利用甲烷/氢微波等离子体CVD工艺在纯钛基底上沉积纳米金刚石薄膜

与微米金刚石薄膜不同，纳米金刚石薄膜表面平滑。因此，在摩擦学应用领域中，纳米金刚石薄膜是最理想的。表研究利用CH4／H2微波等离子体CVD工艺在纯钛上沉积出纳米金刚石薄膜和微米金刚石薄膜。采用的沉积条件为：沉积温度约为1173K；沉积压力为8．0kPa；CH4浓度在0．5mol％和5mol％之间变化；沉积时间则从4h到12h不等。金刚石薄膜表面用扫描电镜（SEM）观察。在激光拉曼光谱中，微米金刚石薄膜在1332cm^-1处有sp^3键碳的锐峰。1140cm^-1附近的光谱带与纳米金刚石薄膜的特征有关。并用X射线衍射对金刚石薄膜进行了分析。X射线衍射花样证实，纳米金刚石薄膜存在（111）面和（220）面。金刚石薄膜的表面粗糙度随着CH4浓度的增加而减小。但是，甲烷浓度在2mol％与5mol％之间变化时，金刚石薄膜的表面粗糙度接近50nm。据证实，CH4浓度在2mol％和5mol％之间，利用CH4／H2微波等离子体CVD工艺可以沉积出纳米金刚石薄膜。     

CVD金刚石衬底上抗氧化、增透膜的制备与性能

采用射频磁控反应溅射法在化学气相沉积(chemical vapor deposition,CVD)的金刚石衬底上制备了AlN薄膜以及AlN/Si和AlN/Ge膜。通过X射线衍射分析了衬底加热温度对薄膜微结构的影响和薄膜高温下的氧化行为。结果表明:在衬底加热温度低于380℃时制备的AlN薄膜为非晶态,480℃时AlN薄膜为六方多晶。AlN薄膜在800℃热暴露后开始氧化,900℃时基本被氧化为Al2O3。在CVD金刚石上制备的AlN/Si和AlN/Ge膜都能提高金刚石在长波红外波段(8～10μm)的透过性能,单面最大增透分别为8%和3%。镀有AlN/Ge膜的CVD金刚石在800℃高温热暴露实验中,有AlN/Ge膜保护的金刚石表面未发生刻蚀。高温下AlN/Ge膜对金刚石有很好的保护作用,同时增透效果没有明显下降。     

申请号：201110290577．7专利

名称：一种微型钻头金刚石薄膜涂层的制造方法摘要：本发明公开了一种微型钻头金刚石薄膜涂层的制造方法,对微钻的基底材料进行表面处理,采用多步沉积法,控制热丝化学气相CVD（Chemical？ Vapor？ Deposition化学气相沉淀）金刚石薄膜沉积生长条件：加热热丝的温度、腔体内的压力、反应源气体的选择与流量、热丝的排布、微型钻头顶端与热丝之间的距离、热丝排布间距、薄膜沉积生长时间、微型钻头顶部表面温度等。     

CVD金刚石切削工具

阐述金刚石切削工具在机加工中的重要作用和CVD金刚石的优异性能以及CVD金刚石切削工具的形式.对CVD金刚石薄膜切削工具和CVD金刚石厚膜切削工具的特点和应用范围进行了分析对比,并指出存在问题和发展前景.     

CVD金刚石薄膜技术发展现状及展望(下)

简要描述了CVD金刚石薄膜技术的发展历程。介绍了纳米特别是超纳米金刚石膜、CVD金刚石大单晶的技术特点及其应用。超纳米金刚石膜在MEMS(微机电系统)、电化学和生物医学上的应用和CVD金刚石大单晶是当前的研究热点。简言之,金刚石的发展向着更大或者更小的方向深入进行,即"非大即小"。     

CVD金刚石薄膜技术发展现状及展望(上)

简要描述了CVD金刚石薄膜技术的发展历程.介绍了纳米特别是超纳米金刚石膜、CVD金刚石大单晶的技术特点及其应用.超纳米金刚石膜在MEMS(微机电系统)、电化学和生物医学上的应用和CVD金刚石大单晶是当前的研究热点.简言之,金刚石的发展向着更大或者更小的方向深入进行,即“非大即小”.     

