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Molecular beam epitaxy as a growth technique for achieving free-standing zinc-blende GaN and wurtzite AlxGa1-xN 分子束外延是制备独立锌-闪锌矿GaN和纤锌矿AlxGa1-xN的生长技术
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2017-06-01 DOI: 10.1016/j.pcrysgrow.2017.04.001
S.V. Novikov, A.J. Kent, C.T. Foxon
<div><p>Currently there is a high level of interest in the development of ultraviolet (UV) light sources for solid-state lighting, optical sensors, surface decontamination and water purification. III-V semiconductor UV LEDs are now successfully manufactured using the AlGaN material system; however, their efficiency is still low. The majority of UV LEDs require Al<sub>x</sub>Ga<sub>1-x</sub>N layers with compositions in the mid-range between AlN and GaN. Because there is a significant difference in the lattice parameters of GaN and AlN, Al<sub>x</sub>Ga<sub>1-x</sub>N substrates would be preferable to those of either GaN or AlN for many ultraviolet device applications. However, the growth of Al<sub>x</sub>Ga<sub>1-x</sub>N bulk crystals by any standard bulk growth techniques has not been developed so far.</p><p>There are very strong electric polarization fields inside the wurtzite (hexagonal) group III-nitride structures. The charge separation within quantum wells leads to a significant reduction in the efficiency of optoelectronic device structures. Therefore, the growth of non-polar and semi-polar group III-nitride structures has been the subject of considerable interest recently. A direct way to eliminate polarization effects is to use non-polar (001) zinc-blende (cubic) III-nitride layers. However, attempts to grow zinc-blende GaN bulk crystals by any standard bulk growth techniques were not successful.</p><p>Molecular beam epitaxy (MBE) is normally regarded as an epitaxial technique for the growth of very thin layers with monolayer control of their thickness. In this study we have used plasma-assisted molecular beam epitaxy (PA-MBE) and have produced for the first time free-standing layers of zinc-blende GaN up to 100<!--> <!-->μm in thickness and up to 3-inch in diameter. We have shown that our newly developed PA-MBE process for the growth of zinc-blende GaN layers can also be used to achieve free-standing wurtzite Al<sub>x</sub>Ga<sub>1-x</sub>N wafers. Zinc-blende and wurtzite Al<sub>x</sub>Ga<sub>1-x</sub>N polytypes can be grown on different orientations of GaAs substrates - (001) and (111)B respectively. We have subsequently removed the GaAs using a chemical etch in order to produce free-standing GaN and Al<sub>x</sub>Ga<sub>1-x</sub>N wafers. At a thickness of ∼30<!--> <!-->µm, free-standing GaN and Al<sub>x</sub>Ga<sub>1-x</sub>N wafers can easily be handled without cracking. Therefore, free-standing GaN and Al<sub>x</sub>Ga<sub>1-x</sub>N wafers with thicknesses in the 30–100<!--> <!-->μm range may be used as substrates for further growth of GaN and Al<sub>x</sub>Ga<sub>1-x</sub>N-based structures and devices.</p><p>We have compared different RF nitrogen plasma sources for the growth of thick nitride Al<sub>x</sub>Ga<sub>1-x</sub>N films including a standard HD25 source from Oxford Applied Research and a novel high efficiency source from Riber. We have investigated a wide range of the growth rates from 0.2 to 3<!--> <!-->µm/h. The us
目前,人们对开发用于固态照明、光学传感器、表面净化和水净化的紫外光源非常感兴趣。III-V型半导体UV led现已成功使用AlGaN材料系统制造;然而,它们的效率仍然很低。大多数UV led需要AlxGa1-xN层,其成分介于AlN和GaN之间的中间范围。由于GaN和AlN的晶格参数存在显著差异,因此在许多紫外器件应用中,AlxGa1-xN衬底将优于GaN或AlN衬底。然而,目前还没有任何标准的体生长技术来生长AlxGa1-xN体晶体。纤锌矿(六方)iii族氮化物结构内部存在很强的电极化场。量子阱中的电荷分离导致光电器件结构效率的显著降低。因此,非极性和半极性iii族氮化物结构的生长已成为近年来人们非常感兴趣的课题。消除极化效应的一种直接方法是使用非极性(001)锌-闪锌矿(立方)iii型氮化物层。然而,试图通过任何标准的体生长技术生长锌掺杂氮化镓体晶体都不成功。分子束外延(MBE)通常被认为是一种生长极薄层的外延技术,其厚度由单层控制。在这项研究中,我们使用了等离子体辅助分子束外延(PA-MBE),并首次生产出了厚度达100 μm、直径达3英寸的独立锌掺杂氮化镓层。我们已经证明,我们新开发的PA-MBE工艺用于生长锌掺杂氮化镓层,也可以用于获得独立的纤锌矿AlxGa1-xN晶圆。锌闪锌矿和纤锌矿AlxGa1-xN多型可以分别生长在GaAs衬底-(001)和(111)B的不同取向上。我们随后使用化学蚀刻去除GaAs,以生产独立的GaN和AlxGa1-xN晶圆。在~ 30µm的厚度下,独立的GaN和AlxGa1-xN晶圆可以很容易地处理而不会破裂。因此,厚度在30-100 μm范围内的独立GaN和AlxGa1-xN晶圆可以用作进一步生长GaN和AlxGa1-xN基结构和器件的衬底。我们比较了用于生长厚氮化AlxGa1-xN薄膜的不同射频氮等离子体源,包括来自牛津应用研究公司的标准HD25源和来自Riber的新型高效源。我们研究了从0.2到3µm/h的生长速率范围。高效氮射频等离子体源的使用使PA-MBE成为一种潜在可行的商业工艺,因为独立薄膜可以在一天内完成。我们的研究结果表明,MBE可能在几个重要领域与其他iii族氮化物体生长技术竞争,包括生产独立的锌-铀矿(立方)(Al)GaN和独立的纤锌矿(六方)AlGaN。
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引用次数: 18
Spray pyrolysis deposition of undoped SnO2 and In2O3 films and their structural properties 喷雾热解沉积未掺杂SnO2和In2O3薄膜及其结构性能
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2017-02-01 DOI: 10.1016/j.pcrysgrow.2016.12.001
G. Korotcenkov, B.K. Cho

