石墨烯上远程外延Ge纳米柱

远程外延能够突破传统外延中晶格匹配、热匹配等限制,近年来得到了广泛的关注。Ⅲ-Ⅴ族和Ⅲ-氮化合物半导体已经成功在石墨烯上远程外延生长,但Ⅳ族半导体的远程外延很少被报道。本文首次借助于分子束外延技术在石墨烯上远程外延制备了半导体Ge纳米柱,研究了其生长特性及剥离转移。结果表明:远程外延生长的Ge纳米柱为[111]c晶向,集中分布在石墨烯的褶皱以及衬底Cu-Ni原子台阶处;随着生长温度的提高,Ge纳米柱的高度和密度逐渐下降,但直径差别不大,约为55~65 nm;此外,自组织生长的Ge纳米棒显示无应变的生长状态;引入少量Sn形成GeSn纳米柱,能够显著提升Ge纳米柱的面密度。同时,生长的Ge纳米柱可实现剥离,有望实现异质集成,应用于先进光电子器件等领域。     

Si–Ge–Sn alloys: From growth to applications

In this review article, we address key material parameters as well as the fabrication and application of crystalline GeSn binary and SiGeSn ternary alloys. Here, the transition from an indirect to a fundamental direct bandgap material will be discussed. The main emphasis, however, is put on the Si–Ge–Sn epitaxy. The low solid solubility of α-Sn in Ge and Si of below 1 at.% along with the large lattice mismatch between α-Sn (6.489 Å) and Ge (5.646 Å) or Si (5.431 Å) of about 15% and 20%, respectively, requires non-equilibrium growth processes. The most commonly used approaches, i.e. molecular beam epitaxy (MBE) and chemical vapor deposition (CVD), will be reviewed in terms of crucial process parameters, structural as well as optical quality and employed precursor combinations including Germanium hydrides, Silicon hydrides and a variety of Sn compounds like SnD₄, SnCl₄ or C₆H₅SnD₃. Special attention is devoted to the growth temperature window and growth rates being the most important growth parameters concerning the substitutional incorporation of Sn atoms into the Ge diamond lattice. Furthermore, the mainly CVD-driven epitaxy of high quality SiGeSn ternary alloys, allowing the decoupling of band engineering and lattice constant, is presented. Since achieving fundamental direct bandgap Sn-based materials strongly depends on the applied strain within the epilayers, ways to control and modify the strain are shown, especially the plastic strain relaxation of (Si)GeSn layers grown on Ge.Based on recently achieved improvements of the crystalline quality, novel low power and high mobility GeSn electronic and photonic devices have been developed and are reviewed in this paper. The use of GeSn as optically active gain or channel material with its lower and potentially direct bandgap compared to fundamentally indirect Ge (0.66 eV) and Si (1.12 eV) provides a viable solution to overcome the obstacles in both fields photonics and electronics. Moreover, the epitaxial growth of Sn-based semiconductors using CMOS compatible substrates on the road toward a monolithically integrated and efficient group IV light emitter is presented.     

Investigation of 3C-SiC growth on Si(111) by vapor–liquid–solid transport using a SiGe liquid phase

The crystal growth of 3C-SiC onto silicon substrate by Vapor–Liquid–Solid (VLS) transport, where a SiGe liquid phase is fed with propane, has been investigated. Three sample configurations were used. In a preliminary approach, the VLS growth of SiC was conducted directly onto Si substrate using a Ge film as liquid catalyst. It led to the growth of a thick continuous SiC polycrystalline layer which was floating over a SiGe alloy located between the silicon substrate and the topping SiC layer. In the second configuration, a thin seeding layer of 3C-SiC grown by chemical vapor deposition (CVD) was used and the VLS growth was localized using a SiO₂ mask. The liquid phase was a CVD deposited SiGe alloy. The growth of a few hundred nanometers thick 3C-SiC epitaxial layer was demonstrated but the process was apparently affected by the presence of the oxide which was dramatically etched at the end. In the last configuration, the silicon substrate was patterned down to 10 μm and a thin seeding layer of 3C-SiC was grown by CVD onto this patterned substrate. The liquid phase was again a CVD deposited SiGe alloy. In this last configuration, the presence of epitaxial SiC was evidenced but it grew as trapezoidal islands instead of an uniform layer.     

