微波CVD法合成金刚石薄膜的生长规律及薄膜品质分析

阐述了 微波等离 子化学 气相沉 积 方法 合成 金 刚石 薄 膜的 生长 规 律,并 对 薄膜 品质 作 了分析,指 出加强基 板预处理 、提高工 艺参数控 制精度 是决定薄 膜品质 的关键因 素。     

CVD条件对金刚石薄膜／钼基体界面层的影响

用微波等离子体化学气相沉积法（MPCVD）在Mo基片上沉积金刚石薄膜时,界面层钼的碳化程度与初始沉积条件有关,利用XRD,SEM,EDS,对界面层进行的研究表明：在化学气相沉积的开始阶段,较低的甲烷浓度有利于碳向基体内的扩散从而让表面的Mo充分碳化,形成富含Mo2C的界面层,甲烷浓度过高时有利于金刚石的形核而不利于碳向基体内的扩散,在金刚石薄膜的生长过程中,碳向基体内的扩散很少,界面层的组成结构保持不变。     

Nanodiamond films deposited at moderate temperature on pure titanium substrate pretreated by ultrasonic scratching in diamond powder suspension

Nanocrystalline diamond （NCD） film deposition on pure titanium and Ti alloys is extraordinarily difficult because of the high diffusion coefficient of carbon in Ti, the large mismatch in their thermal expansion coefficients, the complex nature of the interlayer formed during diamond deposition, and the difficulty to achieve very high nucleation density. In this investigation, NCD films were successfully deposited on pure Ti substrate by using a novel substrate pretreatment of ultrasonic scratching in a diamond powder-ethanol suspension and by a two-step process at moderate temperature. It was shown that by scratching with a 30-μm diamond suspension for 1 h, followed by a 10-h diamond deposition, a continuous NCD film was obtained with an average grain size of about 200 nm. Detailed experimental results on the preparation, characterization, and successful deposition of the NCD films on Ti were discussed.     

基片预处理对CVD金刚石薄膜形核的影响

微波辅助等离子体化学气相沉积法是目前低压气相合成金刚石薄膜方法中应用最普遍、工艺最成熟的方法,形核是CVD金刚石沉积的第一步．利用微波辅助等离子体化学气相沉积装置,研究了硅基片预处理方式对金刚石薄膜形核密度的影响．在工作气压为5-8kPa,微波功率为2500—5000W,甲烷流量为4-8cm^3／min,氢气流量为200em3／min,沉积温度为500℃-850℃的条件下,在单晶Si基片上沉积金刚石薄膜．通过扫描电子显微镜形貌观察表明,基片预处理能够显著提高金刚石形核密度,同时用拉曼光谱表征了金刚石薄膜的质量,     

Thermal residual stress analysis of diamond coating on graded cemented carbides

Finite element model was developed to analyze thermal residual stress distribution of diamond coating on graded and homogeneous substrates. Graded cemented carbides were formed by carburizing pretreatment to reduce the cobalt content in the surface layer and improve adhesion of diamond coating. The numerical calculation results show that the surface compressive stress of diamond coating is 950 MPa for graded substrate and l 250 MPa for homogenous substrate, the thermal residual stress decreases by around 24% due to diamond coating. Carburizing pretreatment is good for diamond nucleation rate, and can increase the interface strength between diamond coating and substrate.     

采用Cu／Ti过渡层沉积金刚石薄膜刀具的界面结构

研究了硬质合金基底上Cu／Ti作过渡层化学气相沉积(CVD)金刚石薄膜的界面特性。利用激光Ra—man谱分析了过渡层不同生长阶段金刚石薄膜的质量的影响。采用SEM、EDS对金刚石薄膜硬质合金刀具横截面的结构进行了研究。结果表明：基体中的Co被Cu／Ti作过渡层有效的抑制住；Cu向基体内的扩散改善了基体的性能，提高了界面层金刚石薄膜的质量；Ti的引入促进了金刚石的形核，减少了界面处晶粒间的空隙，提高了金刚石薄膜与基体表面的实际接触面积。     

氢等离子体处理金刚石成核面

通过用氢等离子体对微波等离子体化学气象沉积法在钼基体上制备的金刚石厚膜的成核面进行表面处理,并利用拉曼光谱、扫描电镜和X射线光电子能谱对处理前后金刚石成核面进行表征,比较了处理前后金刚石成核面金刚石相含量、表面粗糙组度,并分析了薄膜中钼原子的化合态及百分含量.结果表明:经过氢等离子体处理后的金刚石成核面的金刚石相含量提高,表面粗糙度增大,钼原子的百分含量由1.64%变为0.83%,且能有效还原成核面上钼的氧化物生成碳化钼和碳化二钼.     

