Electrochemical studies of nano-structured diamond thin-film electrodes grown by microwave plasma CVD

In this paper, we report the investigation of the electrochemical properties of nano-structured diamond thin-film electrodes on porous silicon (PSi) synthesized by microwave plasma chemical vapor deposition (MPCVD). For the application, boron-doped and undoped diamond thin film has been performed and fabricated into an electrode device, and its microstructure, electrical and chemical properties have been studied. In order to enlarge the surface area of diamond electrodes, a negative bias was applied to the MPCVD process to deposit diamond thin film in a nano-structured form, so that its surface remained rough and nano-fine structured. Diamond thin films were analyzed by Raman spectroscopy and SEM. The morphology of boron-doped diamond thin films on PSi reveals nano-rods in the shape of diamond crystallites. Their electrochemical properties were evaluated by performing cyclic voltammetry (CV) measurement in inorganic K₄[Fe(CN)₆] in a K₂HPO₄ buffer solution. Boron-doped diamond thin film on PSi has demonstrated good electrochemical properties, with a larger redoxidation current of CV, due to its rough surface, which provides a more active electrochemical interface.     

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.     

氧化铝基体表面预处理对金刚石薄膜生长的影响

采用微波等离子体化学气相沉积方法,在经不同预处理的氧化铝衬底上沉积金刚石薄膜.用X射线衍射仪、激光拉曼光谱仪、扫描电镜(SEM)对所得薄膜的成分、物相纯度和表面形貌进行表征,比较不同的预处理方式对金刚石薄膜生长的影响.结果表明,基体表面经过熔融碱腐蚀后形成薄膜的膜基结合良好且膜材质量最佳,但表面平整度较低;而基体只经金刚石微粉乙醇悬浊液超声处理则在沉积时金刚石容易成膜,且结构要更为致密;在经过酸腐蚀的基体上沉积金刚石薄膜时,容易在薄膜与基体之间先形成过渡层,而后才进行金刚石薄膜的沉积.所得结果表明熔融碱腐蚀处理是获得电学应用氧化铝基金刚石薄膜复合材料的最适宜的基体表面预处理.     

硼硫共掺杂金刚石薄膜的研究

利用微波等离子体化学气相沉积(MPCVD)技术,以丙酮为碳源．用二甲基二硫和三氧化二硼作掺杂源．在硅衬底上制备了硼与硫共掺杂的金刚石薄膜。用俄歇谱分析金刚石薄膜中硫的含量．用傅里叶红外光谱(FTIR)分析了薄膜表面键结构．用扫描电子显微镜(SEM)观测薄膜的表面形貌．X射线衍射(XRD)和喇曼(Raman)光谱表征膜层的结构。结果表明：微量硼的加入促进硫在金刚石中的固溶度,使硫在金刚石中的掺杂率提高了近50％;随着薄膜中硫含量的增加．薄膜的导电性增加,当薄膜中硫含量达到0．15％(原子分数)时其导电激活能为0.39eV。     

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．     

Synthesis of carbon films containing diamond particles by electrolysis of methanol

Carbon films containing diamond particles were deposited onto a Si (100) substrate by electrolysis of methanol under a direct current potential of 1200 V, with a current density of about 52 mA/cm², at atmospheric pressure and in the temperature range of 50-55 °C. The surface morphology, microstructure and crystalline structure of the deposited films were characterized by scanning electron microscopy (SEM), Fourier transformation infrared (FTIR) spectroscopy, Raman spectroscopy and transmission electron microscopy (TEM) respectively. The SEM images show that the films are formed by particle clusters and a surrounding glassy phase. The Raman spectra of the films indicate that the particle clusters are composed of diamond and that the glassy phase is composed of amorphous carbon. The FTIR measurements suggest the existence of hydrogen which is mainly bonded to the sp³ carbon in the films. The transmission electron diffraction patterns further indicate that the particles in the films consist of single-crystalline diamond. Both TEM and Raman measurements have confirmed unambiguously the formation of diamond crystals in the deposit, although the particles are not uniformly distributed on the entire surface.     