A study of structural perfection of interfaces in Si/SiGe superlattices

A complex investigation into the structural perfection of the Si/SiGe superlattices grown by molecular-beam epitaxy at different temperatures of the Si substrate has been carried out by high-resolution X-ray diffraction analysis, secondary ion mass spectrometry (SIMS), and transmission electron microscopy (TEM). It is demonstrated that the combination of these methods makes it possible to describe in sufficient detail the distributions of the strains and Ge concentrations in the elastically strained superlattices and also to evaluate the sharpness of the layer interfaces. It is shown that the densitometry of electron microscope images of the superlattice cross-sections permits characterization of the relative sharpness of the layer interfaces and a qualitative representation of the Ge distribution throughout the thickness of the SiGe layers.     

Comparison of MOVPE grown GaAs solar cells using different substrates and group-V precursors

We have investigated the influence of substrate type (GaAs vs. germanium) and of group-V precursor (AsH₃ vs. TBAs) on the epitaxial quality of (In)(Al)GaAs layers. We evaluated these layers in terms of morphology, background contamination and doping characteristics. For final benchmarking of the individually optimised processes, we produced p-on-n single junction GaAs solar cells and compared their relative performance. This type of device is an excellent performance monitor for epitaxial layers as the fundamental operating mechanism is drift of minority carriers. The solar cell grown with TBAs on a germanium-substrate has a conversion efficiency under the AM1.5 solar spectrum, which compares favourably with the highest reported value for a p-on-n GaAs solar cell on Ge (Prog. Photovolt. Res. Appl. 8 (2000) 377).     

Strain dependent growth of silicon on Ge/Si–C heterostructures

We report on structural investigations of strain dependent growth of Si on Ge/Si–C heterostructures. Very small islands of Ge were obtained by using a little C precoverage before the Ge deposition. These islands are visualized by scanning tunneling microscopy (STM) and the subsequent Si epitaxy is pursued. STM pictures taken upon some monolayers of Si epitaxy reveal an inhomogeneous growth mode, which leads to ditch like rings formed around the islands. Pictures of the following Si deposition suggest a strain dependent surface diffusion of Si until sufficient material has been deposited which then flattens the surface resulting in perfect epitaxial structures.     

陶瓷衬底上多晶硅薄膜太阳电池研究进展

多晶硅薄膜太阳电池在提高电池效率和大幅度降低成本等方面具有极大潜力.陶瓷材料是高温路线制备多晶硅薄膜电池最常用的衬底材料之一.本文介绍了陶瓷衬底上多晶硅薄膜的制备方法及其电池结构和相关工艺,最后综述了当前该领域的最新研究进展.     

Germanium films with strong in-plane and out-of-plane texture on flexible,randomly textured metal substrates

High efficiencies have been achieved in photovoltaic cells based on III–V compounds grown on single crystal germanium substrates. Since the size of these substrates is limited and their cost is very high, such III–V photovoltaics have not found widespread terrestrial use. The objective of this work is to develop highly textured, epitaxial germanium thin films on inexpensive substrates suitable for roll-to-roll continuous processing to serve as templates for III–V compounds. Germanium films with a high degree of in-plane and out-of plane texture have been demonstrated on randomly textured, flexible nickel alloy substrates by epitaxial growth on template films made by ion beam-assisted deposition (IBAD). In order to achieve epitaxial growth, an intermediate layer of CeO₂ was found to be required between the IBAD MgO template and the Ge film. Our study shows that structural match between Ge and the underlying oxide layer is the key to epitaxial growth. Room temperature optical bandgap of the Ge films was identified at 0.67 eV suggesting minimal residual strain in the film. Refraction index and extinction coefficient values of the epitaxial Ge film were found to match well with that measured from a reference Ge single crystal.     

Isothermal liquid phase epitaxy

The epitaxial growth of semiconductor solid solutions from a liquid phase appears to be possible under stringent isothermal conditions. The driving force of such epitaxy can be liquid phase supersaturation caused by isothermal mixing of liquidus solutions or supersaturation in the solid phase resulting from thermodynamic nonequilibrium of the substrate and the solution. The feature of the method is that film growth requires no control temperature and time of crystallization while the film properties are set by the initial process conditions. Isothermal liquid phase epitaxy (ILPE) makes it possible to form hyperfine films whose component distribution can be controlled.ILPE inevitably starts on the initial stage of a common liquid phase epitaxy, therefore this phenomenon must be taken into consideration. The above mentioned factors account for practical importance of ILPE technique for modern electronics.The present paper reviews the mechanism as well as the main regularities of ILPE for A³B⁵ ternary alloys.     