In this paper the results of structural analysis of the SnO2 and In2O3 films deposited by spray pyrolysis are presented. The main goals of this analysis are summarizing the results obtained in this field, highlighting a correlation between parameters of film deposition and the material structure and formulating some general regularities, typical for metal oxides. Peculiarities and mechanisms of pyrosol deposition as well as advantages and disadvantages of this technology for deposition of the films with required parameters were also discussed. It is shown that this technology has great potential for controlling structural parameters of metal oxides such as thickness, the grain size, texturing, roughness, the grain faceting and the porosity.

本文介绍了喷雾热解法制备SnO2和In2O3薄膜的结构分析结果。本分析的主要目的是总结在该领域取得的成果,强调薄膜沉积参数与材料结构之间的相关性,并提出一些典型的金属氧化物的一般规律。讨论了热溶胶沉积技术的特点和机理,以及热溶胶沉积技术的优缺点。结果表明,该技术在控制金属氧化物的厚度、晶粒尺寸、织构、粗糙度、晶粒饰面和孔隙率等结构参数方面具有很大的潜力。
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引用次数: 32
Atomic layer deposition of high-k dielectrics on III–V semiconductor surfaces 高k介电体在III-V型半导体表面的原子层沉积
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-12-01 DOI: 10.1016/j.pcrysgrow.2016.11.001
Theodosia Gougousi

The goal of this article is to provide an overview of the state of knowledge regarding the Atomic Layer Deposition (ALD) of metal oxides on III–V semiconductor surfaces. An introduction to ALD, the band structure, various defects present on the III–V surface and how they relate to Fermi level pinning are discussed. Surface passivation approaches are examined in detail in conjunction with experimental and computational results. The “interface clean-up” reaction that leads to the formation of a sharp gate oxide/semiconductor interface is related to the surface chemistry and the transport of the surface oxides through the growing dielectric film. Finally, the deposition of metal oxides on semiconductors is discussed in the context of interface quality and some examples of devices using III–V channels and ALD metal oxides are given.