单晶金刚石膜与多晶金刚石膜的制备工艺及性能

本文主要介绍了用微波等离子体化学气相沉积法(以下简称MP CVD法)以甲醇-氢气混合气和丙酮-氢气混合气为源气体,分别以单晶硅的(111)面和人造金刚石的(100)面为衬底材料,制备出了面积为20mm×20mm厚为10μm的多晶金刚石膜和面积为1.0mm×1.0mm厚为5μm的单晶金刚石膜。通过试验发现,源气体配比和衬底温度对薄膜质量起决定性作用。另外,衬底在反应腔中的位置对薄膜的生成也有很大影响。单晶金刚石膜制备过程中衬底金刚石的晶体取向与金刚石薄膜的生长及质量有密切的关系。在金刚石的(100),(110)和(111)面上分别获得了单晶金刚石膜和金刚石多晶粒子。选用扫描电镜、显微激光拉曼、反射电子衍射对多晶金刚石膜及单晶金刚石膜的性能进行了测试。     

微波等离子CVD法在石英玻璃上生长金刚石薄膜

用X射线衍射、Raman谱和光电子能谱对石英玻璃上的金刚石薄膜进行分析,对于难用化学气相沉积在玻璃上生长金刚石薄膜的原因提出了一种解释.     

一种加工金刚石薄膜的新方法

近年来,由于化学蒸气沉积法(CVD)的运用,人造金刚石薄膜的生产日益发展。这种金刚石薄膜具有良好的导热性、光学透明牲、硬度、惰性和半导体特性,在光学和生物医学领域中有重要作用。但由于其极高的硬度和体积较小,要把金刚石薄膜加工为理想的形状较为困难,过去的种种加工方法,或者易使晶体本身产生凹痕,或者加工速度很慢,或者生产成本太高,而使其应用受到限制。近来美国报导了一种新方法,能     

论化学气相沉积(CVD)金刚石技术最新发展

描述了国内外化学气相沉积(CVD)金刚石技术研究及产业最新进展,介绍了CVD金刚石的基本生产方法、加工手段、产品类型及应用领域。通过对国内外CVD金刚石技术及产品研究最新进展情况的介绍,指出了我国与世界先进的(CVD)金刚石技术存在的差距,阐述了CVD金刚石市场发展存在的问题并提出改进的建议。     

Growth and Adhesion Enhancement of Diamond Films Deposited on Steel Substrates by a Cr–N Interlayer

Diamond film deposition onto iron-based substrates by chemical vapor deposition methods is complicated by the formation of black carbon or graphitic soot on the substrate surface prior to diamond nucleation and growth, by fast diffusion of carbon into the iron substrate, and by poor adhesion of the deposited film. These complications suggested the use of a buffer layer between the deposited diamond film and the iron-based substrate. We review different methods used to improve the adhesion of diamond film to steel substrates. In particular we describe in detail our own studies which involve the use of a Cr-N interlayer. The use of a chromium nitride interlayer has been found to improve significantly the adhesion of diamond films deposited on ferrous substrates. This is achieved by hindering diffusion processes of carbon and iron, very stable mechanical and chemical bonding between the interlayer and the diamond film, and good adhesion of the interlayer to the steel substrate. We also report on our studies related to residual stress present in the films, as well as a correlation between the interlayer properties and adhesion strength of deposited films.     

甲烷浓度对金刚石薄膜(100)织构生长的影响

以H2和CH4的混合气体为气源,用微波等离子体辅助化学气相沉积法(MPECVD)在1 cm×1 cm S i(100)基体上沉积了金刚石薄膜。研究了不同的甲烷浓度对金刚石薄膜(100)织构生长趋势的影响。分别采用扫描电子显微镜(SEM),Ram an光谱对金刚石膜的表面形貌、质量进行了分析。结果表明,当基体温度为750℃,气压为4.8×103Pa,甲烷浓度为1.4%时,薄膜表面为(100)织构。     

影响金刚石膜刀具涂层形貌的因素分析

采用高分辨金相显微镜对硬质合金刀生上沉各的ＣＶＤ金刚石薄膜进行了表面形貌和膜／基横截面组织形貌的观察;并利用该显微镜配备的功能测量了金刚石颗粒大小,膜厚;利用显微镜正焦／过焦观察判断了金刚石薄膜的成膜状况。初步观察结果表明：甲烷浓度和基体钴含量对金刚石薄膜的表面形貌和膜／基横截面组织形貌有显著的影响。     

