Transient stages during the chemical vapour deposition of silicon carbide from CH3SiCl3/H2: impact on the physicochemical and interfacial properties of the coatings

Transient chemical vapour deposition experiments were produced from MTS/H₂ mixtures by varying the deposition temperature or the gas flow rates (Q_MTS or Q_H2) versus time. The gas phase, deposition rates and properties of the transient coating (φ_Tr) were investigated and adhesion assessments of SiC/φ_Tr/SiC bilayers were performed by scratch testing. Transient stages resulting from a decrease of Q_MTS or temperature lead to silicon co-deposition, but do not affect interfacial properties. Transient stages resulting from a decrease of Q_H2 eventually lead to carbon co-deposition. Thick and continuous carbon interlayers lead to a poor adhesion whereas thin and discontinuous layers do not.     

R.f.-sputtered SiC coatings on carbon fibres

R.f. sputtering as a new method for the deposition of SiC layers onto carbon fibre substrates was applied at temperatures below 400°C and deposition rates higher than 1 μm h^-1. Optimum conditions for high quality SiC films were selected by variation in the r.f. power, r.f. peak voltage, substrate temperature and gas pressure. The SiC layers were characterized using electron probe microanalysis, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, transmission high energy electron diffraction, IR and UV transmission spectroscopy as well as Vickers' hardness measurements. Amorphous SiC layers were obtained. In the case of discontinuous SiC deposition onto carbon monofilaments the film thickness precalculated from the sputtering parameters was achieved, whereas the continuous process results in film thickness of about one-third of the precalculated value. When fibre bundles with different numbers of monofilaments were used no influence on the resulting SiC layer thickness could be observed. Increasing the SiC film thickness, however, led to a strong decrease in the fibre tensile strength for layers more than 50 nm thick.     

旋转CVI制备C/SiC复合材料

旋转 ＣＶＩ是在 ＣＶＩ原理基础上发展的一种制备 Ｃ／ＳｉＣ复合材料的新工艺,通过石墨衬底的旋转,使预制体的制备与基体的沉积同步进行,能有效消除一般ＣＶＩ工艺过程中存在的“瓶颈”效应．在自制的旋转 ＣＶＩ设备上实验,探索了旋转 ＣＶＩ工艺参数中 ＣＨ_３ＳｉＣｌ_３（ＭＴＳ）的流量与浓度、沉积温度和Ｃ布缠绕线速度对ＳｉＣ基体沉积速度,以及沉积温度对基体结构的影响．并在低压（５ｋＰａ）、高温 （１１００℃）、 ４００ ｍＬ·ｍｉｎ^－１ Ｈ_２、 ２００ ｍＬ·ｍｉｎ^－１Ａｒ、 ＭＴＳ４０℃与Ｃ布以１．１～３．５ｍｍ·ｍｉｎ^－１的线速度连续旋转的沉积条件下,实现了单丝纤维间微观孔隙、纤维束之间以及Ｃ布层间宏观孔隙的致密化同步完成．     

SiC/SiC minicomposites with (PyC/TiC)n interphases processed by pressure-pulsed reactive CVI

(Pyrocarbon/titanium carbide) _n multilayered interphases were prepared within SiC/SiC minicomposites by a new method: pressure-pulsed reactive chemical vapour infiltration (P-RCVI). This method combines P-CVI with reactive chemical vapour deposition (RCVD). Minicomposite tensile tests with unload-reload cycles have shown that the interfacial shear stress depends on the number of TiCl₄ gas pulses used for the processing of TiC sub-layers. TEM observations have shown, that with a few gas pulses, the carbide nucleates as isolated grain islands which disturbs the structural anisotropy of the pyrocarbon. This structure results in a good mechanical fibre/matrix load transfer. By increasing the number of gas pulses, the TiC sub-layers become continuous and it is possible to partially consume the highly ordered pyrocarbon sub-layers, but, in that case, the load transfer is poor. The specimen behaviour in air at 700°C under a constant tensile loading was assessed. Compared with a pure pyrocarbon reference interphase, the interphases containing TiC significantly improve the lifetime of the SiC/SiC minicomposites.     