本文的目的是概述有关III-V半导体表面金属氧化物的原子层沉积(ALD)的知识状态。介绍了ALD、能带结构、III-V表面存在的各种缺陷以及它们与费米能级钉钉的关系。结合实验和计算结果对表面钝化方法进行了详细的研究。“界面清理”反应导致了一个尖锐的栅极氧化物/半导体界面的形成,这与表面化学和表面氧化物通过生长的介电膜的传输有关。最后,从界面质量的角度讨论了金属氧化物在半导体上的沉积,并给出了一些使用III-V通道和ALD金属氧化物的器件的例子。
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引用次数: 27
Single crystal growth by the traveling solvent technique: A review 流动溶剂单晶生长技术的研究进展
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-12-01 DOI: 10.1016/j.pcrysgrow.2016.03.001
S.M. Koohpayeh

A description is given of the traveling solvent technique, which has been used for the crystal growth of both congruently and incongruently melting materials of many classes of intermetallic, chalcogenide, semiconductor and oxide materials. The use of a solvent, growth at lower temperatures and the zoning process, that are inherent ingredients of the method, can help to grow large, high structural quality, high purity crystals. In order to optimize this process, careful control of the various growth variables is imperative; however, this can be difficult to achieve due to the large number of independent experimental parameters that can be grouped under the broad headings ‘growth conditions’, ‘characteristics of the material being grown’, and ‘experimental configuration, setup and design’. This review attempts to describe the principles behind the traveling solvent technique and the various experimental variables. Guidelines are detailed to provide the information necessary to allow closer control of the crystal growth process through a systematic approach. Comparison is made between the traveling solvent technique and other crystal growth methods, in particular the more conventional stationary flux method. The use of optical heating is described in detail and successful traveling solvent growth by optical heating is reported for the first time for crystals of Tl5Te3, Cd3As2, and FeSc2S4 (using Te, Cd and FeS fluxes, respectively).

本文介绍了移动溶剂技术,该技术已被用于多种金属间化合物、硫族化合物、半导体和氧化物材料的全等和非全等熔化材料的晶体生长。使用溶剂,在较低温度下生长和分区过程,这是该方法的固有成分,可以帮助生长大型,高结构质量,高纯度的晶体。为了优化这一过程,必须仔细控制各种生长变量;然而,这可能很难实现,因为大量独立的实验参数可以归为“生长条件”、“生长材料的特性”和“实验配置、设置和设计”。本文综述了流动溶剂技术的原理和各种实验变量。详细的指导方针提供了必要的信息,以便通过系统的方法对晶体生长过程进行更密切的控制。对流动溶剂法和其他晶体生长方法进行了比较,特别是比较传统的固定通量法。详细描述了光学加热的使用,并首次报道了Tl5Te3、Cd3As2和FeSc2S4晶体(分别使用Te、Cd和FeS助焊剂)通过光学加热成功地生长行溶剂。
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引用次数: 26
Recent progress in chemical vapor deposition growth of two-dimensional transition metal dichalcogenides 二维过渡金属二硫族化合物化学气相沉积生长研究进展
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-09-01 DOI: 10.1016/j.pcrysgrow.2016.06.002
Swee Liang Wong, Hongfei Liu, Dongzhi Chi

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) have received significant attention recently due to their unique properties such as a transition from indirect to direct band gap when thinned down to a monolayer and also valley-dependent photoluminescence. In addition, being a semiconductor with considerable mobility, it has been touted as a candidate in next generation electronics. However, a major hurdle to its implementation is the difficulty in producing large areas of these 2D TMDCs with well-defined thicknesses. In this review, we will first introduce the basic properties as well as the various synthesis methods of 2D TMDCs. Focus will be placed on recent advances in chemical vapor deposition (CVD) growth as they currently yield the largest areas. Obstacles present in CVD growth will be presented and existing solutions to them will be discussed in tandem with current characterization methods for evaluation of crystal quality. Through our presentation on the latest approaches to issues in CVD growth, we hope to present the readers a perspective on recent developments as well as providing an outlook on the future of CVD growth of TMDCs.

二维(2D)过渡金属二硫族化合物(TMDCs)由于其独特的性质,如从间接带隙到直接带隙的转变,当薄化到单层时,以及谷依赖的光致发光,最近受到了极大的关注。此外,由于具有相当大的移动性,它被吹捧为下一代电子产品的候选者。然而,其实施的一个主要障碍是难以生产具有良好厚度的大面积2D TMDCs。本文首先介绍了二维TMDCs的基本性质以及各种合成方法。重点将放在化学气相沉积(CVD)增长的最新进展上,因为它们目前产量最大。将介绍CVD生长中存在的障碍,并讨论现有的解决方案,以及当前用于评估晶体质量的表征方法。通过我们对CVD增长问题的最新方法的介绍,我们希望向读者展示最近发展的观点,并对TMDCs的CVD增长的未来提供展望。
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引用次数: 56
Crystallization behavior of solid solutions from aqueous solutions: An environmental perspective 水溶液中固溶体的结晶行为:环境视角
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-09-01 DOI: 10.1016/j.pcrysgrow.2016.05.001
Manuel Prieto , Frank Heberling , Rosa M. Rodríguez-Galán , Felix Brandt