Influence of methane on hot filament CVD diamond films deposited on high-speed steel substrates with WC-Co interlayer

Diamond films were deposited on high-speed steel substrates by hot filament chemical vapor deposition (HFCVD) method. To minimize the early formation of graphite and to enhance the diamond film adhesion, a WC-Co coating was used as an interlayer on the steel substrates by high velocity oxy-fuel spraying. The effects of methane content on nucleation, quality, residual stress and adhesion of diamond films were investigated. The results indicate that the increasing methane content leads to the increase in nucleation density, residual stress, the degradation of quality and adhesion of diamond films. Diamond films deposited on high-speed steel (HSS) substrate with a WC-Co interlayer exhibit high nucleation density and good adhesion under the condition of the methane content initially set to be a higher value (4%, volume fraction) for 30 min, and then reduced to 2% for subsequent growth at pressure of 3 kPa and substrate temperature of 800 °C.     

YT类硬质合金成形铣刀的金刚石涂层工艺研究

针对YT15硬质合金B212型成形铣刀片,以两种不同的化学方式对硬质合金基体进行预处理,而后采用热丝化学气相沉积的方法在其表面沉积微米级金刚石薄膜.使用扫描电子显微镜观察金刚石薄膜颗粒的大小及均匀度,激光拉曼光谱仪检测金刚石涂层的成分,压痕法检验金刚石涂层刀片的膜-基附着强度,并就不同预处理的基体表面对金刚石薄膜的质量、附着性能的影响进行分析.结果表明,经预处理后的YT类硬质合金表面粗糙度较YG类降低约10%,采用平行布置热丝方式和现有的沉积工艺在YT类硬质合金衬底涂覆的金刚石薄膜均匀性较好,且经酸碱预处理的金刚石薄膜表现出良好的附着力,附着强度介于600~1 000 N,醇碱预处理对衬底表面原有的光洁度损坏较小,有助于细化金刚石晶粒,但膜-基附着强度不高.     

燃焰法CVD金刚石薄膜生长过程的实验研究

采用燃焰法在硅基片表面进行了金刚石薄膜沉积实验．介绍了用金刚石微粉研磨基片表面对金刚石成核及生长的影响．根据不同沉积时间基片表面的扫描电子显微照片，分析了金刚石薄膜的生长过程，得出了金刚石薄膜的生长过程是以岛状生长模式形成连续膜的结论．     

辅助气体对分阶段制备金刚石膜的影响

采用形核 甲烷/氢气生长-辅助气体/甲烷/氢气生长的新工艺,在镜面抛光的单晶硅片上制备了金刚石膜,并用扫描电子显微镜和激光拉曼光谱等测试方法对薄膜的表面形貌和质量性能进行了表征;研究了添加辅助气体对已有金刚石晶型生长的影响.结果表明:以甲烷/氢气为气源时,金刚石膜生长率一般为1.8 μm/h,当分别加入氧气、二氧化碳、氮气时,其生长率都有所提高,其中加入二氧化碳时,其生长率是甲烷/氢气为气源的3倍多,但是加入氩气时,其生长率下降;通过新工艺,在加入氮气或氩气时,第一生长阶段为微米,而第二生长阶段为纳米尺寸,最后制备出具有微/纳米双层复合金刚石膜.     

MPCVD法AlN基体上金刚石薄膜的制备

以丙酮和氢气作气源,采用微波等离子体化学气相沉积法（MPCVD）在AlN表面制备金刚石薄膜,并通过拉曼光谱（Raman）,扫描电子显微镜（SEM）对沉积得到的金刚石薄膜进行表征.研究表明：直接在AlN表面沉积因金刚石的形核密度很低而很难得到连续的金刚石薄膜.利用金刚石微粉研磨AlN表面有利于金刚石形核密度的提高,Raman分析和电镜观察发现：所得的金刚石薄膜存在杂质和缺陷,没有明显的刻面特征,而且是由粒径较大的球状颗粒堆积而成.     

Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature—part Ⅱ Simulation of CVD diamond film growth in C—H system and in Cl—containing systems

The growth of {100}-oriented CVD diamond film under two modifications of J-B-H model at low substrate temperatures was simulated by using a revised KMC method at atomic scale,The results were compared both in Cl-containing systems and in C-H system as follows:(1) Substrate temperature can produce an important effect both on film deposition rate and on surface roughness;(2) Aomic Cl takes an active role for the growth of diamond film at low temperatues;(3){100}-oriented diamond film cannot deposit under single carbon insertion mechanism,which disagrees with the predictions before;(4) The explanation of the exact role of atomic Cl is not provided in the simulation results.     