New technology for fabrication of C/SiC composites reinforced by continuous carbon tows

Abstract

Carbon/silicon carbide composites were fabricated using the continuous synchronous composite (CSC) process, which is an improved technology based on conventional chemical vapour infiltration principles to fabricate ceramic matrix composites reinforced with carbon cloth or continuous tows which are not braided to a preform. In the CSC process, a gradient temperature field on the surface of the graphitic substrate, consisting of high (1000–1200°C), intermediate (900–1000°C), and low (700–900°C) temperature regions, was obtained by a bottom heating element. Since the rotation of the substrate accompanied simultaneously the preparation of the reinforcement phase and the deposition of the SiC matrix, micropores were well infiltrated in the intermediate temperature regions by diffusion transport, and macropores were well infiltrated in the high temperature regions with flow transport, respectively. Using methyltrichlorosilane (MTS) as a precursor, with hydrogen as a carrying gas and argon gas as a diluent, in the present studies, densification of C/SiC composites was uniform, and the highest deposition rate obtained was 0.168 mg cm^-2 min^-1), and the conversion efficiency of MTS varied from 31% to a maximum of 47%.     

Graphoepitaxy of High‐Quality GaN Layers on Graphene/6H–SiC

The implementation of graphene layers in gallium nitride (GaN) heterostructure growth can solve self‐heating problems in nitride‐based high‐power electronic and light‐emitting optoelectronic devices. In the present study, high‐quality GaN layers are grown on patterned graphene layers and 6H–SiC by metalorganic chemical vapor deposition. A periodic pattern of graphene layers is fabricated on 6H–SiC by using polymethyl methacrylate deposition and electron beam lithography, followed by etching using an Ar/O₂ gas atmosphere. Prior to GaN growth, an AlN buffer layer and an Al_0.2Ga_0.8N transition layer are deposited. The atomic structures of the interfaces between the 6H–SiC and graphene, as well as between the graphene and AlN, are studied using scanning transmission electron microscopy. Phase separation of the Al_0.2Ga_0.8N transition layer into an AlN and GaN superlattice is observed. Above the continuous graphene layers, polycrystalline defective GaN is rapidly overgrown by better quality single‐crystalline GaN from the etched regions. The lateral overgrowth of GaN results in the presence of a low density of dislocations (≈10⁹ cm⁻²) and inversion domains and the formation of a smooth GaN surface.     

Superstable advanced hydrogen peroxide transducer based on transition metal hexacyanoferrates

We report on a superstable hydrogen peroxide (H(2)O(2)) transducer made by sequential deposition of the iron- and nickel-hexacyanoferrate (NiHCF) layers. Both chemical and mechanical stability of the latter, as well as similarity of its structure to Prussian Blue (PB) provide a substantial stabilization of the most advantageous H(2)O(2) transducer. The electrochemically deposited five bilayers of PB-NiHCF exhibit a complete stability under the continuous wall-jet flow of 1 mM of H(2)O(2) during more than 2 h, maintaining current at a level of 0.2 mA cm(-2), whereas common Prussian Blue loses half of its response within the first 20-25 min. Even being deposited in the open circuit regime on screen-printed electrodes, PB-NiHCF bilayers dramatically improve tolerance of the resulting transducer to alkaline solutions and iron ligands. Despite their 2-2.5 times decreased sensitivity (compared to common Prussian Blue), the sequentially deposited bilayers of PB-NiHCF provide a similar dynamic range of the transducer due to the decreased noise level.     