Modifications of epitaxy in evaporated films by electric charge effects

Modifications of epitaxy in Ge, Si, CdS, β-Sn, and α-Fe films, 100–600 Å in thickness, evaporated onto air-cleaved and vacuum-cleaved (001) NaCl substrates under electron bombardment (∽10¹⁵ electrons/cm² sec, at 200–400 V) or an electric field (dc 100–300 V/cm) applied to the substrate surface were investigated by reflection electron diffraction, transmission electron microscopy and selected-area diffraction. Results indicated that epitaxial temperatures of Ge and Si films were considerably lowered, and a monocrystalline β-Sn film was produced by the application of electron bombardment. The application of electric field resulted in the formation of an epitaxial cubic CdS phase, and a single orientation in an α-Fe film. These results are discussed in terms of current speculation concerning the electric charge effects on alkali halide substrates.     

Reactor problems in modified chemical vapour deposition (i). the collapse of quartz glass tubes

In the case of the so-called “Modified Chemical Vapour Deposition” for the preparation of optical fiber preforms, the quartz glass reactor is identical with the substrate. Therefore, the knowledge of reactor properties such as the viscous flow of the tubes (collapse) and the heat transport through the wall are especially important for a successful control of the process. As a first step, an analysis is presented for the calculation of the viscous flow of the tubes under the real conditions of dynamic heating by a traversing flame. The experimental determination of the material parameters surface tension and viscosity by collapsing experiments yields an approach to the problem of the temperature distribution in the tube wall.     

Developments in the bulk growth of Cd1−xZnxTe for substrates

Single crystal of CdTe or dilute alloys of Cd_1−yZn_yTe (y < 0.04) and CdTe_1−zSe_z (z < 0.04) with low defect density, high purity, and large single-crystal area (>30 cm²) are required as substances for high-quality epitaxial Hg_1−xCd_xTe thin films in the infrared (IR) detector industry. Bridgman or gradient freeze is the most common technique used for commercial production of these materials because of its success in producing large-area substrates of good quality and reproducibility. For epitaxial growth of Hg_1−xZn_xTe, which has been of considerable interest in recent years as an IR detector material, the substrate of choice has been Cd_0.80Zn_0.20Te, for lattice matching with long-wavelength Hg_1−xZn_xTe epitaxial layers (x = 0.15). The primary focus of this paper is on CdZnTe, which is currently the preffered subtrate material and most widely used for both HgCdTe and HgZnTe epitaxy. This paper reviews the current status of bulk substrate technology for IR detector applications, highlighting critical issues and essential research areas for further improvement of these materials.     

衬底用单晶金刚石晶格随温度变化的研究

本文对CVD(Chemical Vapour Deposition,CVD)外延生长中作为衬底的高温高压(HTHP)单晶金刚石进行拉曼光谱测试,利用谱峰半高宽(FWHM)判断了衬底的结晶质量.开展了升温(室温～1000℃)和降温(1000℃ ～室温)过程中衬底晶格变化的X射线原位测量研究.实验表明:衬底的晶格常数随温度...     

Growth of freestanding GaN using pillar-epitaxial lateral overgrowth from GaN nanocolumns

Dislocation-free and strain-free GaN nanopillars, grown on Si by molecular beam epitaxy, were used as nanoseeds for a new form of epitaxial lateral overgrowth (ELO) by metalorganic vapour phase epitaxy (MOVPE) until full coalescence. Such overgrown GaN films are almost relaxed and were used as templates for producing thick GaN layers by halide vapour phase epitaxy (HVPE). The final GaN film is easily separated from the starting Si substrate. This is henceforth a new technology to produce freestanding GaN. The GaN crystal quality was assessed by transmission electron microscopy (TEM), photo- and cathodoluminescence (PL, CL). It was seen that the pillar-ELO is produced from a limited number of nanopillars. Some dislocations and basal stacking faults are formed during the coalescence. However, those that propagate parallel to the substrate do not replicate in the top layer and it is expected that the thickened material present a reduced defect density.     

