化学气相沉积ZnS、ZnSe研究进展

化学气相沉积(CVD)ZnS、ZnSe具有较高的红外透过率及良好的光学、力学性能,是红外军用探测系统首选的红外光学材料。大尺寸、高均匀性ZnS、ZnSe材料的制备是未来研究的重要课题。本文介绍了CVD的原理及在沉积过程中存在的主要问题,阐述了高性能红外材料必备的光学性能,综述和分析了CVD ZnS、CVD ZnSe的研究进展,以及这两种材料主要缺陷形成机理与工艺控制研究。旨在改进生产工艺参数,为批量化制备高性能ZnS、ZnSe材料提供理论参考,以满足其在军事领域上的应用。     

用化学气相沉积(CVD)法制备硫化锌(ZnS)体块材料中晶体缺陷和生长工艺的研究

本文报道了用化学气相沉积(CVD)法制备高质量红外光学体块材料硫化锌(ZnS)的制备工艺,研究了晶体缺陷对其光学性能的影响.XRD,XEM及IR表明,采用优化的沉积工艺和热等静压后处理,减少晶体中杂质、微孔、六方结构ZnS及Zn-H键的形成,使生长的CVD ZnS具有高的红外透过率,提高了材料的光学品质.     

热等静压处理对CVD ZnS/ZnSe复合材料性质的影响

对利用化学气相沉积(CVD)制备的ZnS/ZnSe复合材料进行了显微结构和光学性质的测试和分析.研究表明,热等静压过程使得CVD ZnS/ZnSe晶体内部晶粒尺寸明显增大,减少或消除了内部缺陷,提高了材料的光学透过率.     

ZnS晶体的化学气相沉积生长

本文报道了用化学气相沉积(CVD)法生长ZnS透明多晶体的实验结果,对生长的晶体的物理化学性能进行了测试,讨论了化学气相沉积工艺中影响ZnS晶体质量的因素.结果表明:选用固体硫作原料,用化学气相沉积方法,可以沉积出透明ZnS多晶体;它的透过性能极其优异,在6.2μm处无吸收峰,在中、长波红外透过率可达70;以上.     

化学气相沉积法制备二维过渡金属硫族化合物研究进展

二维过渡金属硫族化合物(TMDs)是继石墨烯之后的新型二维材料,由于其自身的独特物理化学性质在半导体、光电材料、能源储存和催化制氢等方面备受瞩目。化学气相沉积(CVD)是目前适合实现大规模制备二维材料的工艺之一,制备过程中参数的高度可控性使其具有很大优势。本文综述了近期通过CVD制备TMDs的研究进展,探讨了在CVD制备工艺中各种参数对产物生长和最终形貌的影响,包括前驱体、温度、衬底、辅助剂、压力和载气流量等。列举了一些改进的CVD制备工艺,并对其特点进行了总结。最后讨论了目前CVD制备TMDs所面临的挑战并对其发展前景进行展望。     

8～12μm长波红外材料ZnS多晶的制备

真空热压烧结法是最经济、高效地制备ZnS多晶的方法之一.ZnS多晶的红外透过率是衡量材料品质的重要参数.本文运用TEM、XRD和化学分析方法,研究了原料粉末特性和热压工艺参数对热压ZnS多晶红外透过率的影响,并确定了合理的热压工艺参数.运用该方法制备的ZnS多晶6mm厚的试样,8～12μm波段平均红外透过率为66.7;.     

原生CVD ZnS 6.2 μm处吸收峰的消除及机理分析

原生CVD ZnS的特征之一是由于内部与S空位相关的Zn-H络合物的存在而在6.2 μm处形成吸收峰.相对较低的沉积温度和较高的沉积压力以及Zn/H2S是产生这一问题的主要原因.通过改进实验参数(沉积温度、沉积压力、Zn/H2S),能够制备出与经过HIP处理过的ZnS一样的无Zn-H络合物的原生ZnS.本文依据Zn-H络合物产生的原因对沉积温度、压力等作用机理进行了分析,总结出进一步提高CVD ZnS质量的方法.     

工艺参数对CVD ZnS沉积速率的影响

本文报道了CVD法制备ZnS晶体的制备工艺,系统地研究了气体流量、工作气压、基板温度等主要工艺参数对沉积速率的影响规律.实验表明,随着H2S(s)/Zn摩尔流量比的增加,沉积速率逐渐增大;基板温度升高,沉积速率加快;工作气压增大,沉积速率变化不大.在本实验研究的条件下认为,采用合适的H2S(s)/Zn摩尔流量比和沉积温度,在较低的工作气压下生长晶体,能保证较稳定的沉积速率,生长出高质量的晶体.     

用化学气相沉积法制备红外体块晶体ZnS

本文报道了采用化学气相沉积法制备红外ZnS体块晶体的工艺及其性能.并用傅立叶红外光谱仪测试了材料的红外性能,研究了晶体缺陷对材料红外透过率的影响.结果表明:通过优化生长工艺,使反应室的压力在500～1000Pa之间变化,沉积温度控制在550～650℃之间,可以制备出厚度均匀,红外透过率(3-5μm和8～12μm)在70;以上,尺寸达250mm×250mm×15mm高质量的ZnS体块晶体.     

