Mass transport in the three-thermal-zone solute transport method

The mass transport process of the three-thermal-zone solute transport method is analyzed theoretically in this paper. The growth rate of a crystal is depending on the temperature gradient and the size of the curcible. Comparing with the normal temperature gradient solute transport method, this technique can be used to grow crystals in better quality.     

Synthesis of chalcogenide and pnictide crystals in salt melts using a steady-state temperature gradient

Some examples of growing crystals of metals, alloys, chalcogenides, and pnictides in melts of halides of alkali metals and aluminum at a steady-state temperature gradient are described. Transport media are chosen to be salt melts of eutectic composition with the participation of LiCl, NaCl, KCl, RbCl, CsCl, AlCl₃, AlBr₃, KBr, and KI in a temperature range of 850–150°C. Some crystals have been synthesized only using a conducting contour. This technique of crystal growth is similar to the electrochemical method. In some cases, to exclude mutual influence, some elements have been isolated and forced to migrate to the crystal growth region through independent channels. As a result, crystals of desired quality have been obtained using no special equipment and with sizes sufficient for study under laboratory conditions.     

大尺寸电阻加热式碳化硅晶体生长热场设计与优化

大尺寸低缺陷碳化硅(SiC)单晶体是功率器件和射频(RF)器件的重要基础材料,物理气相传输(physical vapor transport, PVT)法是目前生长大尺寸SiC单晶体的主要方法。获得大尺寸高品质晶体的核心是通过调节组分、温度、压力实现气相组分在晶体生长界面均匀定向结晶,同时尽可能减小晶体的热应力。本文对电阻加热式8英寸(1英寸=2.54 cm)碳化硅大尺寸晶体生长系统展开热场设计研究。首先建立描述碳化硅原料受热分解热质输运及其多孔结构演变、系统热输运的物理和数学模型,进而使用数值模拟方法研究加热器位置、加热器功率和辐射孔径对温度分布的影响及其规律,并优化热场结构。数值模拟结果显示,通过优化散热孔形状、保温棉的结构等设计参数,电阻加热式大尺寸晶体生长系统在晶锭厚度变化、多孔介质原料消耗的情况下均能达到较低的晶体横向温度梯度和较高的纵向温度梯度。     

声光晶体TeO2的生长及缺陷研究

本文研究了直接ＴeO２晶体中的主要晶体缺陷形成机理,讨论分析了Ｔ eO2单晶生长的工艺参数对晶体缺陷的影响,结果表明：晶体裂缝的主要与温度梯度有关,温度梯度大于２０－２５℃/cm及出现界面翻转时,易造成晶全的开裂,位错密度增加,晶体中的包裹体主要为气态包裹全,它的形成主要与籽晶的转速和晶体的提拉速率有关,转速１５－１８r/min,拉速０.55mm/h,固液界面微凹,可以减少晶体中的气态包裹体,晶体台阶由晶体生长过程中温度和生长速度的引起伏引起,当台阶间距较宽时,易形成包裹体。     

提拉法晶体生长数值模拟研究进展

数值模拟方法是了解晶体生长过程中各种物理现象和问题的重要手段,可以为晶体生长工艺参数的设定、温场设计等提供参考.本文介绍了最近几十年来数值模拟技术对提拉法生长晶体过程中物理问题的研究进展,同时对晶体生长过程中界面形状、液流、速度场、温度场、各种输运过程以及工艺条件和参数对晶体生长的影响等的数值模拟进行了介绍.     

Analysis and calculation of the formation of grown-in microdefects in dislocation-free silicon single crystals

The physical model of the formation of grown-in microdefects in dislocation-free Si single crystals has been analyzed. The mathematical models used to describe the processes of defect formation in crystals during their growth are proven to be adequate to the physical model. A technique is proposed to determine and calculate the defect structure in dependence of the crystal growth conditions (growth technique, growth rate, temperature gradients, cooling rate). It is shown that the theoretical study of the real crystal structure in the dependence of the thermal growth conditions using an original virtual technique for analyzing and calculating the formation of grown-in microdefects is a new experimental technique.     

