固态材料形成过程中的晶体生长机理探讨

同样由熔体凝固、溶液沉淀或者气相沉积出来,为什么有的材料呈晶相,有的呈非晶相? 晶体生长是由自组装形成的还是由外界条件决定的?是哪项因素决定了晶体生长时原子的有序排列?本文根据实际现象,用晶体生长的热力学理论分析了逆向离子解离对晶体成核及生长的作用机理,并对固态材料的形成与晶体成核生长之间的关系也作了进一步的阐述和分析,由此得出结论认为,由化学键结合的材料在晶体生长时必须伴随着逆向离子解离平衡,正是固态材料形成过程中的逆向离子解离过程,如同时伴随着电离的溶解、熔化及升华过程,决定了晶体生长时原子的有序排列.     

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.     

激光晶体Nd:KGW晶体的表面缺陷观察

本文采用助熔剂籽晶提拉法生长出了Nd:KGW激光晶体.利用光学显微镜对晶体表面进行观察、并拍摄到晶体裂缝、生长丘、生长条纹和包裹物等缺陷的照片.分析其原因,是由于晶体生长工艺的不稳定,尤其是晶体生长过程中的温度梯度不够合适、提拉速度过快、降温速率偏快等所致.并由于生长体系粘度较大,容易形成包裹,晶体包裹物经XRD分析认为其中主要是熔体.     

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.     

基于动态纹理分析的蓝宝石熔体状态识别方法

应用泡生法生产蓝宝石晶体时,引晶必须在熔体温度梯度变化相对较小的条件下进行.针对化料后熔体界面随温度变化波动较大、难以寻找理想的引晶状态这一问题,提出了一种基于熔体界面动态纹理分析的状态识别方法.通过对经典Canny算子边缘检测技术的优化,来增强对晶体生长熔体纹理提取的鲁棒性;利用反映熔体状态的重要特征参数,实现对熔体状态的自动识别.仿真实验验证了该方法的有效性,为实现蓝宝石晶体的智能化制造提供了新途径.     

近化学计量比铌酸锂晶体中机械孪晶的消除

在用掺钾的助熔剂提拉法生长近化学计量比LiNbO3晶体时,长出的晶体尾部很容易出现孪晶裂纹现象,这种孪晶被认为是机械孪晶.这种孪晶的起因是由于晶体生长的收尾和从熔体中提起晶体阶段,在晶体底部产生直径的缩进,在缩进产生的台阶处出现应力集中,从而造成孪晶的成核.通过采用适当的收尾过程,以避免直径台阶的出现,可以很好地消除这种孪晶及其引起的裂纹.     

熔体分层对BaBiBO4晶体生长的影响

研究在用助熔剂法生长BaBiBO4晶体的过程中,熔体分层对晶体生长的影响.以Li2Mo3O10作为助熔剂,采用自发成核和顶部籽晶两种方法来生长晶体.对于这两种方法得到的晶体,用X射线粉末衍射及拉曼光谱进行了表征,结果显示,在晶体生长过程中,由于熔体分层,导致通过自发成核和顶部籽晶分别得到BaMoO4多晶和LiBaB9O15单晶两种不同的物相.     

一种生长异形晶体的技术——导模法

1938年,前苏联科学家Stepanov首次发明了异形晶体的生长方法.1967年,美国Tyco实验室LaBelle发明了导模法晶体生长技术( edge-defined film-fed growth, EFG) ,该技术利用与熔体可浸润的模具材料使坩埚内的熔体通过模具的毛细孔或毛细缝的虹吸效应上升到模具上表面,通过定向...     

用数学模型计算生长大尺寸光学晶体加热系统结构第1部分-对φ400mmCaF2晶体生长加热系统计算的方法和结果

本文的计算方法是根据对晶体生长炉中温场和热交换状态的实验研究提出的.用这种计算已成功地生长出大尺寸的CaF2和BaF2晶体(直径φ400mm),计算方法的准确性已为实验所证实,在许多新建或现有的生长系统中,结果都证明这种计算方法对于解决一些生长和退火问题是有效的.这种方法被广泛地用于估计各种复杂结晶容器的边界条件和在大晶体生长各个阶段的连续温场处理模型.这一点非常重要,因为迄今除了计算以外还没有其它方法可用于分析碱卤化合物材料的熔体-晶体系统的热状态,在用Stockbarger技术中,这些实验结果被成功地用于发展生长设备.     