Hot filament chemical vapour deposition and wear resistance of diamond films on WC-Co substrates coated using PVD-arc deposition technique

Different Cr- and Ti-base films were deposited using PVD-arc deposition onto WC-Co substrates, and multilayered coatings were obtained from the superimposition of diamond coatings, deposited on the PVD interlayer using hot filament chemical vapour deposition (HFCVD). The behaviour of PVD-arc deposited CrN and CrC interlayers between diamond and WC-Co substrates was studied and compared to TiN, TiC, and Ti(C,N) interlayers. Tribological tests with alternative sliding motion were carried out to check the multilayer (PVD + diamond) film adhesion on WC-Co substrate. Multilayer films obtained using PVD arc, characterised by large surface droplets, demonstrated good wear resistance, while diamond deposited on smooth PVD TiN films was not adherent. Multilayered Ti(C,N) + diamond film samples generally showed poor wear resistance.Diamond adhesion on Cr-based PVD coatings deposited on WC-Co substrate was good. In particular, CrN interlayers improved diamond film properties and 6 μm-thick diamond films deposited on CrN showed excellent wear behaviour characterised by the absence of measurable wear volume after sling tests. Good diamond adhesion on Cr-based PVD films has been attributed to chromium carbide formation on PVD film surfaces during the CVD process.     

Investigation of heterostructure between diamond and iridium on sapphire

Diamond thin film has outstanding physical and chemical properties. Diamond-on-iridium configurations have been prepared by several methods, such as microwave enhanced plasma CVD, direct currency plasma CVD, and hot filament CVD. In this study, an Ir interlayer was deposited on single crystal sapphires (Al₂O₃) with A-planes {1120} by an RF magnetron sputtering method after annealing samples. In addition, a diamond thin film was deposited by a microwave enhanced plasma chemical vapor deposition (MPCVD) method using a mixture of hydrogen and methane gases after a bias enhanced nucleation (BEN) procedure.Ir (001) was grown on the A-plane of sapphire by X-ray pole figure measurement. Diamond thin films were synthesized on each Ir/sapphire substrate and characterized by SEM, Raman spectroscopy. D {100} faces were exhibited in substantial areas of diamond films, and a flat D {100} plane was partially obtained. It is considered that diamond thin films on Ir {100} were mainly grown towards the <100> direction and were epitaxially grown in part.     

A study of the initial stages of diamond deposition on ferrous substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates

The use of a nitrided chromium interlayer has been found to improve the interfacial properties of diamond films deposited on ferrous substrates. This is achieved by hindering diffusion process of carbon and iron, good adhesion of the interlayer to the steel substrate, and very stable mechanical and chemical bonding between the interlayer and the diamond film. In the present study the initial stages of diamond deposition on steel substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates are reported. Nitridation of chromium films deposited by electrochemical methods and polycrystalline chromium substrates resulted in the formation of two chromium nitrides phases, CrN and Cr₂N, and a rough surface morphology. The initial stages of diamond deposition were found to be accompanied by carburization of the substrates surface resulting in chromium carbide formation. The incubation time, diamond particle density and growth rate at the very initial stages of the deposition process were found to differ for these two substrates. It is suggested that these differences originate from different carburization rates of the two substrates. Phase transformation, recrystallization and diffusion processes in the near surface regions of both substrates resulted in very stable chemical bonding and good adhesion of the diamond film to the substrates. Raman spectra of the deposited films, on both substrates, show shift of the diamond peak position to higher wave numbers and split of the peak. These effects are associated with compressive stresses in the diamond film. Residual stresses in the deposited films were calculated from the shift of the diamond Raman peak. The residual stresses, as calculated from the Raman spectra, were found to increase with deposition time reaching values of 8.4 and 6.9 GPa for continuous diamond films on steel substrate coated with the nitrided chromium film and on nitrided chromium substrates, respectively. Based on a simple model it was estimated that thermal stress, arising from mismatch between the thermal expansion coefficient of diamond and the underlying substrates, is the major component of the compressive stress in the diamond films.     