Atomic scale KMC simulation of {100} oriented CVD diamond film growth under low substrate temperature-Part II Simulation of CVD diamond film growth in C-H system and in Cl-containing systems

The growth of {100}-oriented CVD diamond film under two modifications of J-B-H model at low substrate temperatures was simulated by using a revised KMC method at atomic scale. The results were compared both in Cl-containing systems and in C-H system as follows: (1) Substrate temperature can produce an important effect both on film deposition rate and on surface roughness; (2) Aomic Cl takes an active role for the growth of diamond film at low temperatures; (3) {100}-oriented diamond film cannot deposit under single carbon insertion mechanism, which disagrees with the predictions before; (4) The explanation of the exact role of atomic Cl is not provided in the simulation results.     

金刚石薄膜的形核研究

本文介绍了当前金刚石薄膜形核的现状及用热丝化学气相沉积法在不同的衬底上沉积金刚石膜，对Si、Ni、Cu三种衬底生长的金刚石膜进行研究如何增大形核密度、提高形核质量。得到了制备高密度和高质量的金刚石膜的方法。     

Preparation of diamond/Cu microchannel heat sink by chemical vapor deposition

A Ti interlayer with thickness about 300 nm was sputtered on Cu microchannels, followed by an ultrasonic seeding with nanodiamond powders. Adherent diamond film with crystalline grains close to thermal equilibrium shape was tightly deposited by hot-filament chemical vapor deposition(HF-CVD). The nucleation and growth of diamond were investigated with micro-Raman spectroscope and field emission scanning electron microscope(FE-SEM) with energy dispersive X-ray detector(EDX). Results show that the nucleation density is found to be up to 1010 cm-2. The enhancement of the nucleation kinetics can be attributed to the nanometer rough Ti interlayer surface. An improved absorption of nanodiamond particles is found, which act as starting points for the diamond nucleation during HF-CVD process. Furthermore, finite element simulation was conducted to understand the thermal management properties of prepared diamond/Cu microchannel heat sink.     

Synthesis of boron-doped diamond/porous Ti composite materials — Effect of carbon concentration

Highly boron-doped diamond films were deposited on porous titanium substrates by hot filament chemical vapor deposition technique.The morphology variation of highly boron-doped diamond films grown on porous titanium substrates was investigated,and the effects of carbon concentration on nucleation density and diamond growth were also studied.The continuous change of surface morphology and structure of diamond film were characterized by scanning electron microscopy.The structures of diamond film and interlayer were analyzed by X-ray diffraction.The quality of boron-doped diamond film was confirmed by visible Raman spectroscopy.The experimental results reveal that surface morphology and quality of boron-doped diamond films are various due to the change of carbon concentration.The thickness of intermediate layer decreases with the carbon concentration increasing.     

燃焰法沉积金刚石薄膜的成核与生长

用扫描电镜研究了燃焰法沉积金刚石薄膜的成核与生长行为．分析了从成核至形成连续膜期间金刚石晶粒的生长特点．研究了沉积时间对金刚石薄膜晶体形态和表面形貌的影响。     

不同硬质合金基体对(类)金刚石薄膜沉积过程的影响

本文采用 CH_4—H_2—O_2微波等离子体化学气相沉积法在硬质合金基体上沉积金刚石薄膜,研究 YG(WC-Co)及 YT(WC—TiC—Co)两类硬质合金作基体对沉积过程及沉积速率的影响.阶段性研究结果表明,在 YT 类硬质合金上沉积金刚石薄膜的沉积速率和硬度均优于在 YG 类上的,TiC 对金刚石薄膜的沉积效果有明显的有利作用.本文还用扫描电镜观察分析了金刚石薄膜的形核长大过程.     

Influence of heat treatment temperature on microstructure and bonding of TiO<Subscript>2</Subscript> film coated on diamond particles surface

TiO₂ films were coated on the surface of diamond particles using a sol-gel method. The effects of heat treatment temperature on the morphology, phase composition and chemical bond of diamond particles coated with TiO₂ films were investigated through SEM, TEM, X-ray diffraction analysis, Raman spectroscopy, FTIR, and XPS. The results showed that when being heat-treated at 600 °C, the amorphous TiO₂ film transfered to the anatase film which bonded well with diamond substrate. Meanwhile, the Ti-O-C bond formed between TiO₂ film and diamond substrate. When being heat-treated at 800 °C, TiO₂ film was still anatase, and partial diamond began to graphitize. The graphitizated carbon could also form the Ti-O-C bond with TiO₂ film, although TiO₂ film would tend to crack in this case.