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 IR Television Scanning Technique as Temperature Field Control for Growing Silicon Crystals

Outgoing from the idea that the temperature field of the growing crystal is the most general as well as characteristic representation of all technological parameters and equipment conditions the ir-television scanning technique was as a method for recording and controlling of temperature distributions at the surface of growing crystals and melts. Using a number of electronic treshold value switches, some video signal amplitude levels can be made visible at the monitor, giving an overlook on the isotherm distribution at the crystal surface. Records of such observations are helpful for reproduction and optimization of crystal growth technologies. For Silicon crystal growth, the process control by ir-television scanning technique is a fast, convenient, and nondisturbing one giving important informations.     

The impact of pressure and temperature on growth rate and layer uniformity in the sublimation growth of AlN crystals

To effectively design a large furnace for producing large-size AlN crystals, a fully coupled compressible flow solver was developed to study the sublimation and mass transport processes in AlN crystal growth. Compressible effect, buoyancy effects, flow coupling between aluminum gas and nitrogen gas, and Stefan effect are included. Two sets of experimental data were used to validate the present solver. Simulation results showed that the distributions of Al and N₂ partial pressures are opposite along the axial direction due to constant total pressure and Stefan effect, with the Al and nitrogen partial pressures being highest at the source and seed crystals positions, respectively. The distributions of species inside the growth chamber are obviously two-dimensional, which can curve a flat crystal surface. Simulation results also showed that AlN crystal growth rate can be increased by reducing total pressure or by increasing seed temperature or by increasing source-seed temperature difference. High nitrogen pressure causes decrease in growth rate, but it is beneficial for obtaining uniform growth rate in the radial direction. Results of simulation also showed that there is an optimized temperature difference (40 °C) in the present furnace for obtaining good homogeneity of growth rate.     

Thermal behavior of biogenic apatite crystals in bone: An X‐ray diffraction study

The thermal behavior of the bovine bone mineral and synthetic stoichiometric hydroxyapatite was investigated by X‐ray diffraction. The bone samples in solid (planar oriented pieces) and in powder form were examined to elucidate how the microstructural and textural properties of bone mineral are modified under heating. As could be expected, the thermal behavior of the bone mineral depends not only on the structural distortions, but also on the crystal habit, texture and ordering of biocrystals in tissue. The temperature growth of biogenic apatite crystals, unlike synthetic hydroxyapatite, is seen to be nonmonotonic and multi‐staged. At 600 to 700°C the biomineral crystallites grow rapidly due to disappearance of the mosaic structure as the lattice imperfections are annealed. After heating between 700°C and 900°C the bone mineral appears to be composed of roughly equidimensional ≥200 nm crystals. The further growth of the crystals in the range from 900 to 1300°C occurs by the mass transport mechanism, supporting the idea that the bone mineral is not a discrete aggregation of crystals, but rather a continuous mineral phase with direct crystal‐crystal bonding. Estimates are presented to show the important role of the surface mass transport mechanism in the growth of apatite crystals. The material obtained by heating a cortical bone fragment between 900°C and 1300°C turns out to be composed of two crystal types: crystals oriented along the bone axis (major morphology) and those of differing shape and orientation (minor morphology). The heating‐induced variations in the longitudinal and transverse dimensions of differing‐morphology crystals are found to be coherent. Small amounts of CaO, MgO and other crystalline phases are seen to be formed in the bone mineral under heating. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Electronic Transport Properties of Thallium Sesquiselenide Single Crystals

Electronic transport measurements were made on single crystal samples of Tl₂Se₃. The crystals were prepared by a special design based on Bridgman technique. The influence of temperature on the electrical conductivity, Hall effect, Hall mobility and the carrier concentration was investigated in the temperature range 200–400 K. The energy gap as well as the ionization energy were calculated. The scattering mechanism of the charge carrier was discussed in the same temperature range.     