BN/SiC复合界面层对SiC纤维和PIP-Mini复合材料力学性能的影响

采用化学气相渗透(CVI)工艺, 在SiC纤维表面沉积BN和BN/SiC复合界面层, 对沉积界面层前后纤维的力学性能进行了评价。采用聚合物浸渍裂解(PIP)工艺进行致密化, 制得以原纤维、BN界面层和BN/SiC界面层纤维增强的三种Mini-SiC_f/SiC复合材料, 研究其微观结构和拉伸性能。结果表明: 采用CVI工艺制得的界面层厚度均匀、结构致密, 其中BN界面层中存在六方相, 晶体尺寸为1.76 nm; SiC界面层结晶性较好, 晶粒尺寸为18.73 nm; 沉积界面层后SiC纤维的弹性模量基本保持不变, 拉伸强度降低。与SiC_f/SiC相比, PIP工艺制备的SiC_f/BN/SiC和SiC_f/(BN/SiC)/SiC-Mini复合材料所能承受的最大拉伸载荷和断裂应变明显提升, BN界面层起主要作用。由断面形貌分析可以看出, SiC_f/BN/SiC和SiC_f/(BN/SiC)/SiC复合材料的纤维拔出明显, 说明在断裂时消耗的能量增加, 可承受的最大载荷增大。     

化学气相沉积碳化硅的热力学分析

根据吉布斯自由能最小原理, 采用FACTSAGE计算软件, 重点对MTS/H₂体系化学气相沉积碳化硅进行了均相平衡计算,评价了体系中主要化合物对沉积碳化硅的作用. 结果表明,低温和高压下, SiCl₄和CH₄的含量最多, 不饱和物质和自由基的含量非常少, 温度的升高和压力的下降可显著提高不饱和物质和自由基的浓度; 高温和低压下, SiCl₂和C₂H₂可能是形成碳和硅的主要先驱体, 其它稳定物质如碳氢化合物、有机硅化合物和硅烷等由于浓度太小和表面反应粘结系数低, 对碳化硅的沉积可以不予考虑; 体系中几乎没有含Si--C和Si--Si键的物质, 说明碳化硅是经过碳和硅独立形成, 二者的相对速率决定了碳硅比.     

The degradation behavior of SiC coated PIP-C/SiC composites in thermal cycling environment

C/SiC composites had been considered as structural material in complex and harsh environments, thermal stability was one of the key issues for C/SiC composites. This study aimed to investigate C/SiC composites in thermal cycling environment. SiC coating on carbon fibers via chemical vapor deposition at time from 0.5 h to 5 h was studied, and then the degradation behavior of coated C/SiC composites had been measured by thermal cycling tests. The results showed that the coating was continuous and uniform, with good surface adhesion. The interface of carbon fibers and SiC coating was partially destroyed during thermal shock tests. The degradation of mechanical properties was closely related to the evolution of the damage in the composites.     

C(B) materials as interphases in SiC/SiC model microcomposites

A specific test procedure has been developed to compare the high temperature lifetimes of SiC/SiC microcomposites with various interphases in air and under mechanical loading. The interphases, namely pure pyrocarbon (PyC) or C(B) materials with uniform or variable boron contents in the thickness, were prepared by chemical vapour deposition (CVD). Uniform addition of boron in PyC interphases improved their oxidation resistance and consequently the lifetimes of the microcomposites. However, room temperature tensile tests have shown that this improvement occurs to the detriment of the mechanical properties even when a non-brittle behaviour is maintained. In the case of variable boron contents, compositional gradient interphases (CGI) in which boron content increases from the fibre interface to the matrix interface allow the mechanical fuse properties of PyC to be combined with the oxidation resistance of a C(B) material. This revised version was published online in November 2006 with corrections to the Cover Date.     

The effect of input gas ratio on the growth behavior of chemical vapor deposited SiC films

In an effort to protect a RBSC (reaction-bonded silicon carbide) reaction tube, SiC films were chemically vapor deposited on RBSC substrates. SiC films were prepared to investigate the effect of the input gas ratios (dilute ratio, = P _H2/P _MTS = Q _H2/Q _MTS) on the growth behavior using MTS (metyltrichlorosilane, CH₃SiCly₃) as a source in hydrogen atmosphere. The growth rate of SiC films increased and then decreased with the decrease of the input gas ratio at the deposition temperature of 1250°C. The microstructure and preferred orientation of SiC films were changed with the input gas ratio; Granular type grain structure exhibited the preferred orientation of (111) plane in the high input gas ratio region ( = 3–10). Faceted columnar grain structure showed the preferred orientation of (220) plane at the low input gas ratios ( = 1–2). The growth behavior of CVD SiC films with the input gas ratio was correlated with the change of the deposition mechanism from surface kinetics to mass transfer.     