以S、Se为原料的CVD ZnS、CVD ZnSe的化学反应分析

本文详细分析了用单质硫或单质硒为原料,在Zn-S-H2-Ar体系或Zn-Se-H2-Ar体系中化学气相沉积生长 ZnS和ZnSe晶体所发生的化学反应,认为在这两种化学气相沉积过程中所发生的化学反应是以锌蒸汽与硫或硒蒸汽反应来实现的.计算出了上述反应的△H、△S和△G这些热力学函数,并将该△G与采用H2S气体(Zn-H2S-Ar体系)和H2Se气体(Zn-H2Se-Ar体系)为原料的CVD ZnS和ZnSe做了对比.实验结果表明,以单质Se为原料生长的CVD ZnSe比以H2Se为原料的CVD ZnSe的努普硬度有显著的提高.     

Modelling of mechanism of agglomeration of KCl crystallization

The article presents an analysis into agglomeration during KCl vacuum crystallization. The theoretical and experimental investigations into the mechanism of agglomeration during mass crystallization result in an extension of the growth phenomena within the known model equations. The basis for this is essentially constituted by the collision model concepts of the theory of floculation in disperse systems. The parameters derived from the microprocess analysis (energy dissipation, content of solids, growth rate of individual grains) lead to model equations which are confirmed by laboratory and test trials.     

Relationship of Morphological Types of Dynamic Forms of Crystals

Crystallography Reports - The relationship of morphological spectra (sets of data on the morphological types of real polyhedral crystals and their probabilities under current physicochemical...     

Velocities of Disappearance and Lifetime of Faces of Growing Crystals

The formulae for absolute R_disap and relative R velocities of disappearance and lifetime τ of faces of growing crystals have been derived for stationary growth. It was shown that the quantities are determined by the relative growth velocity R_A/R_critA of the vanishing face A with respect to the critical growth velocity R_critA and by the geometry of a crystal expressed by the trigonometric functions of interfacial angles β and γ formed between face A and the adjacent faces. R increases and τ decreases with the increase in R_A/R_critA to certain limiting values. The calculations have been verified and illustrated by the experimental results for triclinic potassium bichromate (KBC) crystals. Results enable ones to predict values of velocities of disappearance and lifetimes of undesirable, supplementary faces of any real crystal.     

Development of Pauling's concepts of geometric characteristics of atoms

The evolution of the geometric characteristics introduced by Pauling and their dependence on the specific features of the structure and chemical bonds have been considered. The values of the covalent and van der Waals radii are given as well as their relationships and mutual transitions.     

Dependence of the parameters of equations of viscous flow on chemical composition of silicate melts

The temperature dependence of viscosity of silicate melts is discussed in the framework of the Avramov–Milchev (AM) equation. The composition is described by means of two parameters: the molar fraction, x, and the “lubricant fraction”, l. The molar fraction is the sum of the molar parts x_i of all oxides dissolved in SiO₂, the molar fraction of the latter being 1 ? x. It is shown that, with sufficient precision, two of the parameters of the AM equation can be presented as unique functions of the molar fraction. On the other hand, x is not sufficient to determine properly the reference temperature T_r , at which viscosity is η_r = 10¹³ [dPa.s]. Therefore, additional parameter, “lubricant fraction” l, is introduced. For each of the components, l_i is a product of molar part x_i and a specific dimensionless coefficient 0 ≤ k_i ≤ 1 accounting for the specific contribution of this component to the increased mobility of the system. It is demonstrated that, for l > 0, the reference temperature is related to the “lubricant fraction” l through the reference temperature T_r,SiO2 of pure SiO₂.     

Comparative analysis of two methods of calculation of the orientation of domain walls in ferroelastics

Two types of domain-wall equations are analyzed: the equations derived by the Sapriel method and the equations obtained by interface matching of the thermal-expansion tensor. It is shown that, for W-type domain walls, these methods yield the same equations. For W′-type domain walls, the equations obtained by different methods coincide for proper ferroelastics and differ for improper ferroelastics.     

A review of measurement of thermophysical properties of silicon melt

Measurements of thermophysical properties of Si melt and supplementary study of X-ray scattering/diffraction by the authors' group were reviewed. The values obtained differed variously from those of literature. Density was 2–3% larger, surface tension 20–30% smaller, viscosity up to 40% larger, electrical conductivity 8% smaller, spectral emissivity more or less in good agreement with literature values, and thermal diffusivity a few percent larger. An anomalous density jump was found near the melting point. Surface tension and viscosity also showed anomaly. A strange time-dependent change of density was observed over 3 h after melting. X-ray analyses suggested a slight change in local atom ordering, but showed no sign of cluster formation. An addition of 0.1 at% gallium caused the density jump to disappear, while that of boron caused no change. An EXAFS study of the former melt indicated a strong interaction between Ga and Si atoms as if molecules of GaSi₃ existed. The implications of the measured properties are a possibility of soft-turbulence in an Si melt in a relatively large crucible, a more complicated manner of intake of oxygen depleted molten Si from the free surface region to underneath the growing crystal, and a relaxation of the melt after melting arising from trapped gas species.     

Generation of crystal structures of heteromolecular compounds by the method of discrete modeling of packings

Within the method of discrete modeling of packings, an algorithm of generation of possible crystal structures of heteromolecular compounds containing two or three molecules in the primitive unit cell, one of which has an arbitrary shape and the other (two others) has a shape close to spherical, is proposed. On the basis of this algorithm, a software package for personal computers is developed. This package has been approved for a number of compounds, investigated previously by X-ray diffraction analysis. The results of generation of structures of five compounds—four organic salts (with one or two spherical anions) and one solvate—are represented.