采用正交法研究金刚石偏压形核

在微波等离子体化学气相沉积装置中 ,采用正交试验法研究金刚石在镜面抛光的Si( 1 0 0 )面上的偏压形核过程中 ,形核时间、偏压电压、气压及甲烷浓度对形核密度的影响 ,研究结果表明 :形核密度随形核时间的增加而增加 ,适中的偏压电压和沉积气压有利于金刚石的形核 ,而甲烷浓度的影响很小。正交试验所得的最佳形核条件为偏压 -1 5 0V ;时间 1 2min ;气压 4kPa;CH4 比率 5 % ,在该条件下金刚石的形核密度达到 1 0 1 0 个 cm2 。     

热丝CVD金刚石薄膜制备及碳纳米管形核作用的研究

利用热丝化学气相沉积法 (HF CVD)进行了金刚石薄膜制备和碳纳米管形核作用的研究。获得了制备金刚石薄膜的优化工艺参数。利用碳纳米管作为形核前驱获得了高质量的金刚石薄膜 ,其沉积速率可达 2 5 μm/h ,晶粒生长完美 ,而且没有出现聚晶现象。研究了碳纳米管涂料质量对薄膜沉积特性的影响 ,并对其机理进行了初步探讨     

热丝CVD金刚石薄膜制备及碳纳米管形核作用的研究

利用热丝化学气相沉积法（HF－CVD）进行了金刚石薄膜制备和碳纳米管形核作用的研究。获得了制备金刚石薄膜的优化工艺参数。利用碳纳米管作为形核前驱获得了高质量的金刚石薄膜，其沉积速率可达2．5μm/h，晶粒生长完善，而且没有出现聚晶现象。研究了碳纳米管涂料质量对薄膜沉积特性的影响，并对其机理进行了初步探讨。     

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。     

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。     

金刚石薄膜形核与长大动力学的研究

采用热丝ＣＶＤ法在半底上合成了金刚石薄膜，研究了工艺参数对金刚石形核与长大的影响规律。形核密度随甲烷深度的增加和抛光膏粒度的减小而增加，随衬底工上升而增加至极值后下降，衬底温度过低，形核密度增加但形核为球状。     

大面积高质量金刚石自支撑膜热导率的影响因素研究

通过Raman、XRD、SEM分析方法分别对大面积高质量金刚石自支撑膜的质量、晶体结构、晶粒尺寸进行研究,分析它们对金刚石自支撑膜热导率的影响.研究结果表明,金刚石自支撑膜的质量对热导率的影响较大,质量越好,热导率越接近于天然金刚石的热导率;并且金刚石自支撑膜中晶体[220]取向度越高,热导率越高.形核面晶粒尺寸越大,晶粒间的晶界就减少,有利于提高金刚石自支撑膜的热导率.     

WC和Si衬底生长金刚石薄膜的研究

采用ＳＥＭ,Ｒａｍａｎ光谱等手段,较全面系统地研究了ＨＦＣＶＤ法在ＷＣ和Ｓｉ衬底上生长金刚石薄膜时,衬底预处理、碳源深度、热丝及衬底温度等对金刚石形核、生长的影响。并对两种衬底进行了对比与分析,最后总结出影响金刚石形核密度、形核速率、晶形结构及晶形完善性的关键因素。     

HFCVD金刚石薄膜在Mo基体表面的形核

采用热丝化学气相沉积(HFCVD)方法在Mo基体上沉积金刚石薄膜,使用扫描电镜(SEM)和X射线衍射(XRD)对薄膜样品进行分析检测,研究了表面形核密度随碳源浓度的变化.结果表明:随着碳源浓度增加表面形核密度增大,当碳源浓度达到3%时,表面形核密度质量最佳,当浓度进一步增大时,形核密度下降;随着碳源浓度增加,生长加快,当生长过快时影响形核过程,形核密度下降.     

MPCVD制备金刚石膜的形核与生长过程

简要介绍了金刚石膜的物理化学特性及应用领域。对比分析了主要化学气相沉积方法的优缺点,并指出MPCVD所面临的技术瓶颈。总结了反应腔体内压强、基片温度、基体材料及增强形核技术对金刚石膜形核过程的影响。较低腔体内压力、基片温度,高碳源浓度及等离子体预处理能有效提高形核密度。阐述了各过程参数对金刚石膜生长的影响和微米、纳米、超纳米金刚石膜的技术特点及应用。指出各类金刚石膜制备所面临的技术难题,并综述了解决该技术瓶颈的最新研究工作。     

Synthesis of Diamond Thin Films on TC4 by Using a Scanning Linear Flame

A scanning linear flame is used to deposit diamond films over a large area, and with high quality and good continuity by employing appropriate cooling means for the substrate. It is found that the structure and morphology of the deposited films mainly depend on the substrate temperature, the ratio of 0₂ to C₂H₂ flow rate and the relative position of the substrate with respect to the flame. These factors affecting the structure and morphology of diamond films are interrelated. Moreover, the influences of surface pretreatments on nucleation and growth of diamond films are also studied. The experimental results show that the nucleation density of diamond films is enhanced by scratching the surface of the substrate with diamond grit and initially coating a mechanical pump oil layer. For the substrate surface etched with metallographic etching acid, the nucleation and growth of diamond films are very uniform. In addition, the adhesion between the film and substrate is enhanced. Nucleation is favored on the prominent features of the substrate, i.e. scratch and crystal boundary.     

