Growth of diamond thin films by chemical vapour deposition

Deposition of diamond thin films on non-diamond substrates at low pressures (<760 torr) and low temperatures (<2000°C) by chemical vapour deposition (CVD) has been the subject of intense research in the last few years. The structural and the electrical properties of CVD diamond films grown on p-type 〈111〉 and high-resistivity (>100 kΩ-cm) 〈100〉 oriented silicon substrates by hot filament chemical vapour deposition technique are described in this review paper.     

Investigation into polishing process of CVD diamond films

A new technique used for polishing chemical vapor deposition (CVD) diamond films has been investigated, by which rough polishing of the CVD diamond films can be achieved efficiently. A CVD diamond film is coated with a thin layer of electrically conductive material in advance, and then electro-discharge machining (EDM) is used to machine the coated surface. As a result, peaks on the surface of the diamond film are removed rapidly. During machining, graphitization of diamond enables the EDM process to continue. The single pulse discharge shows that the material of the coated layer evidently affects removal behavior of the CVD diamond films. Compared with the machining of ordinary metal materials, the process of EDM CVD diamond films possesses a quite different characteristic. The removal mechanism of the CVD diamond films is discussed.     

复合抛光对 CVD金刚石薄膜表面光洁度的改进研究

采用激光抛光和热化学抛光相结合的方法，对通过热丝CVD方法生长的金刚石薄膜进行了复合抛光处理．并利用X射线衍射仪（XRD）、拉曼光谱仪（Raman）、扫描电子显微镜（SEM）和原子力显微镜（AFM）对金刚石薄膜进行了表征．结果表明，所合成的金刚石薄膜是高质量的多晶（111）取向膜；经复合抛光后，金刚石薄膜的结构没有因抛光而发生改变，金刚石薄膜的表面粗糙度明显降低，光洁度大幅度提高，表面粗糙度Ra在100nm左右，基本可以达到应用的要求．     

Nanocrystalline diamond films deposited using a new growth regime

Abstract

Time modulated chemical vapour deposition (TMCVD), a new method for depositing nanocrystalline diamond (NCD) coatings, is reported. The key feature of the process is that it utilises modulated methane flow to promote secondary nucleation of nanoscale diamond crystallites. The growth modes of films deposited using both TMCVD and conventional hot filament CVD methods are described. Moreover, a pictorial model showing the key stages of film growth during NCD deposition using TMCVD is presented. The ability of this new process to promote secondary diamond crystallites has been demonstrated.     

大面积高光学质量金钢石自支撑膜的制备

介绍了一种新型的磁控/流体动力学控制的大口径长通道直流电弧等离子体炬，并据此设计建造了100千瓦级高功率DC Arc Plasma Jet CVD金刚石膜沉积系统，讨论了该系统采用的半封闭式气体循环系统的工作原理，以及在气体循环条件下制备大面积高光学质量金刚石自支撑膜的研究结果。     

Polishing of polycrystalline diamond by hot nickel surface

A microwave plasma technique has been employed to deposit polycrystalline diamond film over a molybdenum substrate button using a gas mixture of hydrogen and methane at a substrate temperature of 851°C. A CVD diamond coated molybdenum substrate button was mounted with a load against hot nickel plate and rotated for 3.45 h in a hydrogen ambient. Hot tungsten filament was used as a heat source to maintain the temperature of the nickel block and CVD diamond coated molybdenum button at 848°C. This experiment has reproducibly shown the successful polishing of polycrystalline CVD diamond by hot nickel. A Tencor profilometer and scanning electron microscope have been used to evaluate the surface smoothness and morphology before and after polishing the polycrystalline diamond thin films.     

Cyclic voltammetry and impedance studies of undoped diamond films

The undoped, polycrystalline diamond films were deposited on tungsten wire substrates by hot filament chemical vapor deposition (HF CVD), using a precursor gas mixture of methanol with excess of hydrogen. The morphology and quality of the as-deposited films were monitored by scanning electron microscopy (SEM) and Raman spectroscopy. The surface morphology analyzed by SEM resembles a continuous and well faceted diamond film. Raman results showed essential differences in qualities of diamond films grown at different hydrocarbon concentrations. The electrochemical properties of diamond electrodes were examined with cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS). The CV experiments revealed a large chemical window (>～4.3 V) of undoped diamond. Analysis of the ferrocyanide-ferricyanide couple at a diamond electrode suggests some extent of electrochemical quasi-reversibility, but the rates of charge transfer across the diamond substrate interface vary with diamond quality.     