采用MPCVD法在硅衬底上选择性生长金刚石膜

采用微波等离子体化学气相沉积（MPCVD）法在附有SiO2掩摸的硅衬底上选择性沉积出了金刚石膜。采用扫描电子显微镜（SEM）和Raman光谱仪对金刚石膜的表面形貌和结构进行了表征。并讨论了衬底温度对金刚石薄膜选择性沉积的影响。得出了较佳的沉积条件。     

基片位置对MWPCVD制备金刚石薄膜的影响

在石英钟罩式微波等离子体化学气相沉积实验装置中研究了基片位置对金刚石薄膜沉积质量的影响。扫描电子显微镜显微形貌观察和激光喇曼谱分析表明 ,对微波等离子体化学气相沉积制备金刚石薄膜而言 ,基片位置处于近等离子体球下游区域将有利于改善金刚石薄膜沉积质量。     

气压和偏流对高掺硼金刚石晶体性质的影响(英文)

采用热丝化学气相沉积法,改变工作气压和偏流,在硅基片上沉积了高掺硼金刚石膜。利用扫描电镜(SEM)、拉曼光谱和X射线衍射仪对沉积的金刚石膜表面形貌和结构进行表征。结果显示:当气体压强从3kPa降低到1.5kPa时,金刚石膜有较平的表面形貌和和较好的晶形,薄膜的晶体性质得到良好的改善。但是继续降气体压强,从1.5kPa到0.5kPa时,却呈现出相反的趋势。固定气体压强(1.5kPa),改变偏流,结果表明:适当的偏流(3A)可以改善掺硼金刚石的质量,偏流较高会导致薄膜中非金刚石相增多。     

不同氩气与氢气流量比对硼掺杂纳米金刚石膜的影响

采用直流热阴极PCVD方法,以B(OCH3)3作为硼源,通过改变氩气与氢气流量比,在p型Si衬底上沉积了硼掺杂纳米金刚石膜.研究了不同氩气与氢气流最比对掺硼金刚石膜生长的影响.采用扫描电子显微镜、拉曼光谱仪、X射线衍射仪、霍尔系统等对样品的形貌、结构和导电性能进行了表征.结果表明,随着氩气与氢气流量比的增加,膜的晶粒尺寸由微米级向纳米级转变,并且膜中非晶碳成分增多,膜的导电性能变好.     

无支撑、光学级MPCVD金刚石膜的研制

利用引进的6 kW微波等离子体化学气相沉积设备,进行了无支撑金刚石膜工艺的初步研究。在800~1050℃的基片温度范围内,金刚石膜都呈(111)择优取向;基片相对位置对沉积较大面积、光学级金刚石膜至关重要。制出0.25 mm厚Φ50 mm的无支撑金刚石膜。拉曼光谱和X射线衍射分析表明,合成的金刚石膜晶体结构完整,sp2含量极低;透过率测试结果说明了优良的光学性能:截止波长225 nm,光学透过率(λ≥2.5μm)≥70%。     

CVD diamond layers for electrochemistry

Diamond electrodes of different morphologies and qualities were manufactured by hot filament chemical deposition (HF CVD) techniques by changing the parameters of diamond growth process. The estimation of diamond quality and identification of different carbon phases was performed by Raman spectroscopy measurements. The effect of diamond quality and amorphous carbon phase content on the electrochemical response of an obtained diamond electrode in 0.5 M H₂SO₄ as supporting electrolyte was investigated by cyclic voltammetry with [Fe(CN)₆]^4?/3? as a redox probe. The kinetic parameters such as catalytic reaction rate constant k₀ and electron transfer coefficient α were determined. The obtained results show that the analytical performance of undoped diamond electrodes can be implemented just by the change of diamond layers quality.     

CVD金刚石形核的研究

在钢渗铬层和硅片上进行了化学气相沉积金刚石膜,发现在渗铬层上形成的金刚石膜以球形金刚石为主;用高倍扫描电子显微镜分析显示,渗铬层上的球形金刚石是由大量二次晶核长大的微晶金刚石和非晶碳组成.     

直流热阴极CVD金刚石薄膜生长特性研究

为了获得高质量的金刚石薄膜,采用直流热阴极化学气相沉积系统分别在不同基片温度和不同碳源气体含量条件下生长金刚石薄膜,利用Raman光谱、SEM和XRD检测方法研究了基片温度和碳源气体含量对金刚石薄膜生长特性的影响.结果表明,金刚石薄膜与基片Mo之间有Mo2C的过渡层存在;1000℃的温度能够促进金刚石晶体的生长,抑制其他碳杂质的形成,CH4体积分数为2%适于快速生长高纯度的金刚石薄膜.     