Aqueous–solid solution (AQ-SS) processes have garnered increasing attention from geochemists and environmental engineers because they play major roles in the fate and transport of elements in Earth surface environments. The reasons for this interest include: (i) the primary crystallization of minerals from multicomponent aqueous solutions leads to the formation of solid solutions in which different ions are substituted for one another in equivalent structural positions; (ii) the interaction between pre-existing minerals and water frequently yields surface precipitation and dissolution–recrystallization processes in which such substituting ions redistribute to adapt to new physicochemical conditions; (iii) the concentrations of specific minor elements in biogenic and abiogenic minerals have been shown to correlate with various parameters characterizing the growth environment (temperature, pH, nutrient levels, salinity, etc.) and the corresponding compositional signatures can be powerful tools in reconstructing the past from the sedimentary record; (iv) the aqueous concentration of heavy metals and other harmful ions can be significantly reduced by their incorporation into the structure of suitable host minerals and as such a ‘reduction of solubility’ can be exploited as a remediation strategy or used to design engineered barriers for the retention of metals, radionuclides, and other industrially generated inorganic wastes. In this review, the thermodynamics driving of AQ-SS processes is presented using examples of environmentally-relevant systems. The reaction pathways in AQ-SS processes depend not only on thermodynamic factors but also on kinetic and mechanistic effects, which operate at different scales in space and time. Examples of such effects include non-equilibrium ion partitioning, surface passivation, and compositional (sectorial, concentric, oscillatory) zoning. Finally, we discuss the contribution of both state-of-the-art characterization techniques and molecular simulation methods for the development of predictive models.

水-固溶(AQ-SS)过程在地球表面环境中对元素的命运和迁移起着重要作用,因此越来越受到地球化学家和环境工程师的关注。引起这种兴趣的原因包括:(1)多组分水溶液中矿物的初次结晶导致形成固溶体,其中不同的离子在等效结构位置上相互取代;(ii)先前存在的矿物质和水之间的相互作用经常产生表面沉淀和溶解-再结晶过程,在此过程中,这些取代离子重新分配以适应新的物理化学条件;(iii)生物和非生物矿物中特定微量元素的浓度已被证明与表征生长环境的各种参数(温度、pH、营养水平、盐度等)相关,相应的成分特征可以作为从沉积记录中重建过去的有力工具;(iv)重金属和其他有害离子的水中浓度可以通过将其掺入合适的宿主矿物结构中而显著降低,因此,“降低溶解度”可以作为一种补救策略加以利用,或用于设计工程屏障,以保留金属、放射性核素和其他工业产生的无机废物。本文以环境相关系统为例,介绍了AQ-SS过程的热力学驱动。AQ-SS过程的反应路径不仅取决于热力学因素,还取决于动力学和机理效应,它们在不同的空间和时间尺度上起作用。这种效应的例子包括非平衡离子分配、表面钝化和组成(扇形、同心、振荡)分区。最后,我们讨论了最先进的表征技术和分子模拟方法对预测模型发展的贡献。
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引用次数: 44
Spring and parachute: How cocrystals enhance solubility 弹簧和降落伞:共晶如何提高溶解度
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-09-01 DOI: 10.1016/j.pcrysgrow.2016.07.001
Dhara D. Bavishi, Chetan H. Borkhataria

This article is intended to combine literature on cocrystallization – a tool for enhancing the solubility and for improving the physicochemical properties of an API (an API is the molecule which is responsible for providing the therapeutic effect) with special emphasis on the mechanism responsible for the same. The pharmaceutical industries are witnessing a developing crisis in the process of drug development due to the increasing cost of their R&D departments, the failure of some blockbuster drug candidates exhibiting poor aqueous solubility and the unavailability of newer molecules because of patent limitations. Cocrystallization is an emerging approach to improve solubility, dissolution profile, bioavailability, and other physicochemical and mechanical properties of an API. A pharmaceutical cocrystal is now a new epitome which enables the use of a wide range of active pharmaceutical ingredients without the need to form or break the covalent bonds. The prime focus of this review article is the mechanism on how cocrystals have a solubility advantage over the amorphous form. This review also provides a brief introduction to the nature of cocrystals, their role, principles of crystal engineering and also highlights the nature of supramolecular synthons which are present in cocrystals.