硫化锌窗口上CVD法制备金刚石膜的研究进展

金刚石具有优异的红外透过性能,可作为硫化锌红外窗口的保护膜。但由于CVD金刚石的沉积过程会刻蚀硫化锌衬底,导致在窗口表面直接生长金刚石膜比较困难。本文主要综述了近年来通过添加过渡层沉积金刚石薄膜的方法和光学焊接金刚石厚膜的方法来增强硫化锌窗口的性能,并介绍了CVD金刚石膜的光学应用及其目前所存在的问题,最后对未来CVD金刚石膜发展的方向作出了展望。     

在硅和硬质合金基体上金刚石薄膜生长研究

在硅和硬质合金基体上，用热丝CVD法生长出金刚石薄膜。利用X衍射、拉曼谱和扫描电镜对金刚石薄膜的结构形貌进行了检测，并与天然金刚石对比分析。     

金刚石薄膜的性质、制备及应用

金刚石有着优异的物理化学性质，化学气相沉积金刚石薄膜的研究受到研究人员和工业界的广泛关注。通过评述金刚石薄膜的性质、制备方法及应用等方面的研究成果，着重阐述化学气相沉积金刚石薄膜技术的基本原理，分析了各种沉积技术的优、缺点。结合对金刚石薄膜应用的讨论，分析了金刚石薄膜在工业应用中存在的问题和制备技术的发展方向。分析结果表明：MWCVD法是高速率、高质量、大面积沉积金刚石薄膜的首选方法；而提高金刚石的生长速度、降低生产成本等是进一步开发刚石薄膜工业化应用所需解决的主要问题。     

The versatility of hot-filament activated chemical vapor deposition

In the field of activated chemical vapor deposition (CVD) of polycrystalline diamond films, hot-filament activation (HF-CVD) is widely used for applications where large deposition areas are needed or three-dimensional substrates have to be coated. We have developed processes for the deposition of conductive, boron-doped diamond films as well as for tribological crystalline diamond coatings on deposition areas up to 50 cm × 100 cm. Such multi-filament processes are used to produce diamond electrodes for advanced electrochemical processes or large batches of diamond-coated tools and parts, respectively. These processes demonstrate the high degree of uniformity and reproducibility of hot-filament CVD. The usability of hot-filament CVD for diamond deposition on three-dimensional substrates is well known for CVD diamond shaft tools. We also develop interior diamond coatings for drawing dies, nozzles, and thread guides.Hot-filament CVD also enables the deposition of diamond film modifications with tailored properties. In order to adjust the surface topography to specific applications, we apply processes for smooth, fine-grained or textured diamond films for cutting tools and tribological applications. Rough diamond is employed for grinding applications. Multilayers of fine-grained and coarse-grained diamond have been developed, showing increased shock resistance due to reduced crack propagation.Hot-filament CVD is also used for in situ deposition of carbide coatings and diamond-carbide composites, and the deposition of non-diamond, silicon-based films. These coatings are suitable as diffusion barriers and are also applied for adhesion and stress engineering and for semiconductor applications, respectively.     

镍衬底上定向金刚石膜的成核与生长

提出了一种包括晶粒接种、高温退火、成核、生长四过程的薄膜沉积新方法 ,用射频等离子体增强热丝化学气相沉积系统 ,在Ni衬底上制备了定向金刚石膜。通过对成核和生长两过程工艺条件的研究 ,掌握了提高成核密度和金刚石定向生长规律。实验还表明 ,膜与Ni衬底之间未见Ni C H界面层的形成     

Thermoluminescence properties of CVD diamond for clinical dosimetry use

The application of diamond to dosimetry is desirable because of its tissue equivalence, chemical inertness and small size, but this has not been commercially viable owing to the non-reproducible response of natural diamond. The chemical vapour deposition (CVD) of diamond permits controlled, reproducible and large-scale production of this material at potentially low cost. An investigation of some clinically relevant features like the depth-dose distribution as well as the absorbed dose profile, obtained using thermoluminescence (TL), is reported for several CVD diamond films. The TL characterisation presented here shows that CVD diamond films should be excellent TL-mode detectors in instances of radiotherapy and in vivo radiation dosimetry.     

Cyclic voltammetry response of an undoped CVD diamond electrodes

The polycrystalline undoped diamond layers were deposited on tungsten wire substrates by using hot filament chemical vapor deposition (HFCVD) technique. As a working gas the mixture of methanol in excess of hydrogen was used. The morphologies and quality of as-deposited films were monitored by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy respectively. The electrochemical activity of the obtained diamond layers was monitored by using cyclic voltammetry measurements. Analysis of the ferrocyanide–ferricyanide couple at undoped diamond electrode suggests that electrochemical reaction at diamond electrode has a quasireversibile character. The ratio of the anodic and cathodic peak currents was always close to unity. In this work we showed that the amorphous carbon admixture in the CVD diamond layer has a crucial influence on its electrochemical performance.     

Raman spectroscopy characterization of diamond films on steel substrates with titanium carbide arc-plated interlayer

Diamond chemical vapour deposition (CVD) on steel represents a difficult task. The major problem is represented by large diffusion of carbon into steel at CVD temperatures. This leads to very low diamond nucleation and degradation of steel microstructure and properties. Recent work [R. Polini, F. Pighetti Mantini, M. Braic, M. Amar, W. Ahmed, H. Taylor, Thin Solid Films 494 (2006) 116] demonstrated that well-adherent diamond films can be grown on high-speed steels by using a TiC interlayer deposited by the PVD-arc technique. The resulting multilayer (TiC/diamond) coating had a rough surface morphology due to the presence of droplets formed at the substrate surface during the reactive evaporation of TiC. In this work, we first present an extensive Raman investigation of 2 μm, 4 μm and 6 μm thick diamond films deposited by hot filament CVD on TiC interlayers obtained by the PVD-arc technique. The stress state of the diamond was dependent on both the films thickness and the spatial position of the coating on the substrate. In fact, on the top of TiC droplets, the stress state of the diamond was much lower than that of diamond in flatter substrate areas. These results showed that diamond films deposited on rough TiC interlayers exhibited a wide distribution of stress values and that very large compressive stress exists in the diamond film grown on flat regions of steel substrates with a TiC interlayer. Diamond films could accommodate stresses as large as 10 GPa without delamination.     

