Low-Pressure Chemical Vapor Deposition of Silicon Carbide Thin Films from Organopolysilanes

(Me₃Si)₂SiMe₂, (Me₃Si)₃SiMe and (Me₃Si)₄Si were used as precursors for the deposition of polycrystalline β-SiC thin films on silicon substrates at 1000–1200°C in a low-pressure hot-wall chemical vapor deposition reactor. The thin films were analyzed by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy.     

Laser Photochemistry at Surfaces—Laser-Induced Chemical Vapor Deposition and Related Phenomena

The structural characterization of materials and the tailoring of their properties is an important area of chemical research. A new trend in this area is the recourse to lasers both for analytical as well as preparative purposes, exploiting the fact that lasers, by virtue of their properties (sharp energy, spatial and temporal resolution etc.), offer the most precise and selective interaction of energy and matter that we know. Furthermore, photochemical syntheses and material transformations can proceed “cold” and without causing damage to surface structures. Laser chemistry finds application in thin film deposition, in the formation of surface layers, as well as in (structuring) ablation or etching, and in the initiation and enforcing of reactions at surfaces. In the present paper an introduction to these new possibilities on the general basis of molecule-surface interactions is followed by a brief characterization of lasers suitable for such purposes. Thereafter, four examples are discussed: gas phase deposition from volatile organometallic compounds with photoelectric activation at the surface or photochemical activation of the gaseous species (e.g. by employing molecular beams). In this way (noble) metal contacts can be deposited on various substrates. Instead of surface deposition, nucleation can occur in the gaseous medium, yielding highly disperse powders, e.g. of silicon carbide. Finally, an etching reaction is discussed where the laser does not act as an energy source but as an analytical instrument to provide diagnostic and mechanistic information.     

SiC纤维的化学气相生长与表征

以一甲基三氯硅烷为气源化合物, 二茂铁为催化剂, 噻吩为催化助剂, 用化学气相生长法直接制备SiC纤维. 研究了裂解温度、催化剂及助剂浓度及H2与MTS的配比等因素对裂解产物形态的影响. 分别采用SEM, EDX和XRD对产物的组成和形貌进行了表征. 结果表明, 产物由单一的β-SiC组成. 通过改变反应条件, 无需高、低压气氛及激光辅助, 即可以获得直径为20 nm~1.5 μm、长度从10 μm至数毫米的高长径比SiC纤维.     

Deposition of Silicon Carbide Thin Films from 1,1-Dimethyl-1-Silacyclobutane

1,1-Dimethyl-1-silacyclobutane was used as a single-source precursor to deposit SiC thin films on Si(100) and Si(111) by low-pressure chemical vapor deposition (LPCVD). Polycrystalline β-SiC thin films were grown at temperatures 1100 and 1200°C. At temperatures between 950 and 1100°C, amorphous thin films of silicon carbide were obtained. The films were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and electron diffraction (ED).     

单晶硅上化学气相沉积铜薄膜的机理研究

A versatile metal-organic chemical vapor deposition (MOCVD) system was designed and constructed. Copper films were deposited on silicon (100) substrates by chemical vapor deposition (CVD) using Cu(hfac)2 as a precursor. The growth of Cu nucleus on silicon substrates by H2 reduction of Cu(hfac)2 was studied by atomic force microscopy and scanning electron microscopy. The growth mode of Cu nucleus is initially Volmer-Weber mode (island), and then transforms to Stranski-Rastanov mode (layer-by-layer plus island).The mechanism of Cu nucleation on silicon (100) substrates was further investigated by X-ray photoelectron spectroscopy. From Cu2p, O1s, F1s, Si2p patterns, the observed C=O, OH and CF3/CF2 should belong to Cu(hfac) formed by the thermal dissociation of Cu(hfac)2. H2 reacts with hfac on the surface, producing OH. With its accumulation, OH reacts with hfac, forming HO-hfac, and desorbs, meanwhile, the copper oxide is reduced, and thus the redox reaction between Cu(hafc)2 and H2 occurs.     

化学气相沉积法制备氮化钛

本文以氮化钛的CVD制备为例,说明了源物质的选择对CVD过程的影响.在此基础上,综述了化学气相沉积技术在材料制备领域的最新进展.     

低温溶胶-凝胶法制备高致密度碳化硅陶瓷工艺研究

以柠檬酸为螯合剂,用溶胶-凝胶法制备碳化硅陶瓷烧结前驱粉体,在烧结助剂含量6%、铝钇摩尔比5/3、1850℃低烧结温度烧结1h条件下,获得了体密度为3.219g/cm3、相对密度为98.3%的高致密烧结体,采用IR、XRD、TG/DTA、SEM/EDS等手段对前驱粉体及烧结体进行了表征,讨论了烧结助剂含量、烧结温度等对碳化硅陶瓷烧结体的收缩率、体密度、失重率等特性的影响。     

碳化硅纳米管的制备及表征

Silicon carbide nanotubes (SiCNTs) were prepared by chemical vapor deposition (CVD). Methyltrichlorosilane (MTS) was selected as the SiC gaseous source and, ferrocence and thiophene as the catalyst and the cocatalyst, respectively. The influences of pyrolysis temperature, the content of catalyst and the cocatalyst, and the mole ratio between H₂ and MTS, on the shape of the pyrolysis products were investigated, respectively. The products were characterized by SEM, EDX, XRD and HRTEM, respectively. Novel type of multi-walled SiCNTs, with 30～80 nm and 15～20 nm outer and inner diameters, respectively, were observed.     