CH_3SiCl_3-BCl_3-H_2体系气相沉积的热力学计算

利用FactSage software软件进行热力学计算,获得了CH3SiCl3(MTS)-BCl3-H2体系在化学气相沉积环境中Si-B-C陶瓷的热力学产物图和相图。讨论了在高温(900～1100℃)、低压(2 kPa、5 kPa和12 kPa)条件下系统总压、温度和反应气体比例等参数对主要产物产率的影响。结果表明,在所研究的参数范围内,系统总压、温度和气体比例对B4C相的产率影响比较明显,而对SiC相的产率影响不明显。气体比例对C相的产率影响比较明显,温度和系统总压对C相的产率影响不明显。各参数的变化对主要气态产物(BHx、CxHy、SiClx等)的产率有一定程度的影响。稀释气体分压的增加有利于富B相的生成,MTS分压的增加有利于SiC的生成。     

Characterization of SiC/C (B)/SiC microcomposites by transmission electron microscopy

Uniform or composition-graded C(B) (i.e., boron-containing carbon) interphases in SiC/SiC model microcomposites were characterized by transmission electron microscopy after tensile tests and thermal ageing in air. A specific method was developed to prepare thin longitudinal sections of the tested specimens. Deflection of matrix cracks occurs within the uniform C(B) interphase, as long as its anisotropy remains high enough (i.e., when the boron content is not too high). It takes place close to the most anisotropic layer (i.e. that containing 8 at% of boron) in composition-graded interphases. In both cases, the crack deflection path does not reach the fibre, a feature which is consistent with the good mechanical properties. After ageing in air under tensile loading beyond the proportional limit (600°C; σ=800 MPa), the composition-graded interphase (made of five sublayers in which the boron content increases from 0 at% near the fibre to 33 at% near the matrix) was observed to act as a glass-forming protection, the pyrocarbon sublayer (at the fibre surface) remaining unoxidized. This revised version was published online in November 2006 with corrections to the Cover Date.     

XPS study of the a-C:H/Ti and a-C:H/a-Si interfaces

In this study ultrathin hydrogenated amorphous carbon (a-C:H) films have been grown onto the titanium and amorphous silicon (a-Si) overlayers by direct ion beam deposition using acetylene gas as a hydrocarbon source. X-ray photoelectron spectroscopy (XPS) was used for study of the DLC-Ti and DLC-Si interfaces. It was revealed that a-Si is a good interlayer for improvement of adhesion in the case of diamond-like carbon film deposition onto the steel substrate at room temperature. a-C:H film growth without substantial intermixing occurred on the a-Si. On the other hand, adhesion between the Ti interlayer and the diamond like carbon film was very sensitive to the deposition conditions (presence of the pump oil) as well as structure and stress level of the Ti film. It was explained by strong intermixing between the growing carbon film and Ti. Bad adhesion between the growing DLC film and Ti interlayer was observed despite formation of the TiC. At the same time, formation of the TiO_x was not an obstacle for good adhesion. It is shown that composition of the used hydrocarbon gas, structure of the Ti thin film and mechanical stress in it had greater influence on adhesion with a-C:H film than elemental composition of the Ti interlayer surface.     

Synthesis and analysis of buried SiC layers in monocrystalline silicon

SiC layers were fabricated by implantation using 10–40 keV carbon ions in Si(100) and Si(111) wafers, with subsequent annealing between 800 and 1100°C. Computed and experimental IR curves were compared and the thickness of the film were determined from transmission data. The computed thickness were compared with twice the straggling width. The results lead to the conclusion that the fabricated films are continuous rather than SiC clusters in a silicon matrix.     