铁电铌酸钾锂晶体的生长

用电阻加热引上法生长了不开裂、全透明的具有倍频性能的铌酸钾锂(KLN)晶体.研究了影响晶体开裂的主要因素和晶体生长的稳定性.发现用引上法生长KLN晶体时,要得到全透明、不开裂的KLN晶体,熔体中Li2O的含量应该低于26.5mol;,拉速应低于0.5mm/h,以及生长过程中应该选择凸的固液界面以保证晶体生长的稳定性.在Li2O含量较高的熔体中生长KLN晶体时,[100]取向的籽晶比[001]取向的籽晶更有利于晶体生长.用由Li2O含量为26mol;的熔体中沿[100]取向生长的KLN晶体对Ti:Al2O3激光器输出的820nm的激光倍频,获得410nm的蓝光输出.     

A novel method of temperature control for a crystal growth puller

A facile method to control the contracting rate of the thermal expansible bars for pulling crystal is first suggested. The thermal expansible bars, set in a modified Dewar flask whose vacuum degree is controlled, are heated to designed temperature and then switch off the power to let it cool down at a desired rate, which depends largely on the changeable vacuum degree. This new approach is expected to completely eliminate the effects, which possibly reduces the smooth extent of thermal expansion, caused by the minor temperature fluctuations during crystal growth process and to realize the utmost smooth and slow pulling rate. It is expected to install this apparatus in optical floating zone furnace, instead of traditional motor, to grow peritectic crystal, such as crystal Bi‐2223, since for the peritectic reaction, in principle, the extremely slow growing rate is considerably essential.     

新型有机非线性光学晶体-L-苹果酸脲晶体生长的初步探讨

本文初步探讨了新型非线性光学晶体-L-苹果酸脲的晶体生长,研究结果表明,L-苹果酸脲晶体在甲醇、乙醇和水三种介质中的溶解度温度系数均较大,同温度下L-苹果酸脲晶体在水中的溶解度最大,无水甲醇次之,无水乙醇中最小.L-苹果酸脲晶体在无水甲醇中的成核自由能比在无水乙醇中的低得多,因此在无水甲醇中易于成核,晶核数多,晶体尺寸小,而在无水乙醇介质中,虽然成核相对比较困难一些,但有利于制备大的单晶,且发现低温有利于大晶体的生长.因此宜选择无水乙醇为晶体生长介质.L-苹果酸脲晶体在介质中以非均匀成核方式在试管壁成核长大,晶体呈棱柱状,生长过程中呈现台阶生长的特征.     

GaAs---InP heteroepitaxy and GaAs---InP MESFET fabrication by MOVPE

Lattice-mismatched heteroepitaxy has attracted considerable attention in recent years. A great interest of these systems is the possibility of integrating devices from different materials on a single substrate. 1.3 and 1.5 μm InGaAs(P)/InP laser diodes are essential for optical communication, whereas InP field effect transistor technology is less developed than that of GaAs MESFET. The performances of laser diodes are much more sensitive to a high density of disclocations, so it would be interesting to grow GaAs MESFET on InP for integration with 1.3 and 1.5 μm lasers. Due to the large difference of the thermal expansion coefficient and lattice parameter between GaAs and InP, it is very difficult to grow GaAs epilayers of high quality on it is very difficult to grow of GaAs epilayer high quality on InP substrates due to the large difference of the thermal expansion coefficient and lattice parameter between GaAs and InP. A new method, metalorganic source modulation epitaxy (MOSME), which improves the crystal quality of GaAs epilayers on InP substrates by MOVPE, has been adopted in our laboratory. The lowest full width at half maximum (FWHM) of the double crystal X-ray (DCX) diffraction spectra reaches as low as 120 arcsec for a 5 μm thick layer. Structural properties (misorientation, lattice parameters and crystal quality) of 1.0–5.0 μm thick GaAs layers grown on InP have been measured by DCX diffraction. On GaAs MESFETs grown on InP, we have measured g_m = 100 ms/mm. For these transitions, the current gain cut-off frequency (F_t) is around 12 GHz and the maximum frequency of oscillation (F_max) is higher than 30 GHz.     