Silicon Carbide Nanostructures from Reactions between Vapors of Organochlorosilanes and Liquid of Sodium‐Factors Affecting Morphology and Composition

Cubic shells and spherical nanoparticles of β‐SiC were produced at 1273 K by processing the ceramic precursors formed from the reactions between vapors of organochlorosilanes, Me₂SiCl₂, MeSiCl₃, MeSiHCl₂, and PhSiCl₃, and liquid Na at 523‐723 K. From Me₂SiCl₂, a flexible linear polycarbosilane precursor was synthesized and covered the NaCl byproduct surface to form a cubic shape. Hollow cubic β‐SiC shells were produced after the NaCl templates were removed. From MeSiCl₃, a rigid cross‐linked polycarbosilane was produced and phase segregated from the NaCl byproduct. The precursor was transformed into nanoparticles without special morphology. MeSiHCl₂ produced a cross‐linked polysilane precursor at low temperatures, which can be converted into a mixture of β‐SiC and Si nanoparticles. At high temperatures, the polysilane converted to polycarbosilane and produced hollow cubic β‐SiC shells. The carbon‐rich PhSiCl₃ generated cube‐like particles as the final product, which contained β‐SiC and carbon.     

Ce16Si15O6N32—An Oxonitridosilicate with Silicon Octahedrally Coordinated by Nitrogen

A rarity in solid‐state chemistry is octahedrally coordinated silicon. Ce₁₆Si₁₅O₆N₃₂ is the first nitridosilicate with this structural motif. Most oxosilicates containing octahedrally coordinated silicon are high‐pressure phases. In contrast to that Ce₁₆Si₁₅O₆N₃₂ has been synthesized under ambient pressure. An SiN₆ octahedron that is surrounded by two parallel rings formed from six Si(O,N)₄ tetrahedra is depicted.     

Glass—A Continuing Challenge to Chemistry

This review of the modern chemistry of glass shows that silicate glasses are extremely reactive materials. Compositions, phases, surfaces, and structures can be manipulated in endless variety, and there is no foreseeable limit to the benefits of research in this area.     

A Global Model of Chemical Vapor Deposition of Silicon Dioxide by Direct-Current Corona Discharges in Dry Air Containing Octamethylcyclotetrasiloxane Vapor

A model of the electron distribution in direct current corona plasmas is combined with a global chemistry model and a two-dimensional transport model to predict the rate of chemical vapor deposition of silicon dioxide on the discharge wire in both positive and negative discharges in dry air containing octamethylcyclotetrasiloxane. The gas-phase chemistry includes reactions to form atomic oxygen (O) and additional global reactions to form gaseous silicon dioxide precursors by the impact reactions of electrons and atomic oxygen with silicone molecules. Surface chemistry is approximated by a single step global reaction from gaseous to solid silicon dioxide. The rate coefficient between atomic oxygen and octamethylcyclotetrasiloxane is estimated from prior experiments to be on the order of 10^–12 cm³/molecule-s. The effects of discharge polarity, current, wire radius and air velocity (Peclet number for mass transfer) on the deposition rate are considered. Deposition rates can be minimized by using positive coronas instead of negative coronas for Peclet number less than 18.5. At higher Peclet numbers, the deposition rate is slightly higher in positive corona discharges, but devices used indoors should continue to use the positive corona in order to minimize the production of ozone. The deposition rate in the positive corona is relatively insensitive to air velocity for velocities from 0.044 to 10 m/s^–1 . However,it may be minimized by operating the corona with the lowest current that provides adequate performance (e.g., particle charging) and the smallest wire that provides adequate mechanical strength.     

利用康普顿散射分析碳化硅陶瓷在高温下使用氧化后组成的变化

用波长色散X射线荧光光谱仪,通过测量散射体(样品)对铑的康普顿散射线(RhKα-C)强度的变化,实现了碳化硅陶瓷在高温下使用时氧化情况的监控。用一套8只碳化硅校准样品建立了康普顿散射强度与样品平均原子序数之间关系的数学模型。利用此模型计算了碳化硅氧化后组成含量的变化。结果表明:用此方法测得的样品中碳、硅及氧的相对含量与X射线光电子能谱法所测结果相符,两者间的相对偏差均小于1%。据此认为,此方法所测得的数据是可以接受的。     

Limiting Size of Monolayer Graphene Flakes Grown on Silicon Carbide or via Chemical Vapor Deposition on Different Substrates

Russian Journal of Physical Chemistry A - The maximum size of homogeneous monolayer graphene flakes that form during the high-temperature evaporation of silicon from a surface of SiC or during...     