SiC在异质衬底生长金刚石膜的作用分析

利用扫描电子显微镜 (SEM)、Raman光谱分析了Si衬底上金刚石膜核化和生长的过程 ,并着重分析了核化过程产生的SiC的性能。利用划痕法测量了在WC衬底上沉积SiC和未沉积SiC时生长金刚石膜的粘附力 ,同时还分析了WC衬底上有和没有SiC沉积层时表面附近金刚石膜的内应力。结果表明 ,SiC层大大地增强了含碳粒子的聚集和金刚石膜与衬底之间的粘附性 ,降低了金刚石膜与衬底之间的内应力     

Effects of low temperatures, low pressures and seeding over the crystalline quality, yield and stress of diamond films grown by ECR-assisted chemical vapor deposition

We have studied diamond films grown by electron cyclotron resonance (ECR)-assisted chemical vapor deposition (CVD) on Si (100) substrates seeded with diamond, boron nitride and unseeded. Relatively low temperatures (550–710°C) and low pressures (1–2 Torr) were employed. Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) were used to characterize the crystalline quality, diamond yield, and stresses developed in these films. Most of the diamond films exhibit a Raman blue-shift with respect to natural diamond, indicating that the net stress is compressive. However, this net stress is significantly more compressive than the one estimated by taking into account the thermal interfacial stress and the stress developed at the grain boundaries. In addition, this net stress exhibits an inverse correlation with diamond yield, and a direct correlation with crystalline quality. These results were interpreted in terms of the critical interplay between the supply of precursor species to the growing surface and the surface mobility of adsorbed species. The excess (or intrinsic) compressive stress shows an inverse correlation with diamond crystalline quality, indicating that the creation of point defects serves as a stress-relieving mechanism. Seeding effects, in general, are deleterious to diamond quality, in this temperature and pressure regime studied. Seeding with boron nitride had the effect of reversing the net stress from compressive into tensile, but this effect was rapidly lost as the diamond yield increased.     

Mechanical properties of diamond thin films

Abstract

The mechanical properties of diamond films deposited via hot filament chemical vapour deposition have been determined using a range of techniques, and related to the composition and morphology of the diamond films as determined by laser Raman spectroscopy. As the quality of the film increases, its hardness (as determined by the volume law of mixtures hardness model) also increases until it is larger than values often reported for polycrystalline bulk material, a consequence of the very small grain size in the films. Coating adhesion, as determined from indentation adhesion tests, also appears to improve with coating quality. Variations in the behaviour of the friction coefficient between diamond films and diamond and steel counterfaces are less well defined, but it appears that the surface morphology of the film is important in dictating the behaviour rather than the quality of the diamond. These results are discussed in the context of the potential use of diamond coatings in tribological applications.

MST/1695     

Synthesis of diamond films by pulsed liquid injection chemical vapor deposition using a mixture of acetone and water as precursor

A chemical vapor deposition reactor based on the flash evaporation of an organic liquid precursor was used to grow diamond films on Si substrates. An effective pulsed liquid injection mechanism consisting of an injector, normally used for fuel injection in internal combustion engines, injects micro-doses of the precursor to the evaporation zone at 280 °C and is instantly evaporated. The resulting vapor mixture is transported by a carrier gas to the high-temperature reaction chamber where the diamond nucleates and grows on the substrate surface at temperatures ranging from 750 to 850 °C. The injection frequency, opening time, number of pulses and other injector parameters are controlled by a computer-driven system. The diamond film morphology and structure were characterized by scanning electron microscopy and Raman spectroscopy. The as-deposited diamond films show a ball-shaped morphology with a grain size that varies from 100 to 400 nm, as well as the characteristic diamond Raman band at 1332 cm^− 1. The effects of the experimental parameters and operation principle on the diamond films quality are analyzed and discussed in terms of crystallinity, composition, structure, and morphology.     

用氢气/甲醇混合气体在微波等离子体CVD中合成纳米晶粒金刚石膜

用微波等离子体增强化学气相沉积方法(MPECVD),利用氢气和甲醇的混合气体,在硅片上沉积出纳米晶粒的金刚石薄膜.用扫描电子显微镜(SEM)、拉曼光谱(Raman)、原子力显微镜(AFM)及扫描隧道显微镜(STM)对薄膜的晶粒平面平整性及纯度进行了表征.通过SEM发现,提高甲醇浓度或降低沉积温度可以减小金刚石膜的晶粒尺寸.拉曼光谱显示薄膜中确实存在纳米晶粒的金刚石,并且薄膜的主要成分为金刚石.用AFM测得薄膜表面的粗糙度Rms＜80m,STM观测晶粒的平均尺寸在10～20m之间.研究结果表明,用MPECVD方法,利用氢气和甲醇的混合气体是制备纳米晶粒金刚石膜的一种理想方法.     

基片预处理对MWPCVD金刚石薄膜的影响

利用自行研制的石英钟罩式微波等离子体化学气相沉积金刚石薄膜装置，研究了硅基片的不同预处理方式对沉积结果的影响。通过扫描电子显微镜形貌观察和喇曼谱分析表明，基片预处理能提高形核密度；用于预处理的金刚石研磨膏的粒度不同，影响金刚石薄膜沉积时的形核密度、晶形和薄膜的质量；表面划痕对沉积金刚石薄膜的影响具有双重性。