人造金刚石单晶薄膜的制备及表面形貌优化

人造金刚石作为一种高效的热管理衬底,在宽禁带半导体电子器件领域具有广泛的应用前景。然而微波等离子体化学气相沉积(MPCVD)法外延金刚石单晶的生长速率慢,表面粗糙度高,难以满足半导体器件的衬底需求。对此,本文采用MPCVD法制备金刚石单晶薄膜,通过分阶段生长监控样品的生长速率,结合显微镜照片和AFM表征样品的表面形貌和表面粗糙度,根据拉曼光谱和XRD分析外延薄膜的晶体质量,最终采用高/低甲烷浓度的两步法外延工艺,实现了金刚石单晶薄膜的高速外延,生长速率达到20 μm/h,同时获得了较为平整的表面形貌。本文所研究的甲烷调制两步法外延工艺能够起到表面形貌优化的作用,有利于在后续的相关器件研发中提供平整的金刚石衬底,推动高功率电子器件的发展。     

Study of ZnSe and CdSe thin film epitaxy on germanium and silicon substrates

The parameters of vaporization, mass-transfer, condensation, and epitaxial growth by hot wall technique (HWT) of ZnSe and CdSe thin films on monocrystalline Ge and Si substrates are studied (Bubnov et al.). It is shown, that the layers structure is improved as the mass transfer mechanism approaches to gasodinamical vapor flow. The influence of condensation temperature of the layers on their crystallographic structure is shown. The increase of the temperature gradient from the source towards the substrate as well as the substrate temperature conditions for growing layers of hexagonal modification. The decrease of the temperature gradient leads to cubic modification. The electron diffraction study revealed the stepwise character of the zinc selenide and cadmium selenide film growth. The knowledge of the parameters of ZnSe and CdSe thin films on monocrystalline Ge and Si by hot wall technique at relatively low substrate temperatures allows to obtain layers, suitable for formation of solid state devices for registration and reflection of optical information.     

少铅/无铅钙钛矿太阳能电池研究进展

钙钛矿太阳能电池作为一种新型的低廉高效的光伏材料在近年来备受关注。铅基钙钛矿太阳能电池有光电转换效率高、成本低、易制备等优点,然而由于铅的毒性以及由此带来的环境污染问题在很大程度上限制了其进一步商业化应用。因此人们开发出一系列新型无毒或低毒钙钛矿材料用于制备环境友好的少铅/无铅钙钛矿太阳能电池。本文简明扼要地介绍了钙钛矿材料的结构和形成条件,着重回顾了Sn基钙钛矿太阳能电池的发展历程,对ⅣA族元素Ge,ⅡA族元素Mg、Ca、Sr和Ba,ⅤA族元素Bi和Sb,ⅢA族元素In以及过渡金属元素Cu等取代或部分取代Pb,以及通过调节卤素X与正离子A的组成及配比来调控少铅或无铅钙钛矿材料性能进行了总结,对少铅/无铅钙钛矿太阳能电池器件研究进展进行了综述,并对其未来的发展方向进行了展望。     

Epitaxy in solar cells

This paper is intended to give an overview of the applications of epitaxial growth to photovoltaic solar cells. In order to introduce those operating parameters which can be improved by epitaxy, we begin by describing how a solar cell functions. Then we discuss the contribution of epitaxial growth to higher cell performance through improved crystalline perfection and purity, controlled doping levels and compositions, and preparation of homo- and heteroepitaxial interfaces.     

Crystal growth of gallium nitride

A review is given of the methods which have been used to grow single crystals and epitaxial layers of gallium nitride. In view of the problems in growing bulk crystals, the main emphasis is on heteroepitaxy. Sapphire has been the most popular substrate material, but leads to severe stress because of lattice and expansion mismatch. The use of an intermediate AlN layer appears to alleviate this problem. Chemical vapor deposition using gallium chloride and ammonia has given the highest quality layers to date, but a native donor remains a persistent problem. The use of high pressures of nitrogen offers promise as a means of reducing the native donor concentration. Atomic layer epitaxy is an alternative technique which looks promising for film deposition under well-controlled conditions. The properties of GaN and device considerations are included briefly in this review.     

基于碳化硅衬底的宽禁带半导体外延

宽禁带半导体具备禁带宽度大、电子饱和飘移速度高、击穿场强大等优势,是制备高功率密度、高频率、低损耗电子器件的理想材料。碳化硅(SiC)材料具有热导率高、化学稳定性好、耐高温等优点,在SiC衬底上外延宽禁带半导体材料,对充分发挥宽禁带半导体材料的优势,并提升宽禁带半导体电子器件的性能具有重要意义。得益于SiC衬底质量持续提升及成本不断降低,基于SiC衬底的宽禁带半导体电子市场占比呈现逐年增加的态势。在SiC衬底上外延生长高质量的宽禁带半导体材料是提高宽禁带半导体电子器件性能及可靠性的关键瓶颈。本文综述了近年来国内外研究者们在SiC衬底上外延SiC、氮化镓(GaN)、氧化镓(Ga₂O₃)所取得的研究进展,并展望了SiC衬底上宽禁带半导体外延的发展及应用前景。