气相输运沉积制备化合物薄膜材料的研究进展

相比用于制备晶体材料的化学气相输运(Chemical Vapor Transport,CVT)方法,近空间气相输运沉积(Close-spaced Vapor Transport Deposition,CSVT)及气相输运沉积(Vapor Transport Deposition,VTD)方法不为人们所熟知.近几年来,气相输运沉积逐渐应用于锑基薄膜(Sb2 Se3、Sb2 S3及Sb2(Se,S)3)、锡基薄膜(SnS、SnS2)及铋基薄膜(Bi2 Se3、Bi2 Te3)等材料的制备,有可能成为一种重要的材料制备方法.本文综述了气相输运沉积用于化合物薄膜制备的研究进展,对其特点进行分析,并对其发展趋势进行了展望.     

Recent progress in chemical vapor deposition growth of two-dimensional transition metal dichalcogenides

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.     

Kinetics and mechanisms of surface reactions in epitaxial growth of Si from SiH4 and Si2H6

Surface science and kinetic modelling studies of the surface chemical mechanisms active during low pressure chemical vapor deposition (CVD) and chemical beam epitaxy (CBE) growth of Si from mono- and disilane are summarized. Time-of-flight direct recoiling (DR) is discussed as an in situ method to analyze the composition of the growth interface. Steady state measurements of surface hydrogen coverage (θ_H) are made by DR in situ during CBE Si growth from Si₂H₆ and SiH₄, and are illustrated here. Key results using other experimental methods are briefly discussed.     

大尺寸单晶金刚石薄膜的外延生长

用电子回旋共振等离子体增强的化学汽相沉积法, 在单晶硅衬底上外延生长出了近于100μm2的单晶金刚石薄膜.使用的原料气体是高纯的氢气和甲烷,生长前没有对衬底做划痕和研磨等预处理.生长中是把衬底放在ECR共振区,并施加了射频负偏压.研究证实,在单晶金刚石薄膜的外延中,硅衬底表面形成高质量结晶的β-SiC过渡层是外延生长金刚石单晶的关键条件;而射频负偏压对于β-SiC过渡层的形成是致关重要的条件.     

Controlled synthesis of barium chromate microcrystals

Barium chromate (BaCrO₄) microcrystals with various morphologies such as shuttle‐like, x‐shaped, ellipsoid, leaf‐like crystals were synthesized from aqueous solutions using poly (sodium 4‐styrenesulfonate) (PSS) as template agent at room temperature. The characterization results show that pH values and concentrations of reactants and PSS are important parameters in the morphology and size evolution of BaCrO₄. The possible formation mechanism of BaCrO₄ crystals with different morphologies was proposed. PSS complexes Ba²⁺ first, then affects the nucleation and crystallization process by interacting with the plane face of crystal, which finally results in various morphologies and sizes of crystals. In addition, the possible mechanism of photoluminescence (PL) spectra was also proposed.     

A detailed study of gold single crystal growth in a silica gel

Gold single microcrystals have been fabricated by electrochemical growth in a silica gel. Structural characterization of the single crystals by backscatter electron diffraction showed a preferred orientation of Au (1 1 1) and a minor orientation of Au (1 0 0). In addition, the influence of additives on the nucleation and growth of gold microcrystals has been studied. It was found that the inclusion of chemical additives in the growth solutions altered the characteristics of the gold crystals. Possible mechanisms for nucleation and growth of these crystals are discussed.     

Crystal growth in c direction and crystallographic polarity in ZnO crystals

The c-axis polarity of ZnO crystals growing in the c direction was investigated for crystals grown by chemical reaction in the vapor, by VLS mechanism and by chemical vapor deposition. In the initial growth stage ZnO crystals nucleate both in the +c and -c directions in each type of growth. In growth by chemical reaction in the vapor, a higher growth rate of the crystal in the +c direction results in dominant growth of large crystals in this direction. The difference in the growth rate is attributed to a higher effective surface energy of the Zn atom surface than that of the O atom surface. On the other hand, in VLS growth long whiskers and needles grow in both c directions. This fact indicates that the difference in the growth rates between the two c directions decreases in VLS growth.     