Experimental Verification of the Numerical Model for a CaF2 Crystal Growth Process

Large calcium fluoride (CaF₂) single crystals are required for the fabrication of lenses in so‐called wafer‐steppers of future IC‐lithography technologies operating at 193 nm and 157 nm. Numerical simulation plays an important role to design an adequate growth setup and processing conditions for the growth of high quality crystals. An important issue is the consideration of the internal heat transfer by radiation in the semitransparent CaF₂ during the crystal growth process. Results of the numerical modeling of the heat transport are presented, which are obtained by using the software package CrysVUn++ with different models considering the internal heat transport in CaF₂. To improve the availability of experimental data on CaF₂ bulk growth, an especially designed R&D‐facility was built. This growth system is equipped with a variety of in‐situ measurement systems to detect the temperature distributions in the crystal and melt region. Calculated temperature distributions are compared with experimental data. Also first results on single crystal growth will be reported.     

Protein crystallization under microgravity conditions. Analysis of the results of Russian experiments performed on the International Space Station in 2005−2015

Conditions of mass transport to growing crystals have a considerable effect on the crystal size and quality. The reduction of convective transport can help improve the quality of crystals for X-ray crystallography. One approach to minimizing convective transport is crystallization in a microgravity environment, in particular, in space. The data obtained by our research team in protein crystallization experiments on the International Space Station are surveyed and analyzed.     

Influence of growth conditions on microstructure and properties of GaSe crystals

GaSe crystals have been grown from melt. There are several reasons why it is difficult to meet ideal demands for nonlinear optic material, GaSe single crystal. First, these crystals have a tendency towards lamination because of great difference in a and c crystal lattice parameters and very weak Vander der Waals forces in c direction. Next, there is a great difference in saturation vapor pressure of the components, which can cause nonstoichiometry of a melt-grown crystal composition. Another obstacle in the growth of perfect GaSe crystals is dendrite formation caused by instability of the growth front. To overcome this obstacle we used Bridgman technique and have found the temperature and pressure conditions, and growth velocity which provide growth of perfect bulk single crystals of about 100 mm in length and 20 mm in diameter. Sharp Laue patterns and a rocking curve confirm perfect structure of the grown crystals. Electron-probe X-ray microanalysis shows stoichiometric composition of GaSe crystals and X-ray phase analysis reveals presence of single-phased hexagonal structure.     

Flux process for growth of large crystals with application to beryllia

A procedure is described for flux-growth of beryllia crystals, applicable to other crystals. Growth is promoted in a solvent flux by continuous transport of BeO solute in a steady-state thermal gradient. Prepared seeds are mounted on a support structure, submerged in the flux at thermal equilibrium, and rotated during the growth period. The character of growth depends on multi-parameter growth conditions including proper seed crystal structure and preparation, flux composition and impurities, temperature, and operational procedures.     

Growth, morphological, mechanical and dielectric studies of semi organic NLO single crystal: l-argininium perchlorate

Optically good quality single crystal of l-argininium perchlorate (abbreviated as LARPCL), a promising analog of LAP was successfully grown by slow solvent evaporation technique at room temperature. The unit cell parameters and the morphology of LARPCL single crystals were determined by single crystal XRD. The Vickers microhardness measurements were carried out on the grown crystals to estimate the mechanical properties. The dielectric constant and dielectric loss of the crystal were measured as a function of frequency and temperature, and the results are discussed.     