Production of single crystal diamond needles by a combination of CVD growth and thermal oxidation

Single crystal diamond needles were produced by combining chemical vapor deposition of a thin polycrystalline diamond film and its subsequent thermal oxidation. The deposition process has been carried out in a direct discharge activated hydrogen–methane gas mixture with parameters providing (100) textured diamond film growth. The oxidation has been performed by heating the deposited film in an air atmosphere with a temperature allowing the selective etching of the smallest fraction of the diamond crystallites in the film. As a result of this procedure, perfectly shaped micrometer sized single crystal diamond pyramids were obtained. The pyramids have a rectangular base plane with an apex tip curvature radius of about 2 to 10 nm. The atomic structure of the pyramids was established using high resolution transmission electron microscopy. We propose a model explaining the mechanism of the pyramids' formation.     

Influence of substrate nature on the d.c.-glow discharge induced nucleation of diamond

The nature of the nucleation centers, formed during the so called bias enhanced nucleation (BEN) of chemical vapor deposition (CVD) diamond is still an open question. We address this question by investigating the chemical composition and structure of the material deposited during the “nucleation” stage on various substrates by near edge X-ray absorption fine structure technique (NEXAFS) and Raman spectroscopy.The key step of the BEN of diamond in hot filament CVD systems is the generation of a stable d.c.-glow discharge between the grounded substrate and a positively biased electrode. This process results in the deposition of a carbon based film which contains the diamond nucleation and growth centers. Different materials, such as Si(100), CVD diamond films, and Si(100) onto which thin films of Ni were evaporated were used as substrates.It was found that the structure of the material deposited during the d.c.-glow discharge process is affected by the nature of the substrate. The d.c.-glow discharge process applied to the Si substrate resulted in the formation of a graphite-like film in the earlier stages (5 min), which after prolonged treatment time (30 min) was predominantly composed of nanosized diamond. The CVD diamond film, used as a substrate, promoted the formation of nanosized diamond particles even after 5 min of the d.c.-glow discharge process. However, C-13 labeling experiments have shown that microcrystalline diamond does not grow on the pre-existing CVD diamond substrate under the d.c.-glow discharge conditions. In the case of the Ni modified Si, the deposited film was graphitic in nature both after short and prolonged d.c.-glow discharge treatment times.     

Microstructure of c-BN thin films deposited on diamond films

Diamond films were used as substrates for cubic boron nitride (c-BN) thin film deposition. The c-BN films were deposited by ion beam assisted deposition (IBAD) using a mixture of nitrogen and argon ions on diamond films. The diamond films exhibiting different values of surface roughness ranging from 16 to 200 nm (in R_rms) were deposited on Si substrates by plasma enhanced chemical vapor deposition. The microstructure of these c-BN films has been studied using in situ reflexion electron energy loss spectroscopy analyses at different primary energy values, Fourier transform infrared spectroscopy and high resolution transmission microscopy. The fraction of cubic phase in the c-BN films was depending on the roughness of the diamond surface. It was optimized in the case of the smooth surface presenting no particular geometrical effect for the incoming energetic nitrogen and argon ions during the deposition. The films showed a nanocrystalline cubic structure with columnar grains while the near surface region was sp² bonded. The films exhibit the commonly observed layered structure of c-BN films, that is, a well textured c-BN volume lying on a h-BN basal layer with the (00.2) planes perpendicular to the substrate. The formation mechanism of c-BN films by IBAD, still involving a h-BN basal sublayer, does not depend on the substrate nature.     

A study of the crystalline growth of highly boron-doped CVD diamond: preparation of graded-morphology diamond thin films

An investigation was made of graded-morphology diamond thin films deposited on Si substrates by use of the microwave plasma chemical vapor deposition (CVD) technique. The preparation of graded diamond thin films not only offers new perspectives into functional materials, but it also gives clues to the growth mechanism of CVD diamond. Although it is clear that the substrate temperature and the deposition time affect the grain size in particular, the difference depending on the boron concentration in the growing process was studied in the present work. As a result, in highly boron-doped (10⁴ ppm) diamond films, the Raman peak which was ascribed to the boron-doping was not observed at the very initial growth stage. However, the crystal growth process was almost irrelevant for the boron-doping quantity. Furthermore, we showed the morphology dependence of electrochemical properties as one example of the excellent functions of the graded-morphology highly boron-doped diamond film.