Mechanical and electromagnetic wave absorption properties of C_f-Si_3N_4 ceramics with PyC/SiC interphases

Aiming to obtain microwave absorbing materials with excellent mechanical and microwave absorption properties, carbon fiber reinforced Si_3N_4 ceramics(Cf-Si_3N_4) with pyrolytic carbon(PyC)/SiC interphases were fabricated by gel casting. The influences of carbon fibers content on mechanical and microwave absorption properties of as-prepared Si_3N_4 based ceramics were investigated. Results show that chemical compatibility between carbon fibers and Si_3N_4 matrix in high temperature environment can be significantly improved after introduction of Py C/SiC interphases. As carbon fibers content increases from 0 to 4 wt%, flexural strength of Si_3N_4 based ceramics decreases slightly while fracture toughness obviously increases. Moreover, both the real and imaginary parts of complex permittivity increase with the rising of carbon fibers content within the frequency range of 8.2–12.4 GHz. Investigation of microwave absorption shows that the microwave attenuation ability of Cf-Si_3N_4 ceramics with Py C/SiC interphases is remarkably enhanced compared with pure Si_3N_4 ceramics. Effective absorption bandwidth(-10 d B) of10.17–12.4 GHz and the minimum reflection less of-19.6 d B are obtained for Si_3N_4 ceramics with 4 wt%carbon fibers in 2.0 mm thickness. Cf-Si_3N_4 ceramics with Py C/SiC interphases are promising candidates for microwave absorbing materials with favorable mechanical property.     

反应器长径比对化学气相沉积SiC沉积动力学的影响

以三氯甲基硅烷(MTS)和H2为前驱体,在沉积温度900～1 050℃,H2和MTS摩尔比为4～20和滞留时间0.4～1 s下,采用化学气相沉积(CVD)工艺研究沉积反应器长径比分别为7∶6和7∶2时的碳化硅(SiC)沉积动力学.结果 发现,不同尺寸反应器中SiC沉积速率随工艺参数变化的规律性差异明显.长径比7∶6的反...     

Finite element simulation of the effects of process parameters on deposition uniformity of chemical-vapor-deposited silicon carbide

A two-dimensional model was developed to simulate chemical vapor deposition process for preparing SiC coating by MTS + H₂ system in a vertical hot-wall reactor. The effects of process parameters, including deposition temperature, the flux of mixed gases, the ratio of H₂ and Ar, and the volume ratio of MTS and mixed gases, on deposition uniformity of SiC coating were calculated by finite-element method. The CVD process was optimized by an orthogonal L₉(3)⁴ test to deposit uniform SiC coating. The results show that the deposition uniformity of SiC is influenced greatly by the deposition temperature and the ratio of H₂ and Ar, and little by the flux of mixed gases and the volume ratio of MTS and mixed gases. The optimal deposition uniformity of SiC can be obtained under the operating condition as follows: deposition temperature 900 °C, the flux of mixed gases 0.6 l/min, H₂: Ar = 1:0, and the volume ratio of MTS and mixed gases 1:10. Part of calculated results is validated by corresponding experimental data, which implies that this model is valid and reasonable to characterize CVD process of SiC coating.     

Remote catalyzation for direct formation of graphene layers on oxides

Direct deposition of high-quality graphene layers on insulating substrates such as SiO(2) paves the way toward the development of graphene-based high-speed electronics. Here, we describe a novel growth technique that enables the direct deposition of graphene layers on SiO(2) with crystalline quality potentially comparable to graphene grown on Cu foils using chemical vapor deposition (CVD). Rather than using Cu foils as substrates, our approach uses them to provide subliming Cu atoms in the CVD process. The prime feature of the proposed technique is remote catalyzation using floating Cu and H atoms for the decomposition of hydrocarbons. This allows for the direct graphitization of carbon radicals on oxide surfaces, forming isolated low-defect graphene layers without the need for postgrowth etching or evaporation of the metal catalyst. The defect density of the resulting graphene layers can be significantly reduced by tuning growth parameters such as the gas ratios, Cu surface areas, and substrate-to-Cu distance. Under optimized conditions, graphene layers with nondiscernible Raman D peaks can be obtained when predeposited graphite flakes are used as seeds for extended growth.