利用界面调控制备二维有机半导体晶体及其机制研究

二维有机半导体晶体是利用分子间的范德瓦耳斯力进行自组装生长的单晶材料。本质上的单晶属性使其具备优异的电学特性。更重要的是,二维极限下增强的界面特性能够大幅调控器件行为,为构建多功能界面器件提供可能。此外,充分暴露的电荷输运沟道和极少的晶面内缺陷能够为研究本征的有机电子输运特性创造可能。目前,对于二维有机半导体晶体的生长工艺研究已经取得了较大的进展,但是从理论层面上研究二维晶体生长的自组装过程仍然十分匮乏。本工作利用添加剂辅助结晶技术成功制备出二维有机半导体晶体,并通过偏光显微镜和原子力显微镜对二维晶体进行了全面的表面形貌和结构表征。通过SEM结合EDS技术对关键的形核界面进行了结构和组成的表征以研究晶体生长的机制。研究结果表明:在添加剂界面上,生长材料能够稳定形核,并计算出添加剂构建的有利界面能够将形核势垒降低为SiO₂界面上的1/5。这项工作充分展现了生长界面对于晶体生长的关键作用,并从理论上揭示了界面的调控行为,为二维有机半导体晶体的生长工艺设计提供了可靠的思路。     

System of Mathematical Models for the Analysis of Industrial FZ-Si-Crystal Growth Processes

A system of coupled mathematical models and the corresponding program package is developed to study the interface shape, heat transfer, thermal stresses, fluid flow as well as the transient dopant segregation in the floating zone (FZ) growth of large silicon crystals (diameter more than 100mm) grown by the needle-eye technique. The floating zone method with needle-eye technique is used to produce high-purity silicon single crystals for semiconductor devices to overcome the problems resulting from the use of crucibles. The high frequency electric current induced by the pancake induction coil, the temperature gradients and the feed/crystal rotation determine the free surface shape of the molten zone and cause the fluid motion. The quality of the growing crystal depends on the shape of the growth interface, the temperature gradients and corresponding thermal stresses in the single crystal, the fluid flow, and especially on the dopant segregation near the growth interface. From the calculated transient dopant concentration fields in the molten zone the macroscopic and microscopic resistivity distribution in the single crystal is derived. The numerical results of the resistivity distributions are compared with the resistivity distributions measured in the grown crystal.     

非对称扩散工艺制备近化学计量比钽酸锂晶体的研究

利用气相平衡输运法制备的近化学计量比钽酸锂晶体质量好,制备工艺简单,但受固体扩散速率低的影响,该方法较难制备大厚度晶体。本文基于钽酸锂晶体的扩散机制,采用待扩散晶片一侧为富锂气氛,另一侧为同成分气氛的非对称扩散工艺,对钽酸锂晶体进行了扩散处理,并对组分和畴反转电场进行表征。结果表明,非对称扩散工艺为反位钽离子的扩散提供了通道,提高了晶体中反位钽离子和锂离子的扩散速率,有利于制备大厚度近化学计量比钽酸锂晶体。     

名义纯及掺杂铌酸锂晶体内偏置场的实验研究

铌酸锂晶体的内偏置场对铁电应用、电光应用和非线性光学应用等均有直接影响。本工作建立了铌酸锂(LN)晶体内偏置场测试方法,对同成分铌酸锂(CLN)晶体、近化学计量比铌酸锂(nSLN)晶体、掺杂铌酸锂(doped LN)晶体的内偏置场和矫顽场进行测量。结果表明,CLN晶体内偏置场最高(E_int=2.53 kV/mm),nSLN晶体的内偏置场大幅降低,其中富锂熔体法生长和气相输运平衡(vapor transport equilibration, VTE)法结合得到的nSLN晶体的内偏置场最小,与CLN晶体相比降低了约两个数量级;掺杂铌酸锂晶体的内偏置场与CLN晶体相比也普遍降低,其中掺6.5%(摩尔分数)Mg的CLN晶体的内偏置场约为CLN晶体的四分之一,掺7%(摩尔分数)Zn的CLN晶体的内偏置场约为CLN晶体的六分之一。最后对组分和掺杂影响内偏置场的因素进行了简要分析。