溶剂蒸汽退火辅助微距升华法制备C8-BTBT单晶

有机半导体单晶由于具有内部长程有序的分子排列结构、缺陷及晶界少等优点,表现出优异的光电性能,是实现有机半导体器件实用化的一种重要材料。目前,研究者们已经发展出多种可应用于有机单晶的生长方法,其中,微距升华法是一种可以在大气环境下采用蒸镀的方式制备有机微/纳单晶的方法。然而,当将这种方法应用于C8-BTBT时发现,由于分子的熔点较低,蒸镀得到的是分子直接从液态凝固为无定形/多晶的结构。在本工作中,通过使用溶剂蒸汽退火的方式对其进行后处理,成功地将这种无定形/多晶结构转化为分立的单晶。为了表征所得到的晶体形貌和结构,分别使用光学显微镜、X射线衍射和原子力显微镜等仪器对其进行了表征,发现所制备的晶体结构具备单晶的典型特征。     

Growth and characterization of titanium sesquioxide crystals

Ti₂O₃ crystals are grown by chemical transport reactions as platelets and by the tri-arc method as bulky crystals. The use of TiCl₄ as a transport agent is specifically well suited to this growth, as compared to TeCl₄ in use for the growth of higher oxides. The electrical properties as well as the thermodynamical ones are quite similar for the crystals grown by these two methods. However, definite differences are found in the EPR results. They can be reasonably ascribed to minimal thermal stresses in the crystals grown by chemical transport.     

Growth of ZnO bulk crystals: A review

A critical review is proposed of the different techniques of bulk growth of ZnO crystals for their use as a substrate in the homoepitaxial growth of this attractive compound. The crystals are assessed from their structural and electrical properties and from the structural properties and purity of homoepitaxial films grown on them by various techniques such as plasma-assisted molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, chemical vapor deposition, metalorganic chemical vapor epitaxy, liquid phase epitaxy.     

硒化铟材料的发展及其光电器件应用

自2004年发现石墨烯以来,二维材料以其丰富的带隙结构、独特的光电特性和无悬挂键的范德瓦耳斯表面等,极大地拓宽了半导体电子、光电子器件的设计维度。其中二维硒化铟材料成为最具竞争力的未来高迁移率光电子器件用候选材料,被诺贝尔奖获得者Andre Geim认为是“硅和石墨烯的‘黄金分割点’”。但人们对二维硒化铟材料的研究仅有不到十年的时间,对其制备及应用的认识仍然不足。本文综述了二维硒化铟材料及其光电器件的研究现状。另外,考虑到目前绝大多数二维硒化铟材料的研究是基于块状单晶体材料的机械剥离开始的,因此本文首先回顾了硒化铟晶体结构的认识及其制备方法的发展历程,在此基础上综述了二维硒化铟材料制备及其性能表征的前沿研究结果,探讨了器件结构、材料制备方法等因素对二维硒化铟场效应晶体管和光探测器电学输运特性的影响,最后分析了未来硒化铟材料及器件应用面临的机遇与挑战。     

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.     

利用界面调控制备二维有机半导体晶体及其机制研究

二维有机半导体晶体是利用分子间的范德瓦耳斯力进行自组装生长的单晶材料。本质上的单晶属性使其具备优异的电学特性。更重要的是,二维极限下增强的界面特性能够大幅调控器件行为,为构建多功能界面器件提供可能。此外,充分暴露的电荷输运沟道和极少的晶面内缺陷能够为研究本征的有机电子输运特性创造可能。目前,对于二维有机半导体晶体的生长工艺研究已经取得了较大的进展,但是从理论层面上研究二维晶体生长的自组装过程仍然十分匮乏。本工作利用添加剂辅助结晶技术成功制备出二维有机半导体晶体,并通过偏光显微镜和原子力显微镜对二维晶体进行了全面的表面形貌和结构表征。通过SEM结合EDS技术对关键的形核界面进行了结构和组成的表征以研究晶体生长的机制。研究结果表明:在添加剂界面上,生长材料能够稳定形核,并计算出添加剂构建的有利界面能够将形核势垒降低为SiO₂界面上的1/5。这项工作充分展现了生长界面对于晶体生长的关键作用,并从理论上揭示了界面的调控行为,为二维有机半导体晶体的生长工艺设计提供了可靠的思路。     

Crystal growth of the CdGa2(1‐x)Cr2xSe4 compounds by chemical transport method

Single crystals of CdGa_2(1‐x)Cr_2xSe₄ compounds for 0 ≤ x ≤ 1 have been grown by using the chemical vapor transport technique in a closed system. The transporting agent was CdCl₂ in a proportion of 0.75 mg/cc of capsule. The starting material was previously synthetized. The structural characterization on the crystals were done by powder x‐ray diffraction studies. The results show three different phases for various Cr concentration ranges: spinel structure for x ≥ 0.7, rombohedral for 0.6 ≥ x ≥ 0.5 and tetragonal for 0.4 ≥ x ≥ 0. That is, the chromium dilution in the CdCr₂Se₄ compound by Ga atoms produces very significant changes in the structural atomic arrangement. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth and characterization of the CMR compound La1.2(Sr,Ca)1.8Mn2O7

