Effect of gravitation vector orientation relative to the solidification front on the micro- and macrohomogeneity of semiconductor crystals grown under terrestrial and space conditions

The influence of gravitation vector orientation relative to the solidification front on the dopant distribution micro- and macrohomogeneity in vertical oriented crystallization of highly Ga-doped Ge crystals has been investigated using computer simulation. The deviation of the axis for crystal growth relative to the g ₀ vector, when a free surface of the melt is present, has been found to provide the formation of striations with a reduced dopant concentration. The influence of the solidification rate, convective and diffusion mass flows on the dopant distribution macrohomogeneity has been investigated.     

Dislocation Generation in Dislocation-Free Germanium

A dislocation structure is studied in germanium single crystals grown in a regime of minimum temperature gradients at the crystallization front and low supercooling. The investigations show that the distortion of the flat crystallization front arising during crystal droplet detachment in the completion growth stage results in the dislocation generation in the lower parts of dislocation-free single crystals. The dislocations are generated at the phase boundary and propagate in the thermoplasticity zone. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 21–24, May, 2005.     

Experimental evidence and theoretical analysis for the chiral symmetry breaking in the growth front of conglomerate crystal phase of 1,1'-binaphthyl

Chirally asymmetric states, chemical oscillations, propagating chemical waves, and spatial patterns, are examples of far-from-equilibrium self-organization. We have found that the crystal growth front of 1,1(')-binaphthyl shows many of the characteristics of an open system in which chiral symmetry breaking has occurred. From its supercooled molten phase, 1,1(')-binaphthyl crystallizes as a conglomerate of R and S crystals when the temperature is above 145 degrees C. In addition, 1,1(')-binaphthyl in its molten phase is always racemic due to its high racemization rate. Under appropriate conditions, bimodal probability distribution of enantiomeric excess (ee) with maxima around 60% was observed. The ee was mass independent, indicating that the growth front maintains a constant ee. A kinetic model that theoretically analyzes the chiral symmetry breaking transition in the growth front of a conglomerate crystal phase was formulated. Computer simulation of the model reproduced not only the average but also the large variation of the ee observed in crystallization experiments.     

On the problem of the consistency of the high-temperature precipitation model with the classical nucleation theory

The adequacy of the model of high-temperature precipitation in dislocation-free silicon single crystals to the classical theory of nucleation and growth of second-phase particles in solids has been considered. It has been shown that the introduction and consideration of thermal conditions of crystal growth in the initial equations of the classical nucleation theory make it possible to explain the precipitation processes occurring in the high-temperature range and thus extend the theoretical basis of the application of the classical nucleation theory. According to the model of high-temperature precipitation, the smallest critical radius of oxygen and carbon precipitates is observed in the vicinity of the crystallization front. Cooling of the crystal is accompanied by the growth and coalescence of precipitates. During heat treatments, the nucleation of precipitates starts at low temperatures, whereas the growth and coalescence of precipitates occur with an increase in the temperature. It has been assumed that the high-temperature precipitation of impurities can determine the overall kinetics of defect formation in other dislocation-free single crystals of semiconductors and metals.     

Crystal Growth of Isotactic Polystyrene in Ultrathin Films: Thickness and Temperature Dependence

The growth rate and morphology of isotactic polystyrene crystals grown in ultrathin films have been examined experimentally in terms of the dependences both on the film thickness and on the crystallization temperature. We have found that the thickness dependence of growth rate, G, shows a crossover change when the film thickness becomes comparable with the lamellar thickness of the polymer crystals, irrespective of the temperatures. The morphology of crystals grown in ultrathin films shows a branching typical of dendrites, the growth of which is supposed to be controlled by a diffusion field. The change in the tip width of the dendrites with crystallization temperature follows the expected dependence of the Mullins–Sekerka stability length, ?_MS ∝ (D/G)^1/2, determined by the diffusion coefficient, D, and the growth rate. The results confirm that a diffusion field plays an essential role in the evolution of the structure.     

