氮化镓单晶生长研究进展

氮化镓(GaN)作为第三代宽禁带半导体核心材料之一,具有高击穿场强、高饱和电子漂移速率、抗辐射能力强和良好的化学稳定性等优良特性,是制作宽波谱、高功率、高效率光电子、电力电子和微电子的理想材料.受制于氮化镓单晶衬底的尺寸、产能及成本的影响,当前的GaN基器件主要基于异质衬底(硅、碳化硅、蓝宝石等)制作而成,GaN单晶衬底的缺乏已成为制约GaN器件发展的瓶颈.近年来,国内外在GaN单晶衬底制备方面取得了较大的进展.本文综述了氮化镓单晶生长的最新进展,包括氢化物气相外延法、氨热法和钠助熔剂法的研究进展,分析了各生长方法面临的挑战与机遇,并对氮化镓单晶材料的发展趋势讲行了展望.     

氮化镓单晶的液相生长

氮化镓(GaN)具有高击穿场强、高饱和电子漂移速率、抗辐射能力强和良好的化学稳定性等优良特性,是制作宽波谱、高功率、高效率光电子、电力电子和微电子的理想衬底材料.除气相法(包括HVPE(氢化物气相外延)、MOCVD(金属有机化合物化学气相沉淀)、MBE(分子束外延))生长GaN单晶外,液相法(包括氨热法和助熔剂法)近几年在制备GaN单晶方面取得了较大的进展.本文介绍了氨热法和助熔剂法的生长原理、装备特点及生长习性;综述了两种液相生长方法的研究历程及研究进展,并对液相法生长GaN单晶的发展趋势及主要挑战进行了展望.     

氮化镓单晶衬底制备技术发展与展望

氮化镓(GaN)是第三代半导体材料中的典型代表.因其良好的物理化学性能与热稳定特性,是制作光电子器件及电力电子器件的理想材料.采用同质外延技术在GaN单晶衬底上制备GaN基器件是实现其高性能的根本途径.本文综述了GaN单晶衬底制备的氢化物气相外延技术、三卤化物气相外延技术、氨热法及助熔剂法(钠流法)的研究进展,并对未来可能的发展方向提出了展望.     

氢化物气相外延生长氮化镓单晶衬底的研究进展

氮化镓(GaN)晶体是制备蓝绿光激光器、射频微波器件以及电力电子等器件的理想衬底材料,在激光显示、5G通讯及智能电网等领域具有广阔的应用前景.目前市场上的氮化镓单晶衬底大部分都是通过氢化物气相外延(Hydride Vapor Phase Epitaxy,HVPE)方法生长制备的,在市场需求的推动下,近年来HVPE生长技术获得了快速的发展.本论文综述了近年来HVPE方法生长GaN单晶衬底的主要进展,主要内容包含HVPE生长GaN材料的基本原理、GaN单晶中的掺杂与光电性能调控、GaN单晶中的缺陷及其演变规律和GaN单晶衬底在器件中的应用.最后对HVPE生长方法的发展趋势进行了展望.     

Na助熔剂法生长氮化镓晶体的研究进展

以高质量GaN单晶基片作为衬底实现GaN的同质外延生长,是获得GaN半导体器件优异性能的基础.高质量GaN单晶基片的缺乏已成为国际范围制约GaN器件发展的瓶颈.在GaN体单晶的几种生长方法中,由于Na助熔剂法的生长条件相对温和且成本相对较低,近年来发展较快.本文从Na助熔剂法的原理、生长工艺、助熔剂种类以及得到晶体尺寸和质量等几方面进行了综述,分析了目前Na助熔剂法生长GaN单晶中的技术问题并提出了进一步研究的一些建议.     

基于钠助熔剂法的GaN单晶生长研究进展

宽禁带氮化镓(GaN)材料以其独特的性质和应用前景成为国内外研究的热点,高质量GaN单晶衬底的制备是获得性能优异的光电子器件和功率器件的基础。钠助熔剂法生长条件温和,易获得高质量、大尺寸的GaN单晶,是一种具有广阔商业化前景的GaN单晶生长方法。钠助熔剂法自20世纪90年代末期被发明以来,经过20多年的发展,钠助熔剂法生长的晶体在尺寸与质量上都取得了长足的进步。本文从晶体生长原理和关键工艺(籽晶选择、温度梯度以及添加剂)等方面综述了钠助熔剂法生长GaN单晶研究进展,并对其面临的挑战和未来发展趋势进行了展望。     

蓝宝石衬底材料的研究及应用进展

蓝宝石因为其生产技术成熟、稳定性好、性价比高而被广泛应用于光电领域,成为GaN基光电器件的主要衬底材料.传统的蓝宝石衬底生长GaN薄膜存在许多问题,如由晶格常数不同产生的晶格失配、热应力失配等,且GaN薄膜结晶质量较差、光线提取效率低.介绍了图形化蓝宝石衬底技术在制作GaN基LED器件中的应用,比较了几种图形化衬底对LED的发光性能的影响.在图形化蓝宝石衬底上采用PVD法生长AlN薄膜,可以降低GaN薄膜的螺旋位错和刃位错、提高MOCVD生长效率、显著提高设备利用率.另外,介绍了蓝宝石衬底在SOS领域的应用,列出了SOS工艺对蓝宝石衬底的具体要求.蓝宝石作为一种重要的衬底材料,未来的发展前景会更加广阔.     

异质衬底上HVPE法生长GaN厚膜的研究进展

氮化镓基(GaN)光电器件的快速发展,对GaN的质量提出更高的要求,同质外延可以避免由于失配引起的缺陷,厚膜生长是解决GaN体材料生长困难的有效手段.氢化物气相外延(HVPE)是目前最普遍的制备氮化镓厚膜的方法.衬底对于GaN厚膜的影响不可忽视,本文总结了在蓝宝石、碳化硅和铝酸锂衬底上制备GaN厚膜的研究进展,讨论了今后的研究方向.     

GaN体单晶的氨热生长及应力调控

采用氨热法在碱性条件下生长了GaN体单晶,SEM照片显示晶体表面有大量裂纹.用拉曼光谱测量GaN晶体的E2 (high)声子拉曼峰,结果表明晶体内部应力波动较大.通过减小温度梯度、籽晶优选及降温程序优化后,得到了无裂纹的氮化镓晶体,(002)和(102)的X射线摇摆曲线FWHM分别为48 arcsec和54 arcsec,显微拉曼光谱表明经过工艺优化后的晶体应力显著降低,应力的来源主要为生长过程中杂质的引入.     

不同生长方向的GaN纳米线的可控制备与性能表征

采用化学气相沉积法,通过改变催化剂和衬底,以Ga2 O3和GaN的混合粉末为镓源制备出了不同生长方向的GaN纳米线,制备的平躺于衬底的GaN纳米线的直径约为60 nm,长度为10 μm到30 μm之间.垂直于衬底的GaN纳米线阵列的直径约为300 nm,长度约为5μm.使用扫描电子显微镜(SEM)、X射线衍射(XRD)、光致发光谱(PL)和透射电子显微镜(TEM)对样品进行了分析表征,结果表明所得样品为六方纤锌矿结构的GaN单晶纳米线.通过改变催化剂和衬底等生长条件,研究了衬底和催化剂对纳米线生长方向的影响,为以后的大量制备以及纳米器件的制作提供了依据.     

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.     

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.     

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.     

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.