本文旨在结合有关共结晶的文献-一种提高溶解度和改善原料药理化性质的工具(原料药是负责提供治疗效果的分子),并特别强调其机制。制药行业正在目睹药物开发过程中的危机,这是由于研发部门的成本不断增加,一些重量级候选药物由于水溶性差而失败,以及由于专利限制而无法获得新分子。共结晶是一种新兴的改善原料药溶解度、溶解谱、生物利用度和其他物理化学和机械性能的方法。药物共晶现在是一种新的缩影,它可以在不形成或破坏共价键的情况下使用广泛的活性药物成分。这篇综述文章的主要焦点是机制,如何共晶具有溶解度优势的非晶形式。本文还简要介绍了共晶的性质、作用、晶体工程原理,并重点介绍了共晶中存在的超分子合成子的性质。
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引用次数: 136
Development of GaN-based blue LEDs and metalorganic vapor phase epitaxy of GaN and related materials 氮化镓基蓝色led及氮化镓金属有机气相外延及相关材料的发展
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-06-01 DOI: 10.1016/j.pcrysgrow.2016.04.006
Hiroshi Amano

This article combines two papers, “Nobel Lecture: Growth of GaN on sapphire via low-temperature deposited buffer layer and realization of p-type GaN by Mg doping followed by low-energy electron beam irradiation,” Rev. Mod. Phys., 87 (2015) 1133, and “MOCVD of nitrides,” Handbook of Crystal Growth Second Edition, Volume III, Part A, Chapter 16, Elsevier, 683–704, 2015. For more detailed information, please read the two original papers.

本文结合了两篇论文,“诺贝尔奖演讲:低温沉积缓冲层在蓝宝石上生长GaN和通过Mg掺杂和低能电子束辐照实现p型GaN”,Mod. Phys。“氮化物的MOCVD”,Handbook of Crystal Growth Second Edition, Volume III, Part A, Chapter 16, Elsevier, 683 - 704,2015。欲了解更多详细信息,请阅读两篇论文原文。
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引用次数: 27
Introduction to the BCF theory BCF理论简介
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-06-01 DOI: 10.1016/j.pcrysgrow.2016.04.002
Makio Uwaha

Sixty-five years have passed since Burton, Cabrera and Frank (BCF) published the seminal paper (W. K. Burton, N. Cabrera and F. C. Frank, Phil. Trans. Royal Soc. London, 243 (1951), 299). Since then, the paper provided us the basic scheme of growth of crystals. In this lecture, the BCF theory is introduced for beginners as the basis of modern crystal growth study. The BCF theory explained the growth of facets with the help of screw dislocations. It introduced the concept of the roughening transition, which distinguishes the crucial difference of lateral growth of facets and normal growth of round surfaces.

自Burton, Cabrera和Frank (BCF)发表开创性论文(W. K. Burton, N. Cabrera和F. C. Frank, Phil)以来,已经过去了65年。反式。皇家Soc。伦敦,243(1951),299)。从那时起,论文为我们提供了晶体生长的基本方案。本讲座为初学者介绍BCF理论作为现代晶体生长研究的基础。BCF理论借助螺位错解释了晶面的生长。它引入了粗化过渡的概念,区分了切面的横向生长和圆形表面的法向生长的关键区别。
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引用次数: 19
Assembling interferometers and in-situ observation of ambient environments and solid–liquid interfaces 组装干涉仪和现场观测环境和固液界面
IF 5.1 2区 材料科学 Q1 CRYSTALLOGRAPHY Pub Date : 2016-06-01 DOI: 10.1016/j.pcrysgrow.2016.04.022
Yuki Kimura , Kenta Murayama , Tomoya Yamazaki , Takao Maki

The principle of interferometers and its applicability to our research on crystal growth can be understood through assembling interferometers. In particular, practical skills such as techniques for assembling interferometers and selecting optical components, which are not covered by general textbooks, can be learned.

通过组装干涉仪,可以了解干涉仪的原理及其在晶体生长研究中的适用性。特别是实用技能,如组装干涉仪和选择光学元件的技术,一般的教科书没有涵盖,可以学习。
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引用次数: 0
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Progress in Crystal Growth and Characterization of Materials
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