High-quality centimeter-sized single crystals of La_1.2Sr_1.8−yCa_yMn₂O₇ (0.0y0.2) were successfully grown using a floating zone method associated with an image furnace. We present the growth conditions together with a characterization of the single crystals by means of optical and electron microscopy, EDX and ICPAES analysis, DTA-TGA measurements and redox titration, X-ray powder diffraction, Laue X-ray back-reflection and neutron diffraction. We also stress the main aspects of the complex thermodynamical and kinetic behaviors of these compounds.     

Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Preparation and characterization of Ni-incorporated FeS2 single crystals

Nickel-incorporated FeS₂ single crystals with various Ni compositions of Fe_0.99S₂:Ni_0.01, Fe_0.98S₂:Ni_0.02, Fe_0.96S₂:Ni_0.04, and Fe_0.9S₂:Ni_0.1 were grown by chemical vapor transport (CVT) method using ICl₃ as a transport agent. Physical properties of the Ni-incorporated FeS₂ single crystals were characterized using X-ray diffraction, Raman spectroscopy, electrical conductivity, and photoconductivity (PC) measurements. By means of the analyses of the X-ray diffraction patterns, the whole series of Ni-doped FeS₂ single crystals were determined to be single-phase and isostructural. Raman spectroscopy of the Ni-doped FeS₂ crystals was carried out at room temperature. Raman resonant peaks of the Ni-doped FeS₂ crystals demonstrate an energy red-shift behavior with respect to the increase of the dopant densities. Conductivity measurements show the resistivity of the Ni-doped FeS₂ decreased as the doping concentration of Ni is increased. Nickel is an n-type dopant, which behaves like a donor level existed near the conduction band edge of the synthetic FeS₂. On the other hand, dopant effect of nickel on the synthetic FeS₂ also destroys the photoconductive sensitivity in the photoconductivity measurements.     

用热CVD法制备片状碳纳米材料的研究

采用阳极氧化法在草酸溶液中制备了孔径约为100nm的多孔氧化铝(AAO)模板。利用此模板在不负载任何催化剂的条件下,利用热CVD装置制备出片状碳纳米薄膜,并对此片状薄膜做了SEM,TEM显微观察和EDS能谱分析,对其形成条件和生长机理等方面做了探讨分析,为在氧化铝模板上生长包括管状、片状、棒状等形状的碳纳米材料提供了一定的借鉴意义。     

Method for HVPE growth of thick crack-free GaN layers

Twenty-five micrometer thick GaN was grown with hydride vapor phase epitaxy (HVPE) on metal-organic chemical vapor deposition (MOCVD) grown templates on sapphire substrates with the gallium treatment step (GTS) technique with varying buffer layer thickness. The samples are studied with atomic force microscopy (AFM), etching and scanning electron microscopy (SEM), photo-luminescence (PL), X-ray diffraction (XRD) and optical microscopy. The results show that the thickness of the buffer layer is not important for the layer quality once the growth in MOCVD starts to make the transition from 3D growth to 2D growth and HVPE continues in the same growth mode. We show that the MOCVD templates with GTS technique make excellent templates for HVPE growth, allowing growth of GaN without cracks in either sapphire or GaN.     

Growth and characterization of CdSe single crystals by modified vertical vapor phase method

Good quality, large single crystals of CdSe were grown by the modified growth method (i.e., vertical unseeded vapor phase growth with multi-step purification of the starting material in the same quartz ampoule without any manual transfer between the steps). Lower temperature gradients (8–9°C/cm) at the growth interface were used for the crystal growth. As-grown CdSe crystals was characterized by X-ray diffraction, scanning electron microscopy, energy dispersive analyzer of X-rays, high-resistance instrument measurement, and etch-pit observation. It is found that there are two cleavage faces of (1 0 0) and (1 1 0) orientations on the crystal, the resistivity is about 10⁸ Ω cm, and the density of etch pits is about 10^3–4/cm². The crystal was cut into wafers and was fabricated into detectors. The detectors were tested using an ²⁴¹Am radiation source. γ-ray spectra at 59.5 keV were obtained. The results demonstrated that the quality of the as-grown crystals was good. The crystals were useful for fabrication of room-temperature-operating nuclear radiation detectors. Therefore, the modified growth technique is a promising, convenient, new method for the growth of high-quality CdSe single crystals.