利用化学键方法寻找新型光学晶体

利用化学键的观点定量地研究了一些具有各种晶体结构实用材料的介电性质。采用已建立的化学键方法，分析了这些晶体的介电性质与其组成化学键之间的关系。更进一步，基于晶体的化学键方法提出了一个组合方法用于定量确定具有相似晶体结构材料的介电性质。从目前的工作中可以推导出光学晶体非线性起源的结构信息，因此可以在一定程度上帮助人们开展非线性光学晶体工程的研究工作。     

Advancements (and challenges) in the study of protein crystal nucleation and growth; thermodynamic and kinetic explanations and comparison with small-molecule crystallization

This paper reviews advancements and some novel ideas (not yet covered by reviews and monographs) concerning thermodynamics and kinetics of protein crystal nucleation and growth, as well as some outcomes resulting therefrom. By accounting the role of physical and biochemical factors, the paper aims to present a comprehensive (rather than complete) review of recent studies and efforts to elucidate the protein crystallization process. Thermodynamic rules that govern both protein and small-molecule crystallization are considered firstly. The thermodynamically substantiated EBDE method (meaning equilibration between the cohesive energy which maintains the integrity of a crystalline cluster and the destructive energies tending to tear-up it) determines the supersaturation dependent size of stable nuclei (i.e., nuclei that are doomed to grow). The size of the stable nucleus is worth-considering because it is exactly related to the size of the critical crystal nucleus, and permits calculation of the latter. Besides, merely stable nuclei grow to visible crystals, and are detected experimentally. EBDE is applied for considering protein crystal nucleation in pores and hydrophobicity assisted protein crystallization. The logistic functional kinetics of nucleation (expressed as nuclei number density vs. nucleation time) explains quantitatively important aspects of the crystallization process, such as supersaturation dependence of crystal nuclei number density at fixed nucleation time and crystal size distribution (CSD) resulting from batch crystallization. It is shown that the CSD is instigated by the crystal nucleation stage, which produces an ogee-curve shaped CSD vs. crystal birth moments. Experimental results confirm both the logistic functional nucleation kinetics and the calculated CSD. And even though Ostwald ripening modifies the latter (because the smallest crystals dissolve rendering material for the growth of larger crystals), CSD during this terminal crystallization stage retains some traces of the CSD shape inherited from the nucleation stage. Another objective of this paper is to point-out some biochemical aspects of the protein crystallization, such as bond selection mechanism (BSM) of protein crystal nucleation and growth and the effect of electric fields exerted on the process. Finally, an in-silico study on crystal polymorph selection is reviewed.     

General principles of the synthesis of chalcogenides and pnictides in salt melts using a steady-state temperature gradient

The possibilities of growing crystals of metals, alloys, chalcogenides, and pnictides in halide melts using a steady-state temperature gradient are analyzed. Halides of alkali metals and aluminum can be used as transport media. The choice is determined by the melting temperature of salt mixtures. A conducting contour can also be applied to increase transport efficiency. This technique of crystal growth is similar to the electrochemical method. To eliminate interference during migration, some elements can be isolated and forced to migrate through independent channels to the crystal formation region. The technique considered here makes it possible to grow crystals of necessary quality without special equipment; the small crystal sizes are sufficient for laboratory study.     

Chemical bond analysis of the crystal growth of KDP and ADP

The bond valence model is employed to calculate the bond strength of constituent chemical bonds formed between growth units in both potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate (ADP) crystals, with the aim to predict and control the crystal shape. After calculating and comparing the relative growth rates of all selected planes, which are related to the crystallographic structure and chemical bond strength, the natural morphology of both KDP and ADP can be conveniently deduced. To check the calculated results, the crystallites of KDP and ADP are grown under different growth conditions; their morphologies accord well with our theoretical calculations. Meanwhile, the influence of ethanol anti-solvent on crystal morphology is microscopically interpreted, which alters the crystal morphology by changing the supersaturation of the growing solution and influencing the bonding process. When ethanol is added into the growing solution, the crystal shape becomes slender.     

钼酸盐激光晶体的研究进展

对钼酸盐激光晶体材料的结构、生长技术、光谱特性等特点在国内外的研究进行了综述,认为作为激光晶体材料可以利用的钼酸盐分为类白钨矿型和钾钠铅矾型,在合成方法上以提拉法为主,但由于挥发及生长工艺等问题,晶体会出现色心、晶裂等现象.结合前人对该类材料的生长技术研究,我们重点对掺Yb3+离子的白钨矿型钼酸盐激光晶体光谱学特点进行了研究和总结,认为掺Yb3+离子的白钨矿型钼酸盐有望成为新一代的激光晶体材料.     

Growth of NaA zeolites in the presence of triethanolamine (TEA). The influence of water,TEA and Al contents

In order to obtain larger NaA zeolite crystals, the influence of starting materials and preparation conditions on the crystal growth has been studied. It is shown that the growth of NaA is most sensitive to changes in the gel composition. The crystal sizes are limited by subsequent nucleation occurring during the crystallization process. At the optimum gel composition, it is possible to grow crystals up to 75 μm in 100–400 ml reactants.