AlN晶体物理气相传输法生长坩埚的热场分析

采用物理气相传输法在钨制坩埚上制备AlN单晶.通过采用COMSOL软件中的固体传热和磁场模块,对AlN晶体生长的坩埚的热场进行仿真,同时针对不同的线圈直径以及不同的线圈位置对坩埚热场的影响进行模拟,提出了相应的处理方式.结果表明:当线圈直径增大,坩埚结晶区和升华区的温度在相同的加热时间下会增加,并且增加的温度存在峰值.当线圈的垂直位置发生变化的时候,结晶区和升华区的温度场也会发生变化,从上向下移动的过程中仍然存在温度的峰值,并且结晶区和升华区的温度关系会发生翻转,导致温度梯度阻碍晶体生长.在晶体生长过程中升华区和结晶区的温度关系依旧会发生翻转.但是通过线圈跟随籽晶表面生长层的变厚而同步移动,可以保持相对稳定的温度关系,维持晶体正常持续生长.     

Study of the crystallization morphology of VT3-1 alloy during VAR

In this paper, we consider the crystallization morphology formation of VT3-1 titanium alloy in the process of vacuum arc remelting (VAR). Based on experimental data obtained by the method of autoradiography, we numerically determine remelting parameters such as the temperature gradient G at the solidification front and its velocity V. Since practically all kinds of morphology of the crystallization microstructure of metal systems are present in an ingot (planar front, cellular, cellular-dendritic, and dendritic structures), we consider two simple models of transition from one structure to another. The models greatly depend on the parameters G and V. In this paper, the liquidus curve slopes for the alloying elements of VT3-1 alloy are determined and a morphology map is constructed. Also, the results are compared with those obtained earlier by other authors.     

Softening processes in single-crystal tungsten ribbons

Recovery processes in rolling-deformed (001)[110] tungsten single crystals having various degrees of purity are investigated. It is shown that the dislocation structure formed in the plastic deformation of tungsten single crystals is transformed in subsequent high-temperature anneals to a system of dislocation subboundaries; only polygonization, which preserves the single-crystal structure, takes place in samples heated to a temperature close to the melting point. The formation of subboundaries proceeds in two stages with subsequent transformation of the unstable structure to a configuration having an energy minimum. The decisive factor affecting the polygonization rate is the stacking fault energy; the presence of impurities also has a significant influence. Fiz. Tverd. Tela (St. Petersburg) 40, 498–502 (March 1998)     

Laser Rapid Melting Structure and Property for Ni－based Tungsten Carbide Alloy

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LiNbO3单晶体直拉法生长时组分过冷所形成的胞状界面和胞状组织

对于沿[0001]生长的LiNbO₃单晶体,组分过冷形成的胞状界面和胞状组织进行了形态学的研究(组分过冷是由于操作上的原因在熔体中掺入了Al₂O₃而引起的),确定了胞状界面和胞状组织的基本形态。胞状界面是由相毗邻的三角锥组成,三角锥的稜锥面为{0112}面组,毗邻的三角锥体间存在沟漕,其中的熔体中浓集溶质。在长成的晶体中的胞状组织或是由{1210}面构成的其母线平行于[0001]方向的稜柱体,或是由溶质浓集的三{1210}面相交而成的三叉。实验观测证实了白丝、白点、云层及溶质尾迹是胞状组织的某种表现,而温度起伏是形成间歇式胞状组织的原因。通过胞状界面的形态研究,确定了形态干扰的某些具体形式,并证实了破坏界面稳定性的形态干扰与界面邻近流体的动量边界层的稳定性有关。文章最后讨论了高熔点氧化物晶体与金属晶体的胞状组织在形态上的差异,认为是由于两类物质的不同熔化熵而产生的。 关键词：     

细胞色素bc_1复合物结晶的显微共振拉曼光谱

细胞色素ｂｃ１复合物结晶的显微共振拉曼光谱何季平①岳文海①尤乃亭②李晓原②李五湖②陈震华③（①武汉工业大学材料研究与测试中心武汉４３００７０）（②香港科技大学化学系香港九龙清水湾）（③武汉大学化学系武汉４３００７２）ＭｉｃｒｏＲｅｓｏｎａｎｃｅＲａｍ...     