类石墨烯二硫化钨薄膜的化学气相沉积法制备及其应用

类石墨烯过渡金属硫属化合物如MoS₂、WS₂、MoSe₂、WSe₂等因为具有层数依赖的带隙结构而受到了广泛关注。尤其是本征态的WS₂为双极性半导体,它同时具有n型和p型电输运特性,有望在电子电路、存储器件、光电探测和光伏器件方面得以广泛应用。近年来,化学气相沉积技术已经被广泛用于制备大面积二维硫属化合物(如MoS₂, MoSe₂, WS₂ 和WSe₂)原子层薄膜。目前关于其他二维材料体系的综述文献介绍较多,但是针对WS₂介绍的综述文献还鲜有报道。因此,本文综述了类石墨烯WS₂薄膜的化学气相沉积法制备和相关器件的国内外研究进展,讨论了WS₂薄膜的化学气相沉积法制备机理及生长因素如硫粉含量、载气的成分、反应温度、基底材料等对薄膜成膜质量的影响,介绍了WS₂薄膜在晶体管、光电器件及与其他二维材料构成的异质结构器件的最新研究成果,并对可能存在的问题进行了分析和述评。     

高比表面SiC的合成及其在CO氧化反应中的应用

采用蔗糖为碳源, 正硅酸乙酯(TEOS)为硅源, 分别以草酸、硝酸铁、硝酸镍为催化剂, 用溶胶-凝胶法制备碳化硅前驱体, 考察了制备过程中催化剂的种类以及反应温度和时间对凝胶形成的影响. 发现以硝酸铁为催化剂最有利于凝胶的形成, 碳/硅物质的量比为4的前驱体在氩气气氛1350 ℃下加热10 h, 碳热还原反应趋于完成. 以该条件下合成的多孔碳化硅(比表面积133 m2·g-1)作为催化剂载体, 通过等量浸渍法获得Pt/SiC催化剂, 将其应用于一氧化碳氧化的模型反应中. 研究结果表明该催化剂有较好的催化活性和稳定性. 引入镍助剂的PtNi/SiC催化剂能进一步提高一氧化碳催化氧化反应的活性.     

Towards Multipotent Coatings: Chemical Vapor Deposition and Biofunctionalization of Carbonyl‐Substituted Copolymers

Future advances in designing bioactive materials, such as antithrombotic coatings for cardiovascular stents, will require widely applicable and robust methods of surface modification. In this paper, we report on the development of multifunctional polymer coatings made by chemical vapor deposition (CVD) copolymerization. Polymer coatings of various [2.2]paracyclophane derivatives were co‐deposited in controlled ratios and their chemical composition verified by FT‐IR and X‐ray photoelectron spectroscopy. Furthermore, preliminary biocompatibility of these coatings was assessed using human umbilical vein endothelial cells and 3T3 murine fibroblasts. The parallel immobilization of two different antithrombotic biomolecules onto a CVD‐based copolymer is also demonstrated by orthogonal immobilization strategies.

     

Silicon Carbide Supported Palladium‐Iridium Bimetallic Catalysts for Efficient Selective Hydrogenation of Cinnamaldehyde

Selective hydrogenation of α,β‐unsaturated carbonyls into saturated carbonyls is important to obtain remunerative products. However, it is still a challenge to achieve high activity and selectivity under mild conditions. Herein, Pd, Ir and bimetallic Pd‐Ir nanoparticles were uniformly deposited with high dispersity on the surface of SiC by a facile impregnation method, respectively. The as‐prepared Pd/SiC catalysts efficiently hydrogenate cinnamaldehyde to hydrocinnamaldehyde at room temperature and atmospheric pressure, and the activity of Pd/SiC is observed further enhanced by adding Ir component (conversion of 100%). In addition, the dependence of Pd‐Ir catalyst activity on Pd/Ir molar ratio confirms a synergistic effect between Ir and Pd, which originates from the electron transfer between Pd and Ir.     

用热分析技术测定碳化硅粉体对聚乙二醇的吸附量

用热分析技术TG-DTA(thermal gravimetric and differential thermal analysis)测定浆料中碳化硅粉体对分散剂聚乙二醇PEG(polyethylene glycol)的吸附量. 结果显示PEG在Ar气氛中411.5 ℃时完全分解; 碳化硅表面分散剂PEG的吸附量随着pH的增大而下降, 在较高pH下大多数分散剂仍存在于溶液中; 分散剂PEG的吸附量通过公式(1)进行计算. 该方法简单方便, 可以应用于测量氧化物或非氧化物吸附紫外-可见分光光度法不能测定的一些有机聚合物分子.