Field emission studies of CVD diamond thin films: effect of acid treatment

Field emission from CVD diamond thin films deposited on silicon substrate has been studied. The diamond films were synthesized using hot filament chemical vapor deposition technique. Field emission studies of as-deposited and acid-treated films were carried out using ‘diode’ configuration in an all metal UHV chamber. Upon acid treatment, the field emission current is found to decrease by two orders of magnitude with increase in the turn-on voltage by 30%. This has been attributed to the removal of sp² content present in the film due to acid etching. Raman spectra of both the as-deposited and acid-treated films exhibit identical spectral features, a well-defined peak at 1333 cm⁻¹ and a broad hump around 1550 cm⁻¹, signatures of diamond (sp³ phase) and graphite (sp² phase), respectively. However upon acid treatment, the ratio (I_d/I_g) is observed to decrease which supports the speculation of removal of sp² content from the film. The surface roughness was studied using atomic force microscopy (AFM). The AFM images indicate increase in the number of protrusions with slight enhancement in overall surface roughness after acid etching. The degradation of field emission current despite an increase in film surface roughness upon acid treatment implies that the sp² content plays significant role in field emission characteristics of CVD diamond films.     

CVD金刚石成核的最新研究

研究了化学气相条件下金刚石在非均匀研磨硅基底表面及镜面基底和均匀研磨基底边缘及角域处的成核行为。发现ＣＶＤ金刚石成核不仅依赖于沉积区缺陷，更主要由缺陷的锐度决定，即缺陷加强ＣＶＤ金刚石成核的锐度效应。在对无序碳上ＣＶＤ金刚石成核研究的基础上，讨论了ＣＶＤ金刚石成核的机理，并由此阐明了各种表面预处理及负偏压等增强ＣＶＤ金刚石成核的微观过程。     

大面积平整金刚石薄膜的制备

用热丝CVD的方法在3英寸的硅衬底上生长均匀的金刚石薄膜。应用了在热丝上方加石黑电极,在形核阶段相对于热丝施加一直流负偏压的预处理方法,使金刚石的成核密度达到10^10-10^11/cm^2,在3英寸镜面抛光的硅衬底上制备了平整的金刚石薄膜,生长的薄膜用SEM及喇曼光谱进行了测试。实验发现电极的位置是影响金刚石薄膜均匀性的重要因素。     

CVD金刚石膜的场发射机制

利用热灯丝化学气相沉积方法在光滑的钼上沉积了金刚石膜,用扫描电子显微镜和Raman谱对金刚石膜进行了分析。结果表明金刚石膜是由许多金刚石晶粒组成,晶粒间界主要是石墨相,并且在膜内有许多缺陷。金刚石膜的场发射结果表明高浓度CH4形成的金刚石膜场发射阈位电场较低浓度CH4形成的金刚石为低。这意味着杂质（如石墨）和缺陷（悬挂键）极大地影响了膜的场发射性能。根据以上结果,提出了一种CVD金刚石膜的场发射机制即膜内的缺陷增强膜内的电场,石墨增大电子的隧穿系数以增强CVD金刚石膜的场发射。     

Optimization of chemical vapor deposition diamond films growth on steel: correlation between mechanical properties, structure, and composition

In the present work we perform optimization of mechanical and crystalline properties of CVD microcrystalline diamond films grown on steel substrates. A chromium-nitride (Cr-N) interlayer had been previously proposed to serve as a buffer for carbon and iron inter-diffusion and as a matching layer for the widely differing expansion coefficients of diamond and steel. However, adhesion and wear as well as crystalline perfection of diamond films are strongly affected by conditions of both Cr-N interlayer preparation and CVD diamond deposition. In this work we assess the effects of two parameters. The first one is the temperature of the Cr-N interlayer preparation: temperatures in the range of 500 degrees C-800 degrees C were used. The second one is diamond film thickness in the 0.5 microm-2 microm range monitored through variation of the deposition time from approximately 30 min to 2 hours. The mechanical properties of so deposited diamond films were investigated. For this purpose, scratch tests were performed at different indentation loads. The friction coefficient and wear loss were assessed. The mechanical and tribological properties were related to structure, composition, and crystalline perfection of diamond films which were extensively analyzed using different microscopic and spectroscopic techniques. It was found that relatively thick diamond film deposited on the Cr-N interlayer prepared at the temperature similar to that of the CVD process has the best mechanical and adhesion strength. This film was stable without visible cracks around the wear track during all scratch tests with different indentation loads. In other cases, cracking and delamination of the films took place at low to moderate indentation loads.