Crystallization of solutes from droplets

Experiments on crystallization of thiourea and sodium hydroxide from an aqueous solution in a microvolume of 10⁻¹⁰ 1 (100 pl) are described. The phenomenon of dehydration self-organization in such tiny droplets of solution is studied for the first time. The effect of different factors, such as solution concentration, ratio of the components mentioned above in one solution, and substrate properties on the size, structure, and properties of crystals grown. Analysis of the experimental data is performed, and the drying rate of the drops and the supersaturation of the solution are estimated. Insight into the self-organization of solute molecules in a micro-or nanovolume of the drying solution may be of great applied and fundamental value, giving rise to new techniques in micro-and nanotechnology and new classes of problems in the physics of fractals and strongly nonstationary dissipative processes.     

Kinetics of high-temperature precipitation in dislocation-free silicon single crystals

The defect structure of dislocation-free silicon single crystals has been calculated using the approximate solution of the Fokker-Planck partial differential equations. It has been demonstrated that the precipitation starts to occur near the crystallization front due to the disappearance of excess intrinsic point defects on sinks whose role is played by oxygen and carbon impurities.     

Morphology and Structure of Poly(p-phenylene Benzobisthiazole) Crystals

The rigid polymer poly(p-phenylene benzobisthiazole) (PBZT) was crystallized from dilute solution. Electron microscopy showed that, on quenching, flat fibrils several nanometers thick were produced. Subsequent heat treatment in a solvent changed the morphology from fibrillar into “segmented ribbon” structure. Isothermal crystallization at a temperature of about 30°C below the dissolution temperature, in general, resulted in aggregation of rod crystals. The polymer chains were oriented normal to the rod crystals. The width of the rod crystal increased with average molecular length, but saturated to a value much smaller than the average molecular length. In the shorter molecular length range, the rod crystals clustered in a fanned-out manner, while with a medium molecular length (ca. 70–120 nm), all rods crystals in a cluster aligned parallel to each other and were of the same length. With longer molecular length (more than ca. 180 nm), the rod growth slowed because of small diffusion constants of molecular chains to the growing face. Based on observation of the morphology and the crystallization process, an isothermal crystallization mechanism is proposed. Because of the rigidity and wide length distribution of polymer chains, the chain ends were inevitably included within the crystals, resulting in crystal defects such as axial shifts, lattice curvatures, and edge dislocations, all of which were observed directly by lattice imaging.     

Stretch-Induced Shish-Kebabs in Rubbery Poly(L-Lactide)

The oriented crystallization in stretched rubbery poly(L-lactide) has been studied with the aid of in-situ rheo-Fourier transform infrared spectroscopy (FTIR) measurements and morphological observations. The oriented segments that survived after stretching are first transformed into shish structure composed of helical sequences via intra-chain conformational ordering and propagation, followed by the transverse growth of kebabs from the coiled chains in the surrounding matrix. Moreover, the formation of shish structure and kebabs shows different dependences on the stretching temperature as a result of different controlling molecular processes.     

The cellular substructure of zinc single crystals prepared by the Czochralski method

The dependence of the size of cellular substructure on the rate of growth and the temperature gradient of metal single crystals grown from the melt by the Czochralski or Bridgmann method are the same. The dependence of the size of elongated cells are of the same type as in the case of cells. A hypothesis on the mechanism of production of elongated cells is proposed regarding the influence of orientation of single crystals.     

