystal with uniform composition was obtained thanks to the constancy of the growth temperature during growth through the control of the interface position. Our technique opens a possibility to put multicomponent bulk crystal in a practical use.     

ø300 mm直拉硅单晶生长过程中的变晶现象及其影响因素

直拉法生长直径300 mm硅单晶过程中,直径均匀是获得高品质硅单晶的关键。在生产实践中发现,当硅晶体进入等径生长阶段,过高的提拉速度会引起晶体发生扭晶现象,导致晶线断裂随即变晶,对等径生长不利。本文采用数值模拟和理论相结合的方法分析了ø300 mm硅单晶生长过程中扭晶现象的成因,建立了不同提拉速度下晶体直径与熔体温度分布的关系,分析了晶体发生扭晶的影响因素。结果表明,随着提拉速度的增加,熔体自由表面产生过冷区且该过冷区随提拉速度的增加不断扩大,过冷区的产生是导致晶体发生扭晶的主要原因。提出了一种基于有限元热场数值模拟的最大稳定提拉速度的判别方法,并给出了通过改变晶体旋转速度来改善熔体自由表面温度分布的工艺措施建议,从而避免晶体扭晶现象的发生。研究结果对设计大尺寸硅单晶生长热场具有一定的指导作用。