Polymer-mediated and ultrasound-assisted crystallization of ropivacaine: Crystal growth and morphology modulation

The objective of this research was to modify the crystal shape and size of poorly water-soluble drug ropivacaine, and to reveal the effects of polymeric additive and ultrasound on crystal nucleation and growth. Ropivacaine often grow as needle-like crystals extended along the a-axis and the shape was hardly controllable by altering solvent types and operating conditions for the crystallization process. We found that ropivacaine crystallized as block-like crystals when polyvinylpyrrolidone (PVP) was used. The control over crystal morphology by the additive was related to crystallization temperature, solute concentration, additive concentration, and molecular weight. SEM and AFM analyses were performed providing insights into crystal growth pattern and cavities on the surface induced by the polymeric additive. In ultrasound-assisted crystallization, the impacts of ultrasonic time, ultrasonic power, and additive concentration were investigated. The particles precipitated at extended ultrasonic time exhibited plate-like crystals with shorter aspect ratio. Combined use of polymeric additive and ultrasound led to rice-shaped crystals, which the average particle size was further decreased. The induction time measurement and single crystal growth experiments were carried out. The results suggested that PVP worked as strong nucleation and growth inhibitor. Molecular dynamics simulation was performed to explore the action mechanism of the polymer. The interaction energies between PVP and crystal faces were calculated, and mobility of the additive with different chain length in crystal-solution system was evaluated by mean square displacement. Based on the study, a possible mechanism for the morphological evolution of ropivacaine crystals assisted by PVP and ultrasound was proposed.     

均聚物结晶与熔融化转变的稳态和亚稳态统计理论Ⅵ. 分子分凝统计结晶动力学-结晶增长速率对结晶生长机制和溶液浓度和的依赖性

首先对结晶增长速率同浓度和链柔性依赖性进行总结,然后基于微晶核和粒———高分子键组网络结构模型和高分子分子分凝统计结晶动力学,根据高分子链组是微晶粒同连接链段复合体的结构特征及它们间存在的四个相关性(并存性、简并性、顺反式构象共存性和物料守恒性)的事实,成功地把连接链段缩短增长动力方程同微晶粒体积增大增长动力方程有机结合在一起,从理论上创建出一种微晶粒数增长速率和微晶粒尺寸增长速率表达式的一般化计算法,推导出结晶体系的微晶粒数增长速率、微晶粒尺寸增长速率同四种增长机制(近邻折叠,近邻伸直,近邻折叠同近邻伸直并联并存和近邻折叠同近邻伸直串联并存)、结晶温度和和结晶浓度间定量表达式.当把浓度指数同链的构象分数相连后,就又从理论上得到了浓度指数同温度和链柔性间的关系式,并讨论了它们同增长机制间的关系.最后以大量结晶动力学实验数据对上述所得到的关系式进行了验证,结果表明它们均能同实验结果很好符合.     

Obituary: Professor Valery Privalko

Gold decoration was applied to elucidate the morphology of annealed and unannealed oriented structures produced by shearing of polyethylene single crystals of known thicknesses, and the morphology of drawn and undrawn “shish kebabs” obtained by stirrer-induced crystallization. Distinct Au periodicities were observed perpendicular and parallel to the unannealed oriented structure, revealing distinctly the presence of microfibrils and an alternation of crystalline and noncrystalline regions within a given microfibril of which the periodicity is, however, found to be much larger than the corresponding original crystal thickness. Annealing resulted in fibrils being completely replaced by lamellae standing edgewise with the Au particles decorating directly on top of the edge but concentrated mainly on the folds leaving the crystalline region almost entirely void of gold. Deformation studies revealed an unusual ductility associated with the shish kebab structure, with the kebab splitting first, then disappearing with increasing elongation, and finally, resulting in a uniform fiber. The kebab disappearance implies that it is molecularly integrated with the interkebab material and not a completely separate chain-folded lamella attached to it. Distinct Au periodicities were observed perpendicular and parallel to the drawn shish-kebab fibers similar to the sheared single crystals. Annealing experiments and the high ductility suggest that the interkebab material is not of a fully extended-chain morphology.