Fluidized bed micro-machining and HFCVD of diamond films onto Co-cemented tungsten carbide (WC-Co) hardmetal slabs

The effect of fluidized bed (FB) treatment upon hot filament chemical vapor deposition (HFCVD) of polycrystalline diamond films onto WC-Co hardmetal substrates was investigated. Several scenarios to make the substrates ready for HFCVD were, comparatively, evaluated and the resulting diamond films were examined in terms of their morphology and adhesion. The diamond grain density was measured by scanning electron microscopy. The adhesion of continuous diamond film to substrate was evaluated by the reciprocal of the slope of crack radius-indentation load functions. Surface binder dissolution followed by FB treatment (PF pretreatment) allowed very high diamond nucleation density and smaller grain size. The adhesion of films grown on PF pretreated substrates was found to be very close to that of films deposited on hardmetal slabs pretreated by Murakami's reagent followed by Co etching with Caro's acid and seeded with diamond suspension in an ultrasonic vessel (MPS pretreatment). However, diamond coatings on MPS pretreated samples exhibited a rougher surface morphology as a result of both lower diamond nucleation density and larger substrate surface roughening by Murakami's etching. Based upon experimental findings, our newly developed PF pretreatment was found to be a very promising technique in substrates conditioning as well as in promoting adherent, uniform and smooth diamond coatings onto hardmetal tools and wear parts.     

燃焰法沉积金刚石薄膜的实验研究

研究分析了燃焰法沉积金刚石薄膜时基片表面处理状态，燃烧气体流量比基片温度对薄膜成核密度、质量和晶体形态的影响。结果表明，在不同粒度的研磨粉研磨的基片表面上金刚石薄膜成核密度不同；燃烧气体流量配比对金刚石薄膜的质量影响很大；基片温度是影响金刚石薄膜晶体形态的一个重要因素。     

金刚石纳米粉促进的CVD金刚石薄膜的生长行为研究

采用由普通炸药爆轰制备的金刚石纳米粉对光滑硅衬底进行了涂覆预处理,研究了金刚石薄膜经徐覆和研磨预处理的两种衬底上的生长行为及其演化过程．结果表明,纳米粉处理能在显著提高成核密度的同时,大大缩短长成连续膜所用的时间;薄膜的生长由前后相继的两个阶段所构成,即确定晶面形成前球状颗粒的成长与融合和晶面的逐渐显露与晶粒长大过程．经足够长的生长时间后,所得薄膜具有结构致密、晶面清晰、晶形完整和表面平整度高的特征,特别适合于高致密性自支持薄膜的生长．而研磨处理衬底上生长的薄膜一旦成核,便有确定晶面的显露,但却出现明显的二次成核和孪晶,所得薄膜的致密性与表面平整度均不及徐覆处理的好．文中还对结果进行了简要讨论．     

Diamond deposition on copper: studies on nucleation, growth, and adhesion behaviours

This paper presents a systematic study on diamond growth on copper by microwave plasma chemical vapour deposition (MPCVD). It includes the following four main parts. 1. Effect of substrate pre-treatment on diamond nucleation. 2. Effect of deposition conditions on diamond nucleation and growth. 3.Preparation of free-standing diamond films using copper substrate. 4. Adherent diamond coating on copper using an interlayer. In the first part we show that diamond nucleation on copper is strongly affected by the substrate pre-treatment. The residues of abrasives left in the surface of the copper substrate play an important role in the diamond nucleation. In the second part we show that the diamond growth rate increases with microwave power and gas pressure. The effect of the microwave power is mainly an effect of substrate temperature. Increasing methane concentration results in a higher nucleation density and higher growth rate, but at the cost of a lower film quality. Gas flow rate has little influence on the diamond nucleation density and growth rate. In the third part we demonstrate the possibility of preparing large area free-standing diamond films using copper substrate, which has nearly no carbon affinity and usually leads to weak adhesion of the diamond films. The normally observed film cracking phenomenon is discussed and a two-step growth method is proposed for stress release. In the fourth part we show that adherent diamond coating on copper can be obtained using a titanium interlayer. Residual stress in the films is evaluated by Raman spectroscopy. It is found that with increase in the film thickness, the diamond Raman line shifts from higher wave numbers to lower, approaching 1332 cm–1. The stress variation along the depth of the film is also analysed using Airy stress theory.     

偏压技术在金刚石薄膜制备中应用的进展

近年来,用偏压技术进行异质外延单晶金刚石生长并将其尺寸增大到英寸级以上。偏压技术强大的形核能力使其也可用于制备取向金刚石薄膜、纳米金刚石薄膜和超纳米金刚石薄膜。本文综述了国内外关于偏压技术的机理以及偏压的形式和设备等方面的研究现状,以及表面反应模型、热尖峰模型和亚层注入模型的机理。常用的偏压包括直流偏压、直流脉冲偏压、脉冲叠合偏压和双极性脉冲偏压。还介绍了偏压对金刚石薄膜组织和性能的影响,详细阐述了其对取向生长,二次形核率,无定形碳-石墨-金刚石相转变以及生长速率和结合力的作用规律和机理。加偏压能改变轰击粒子能量和特定基团的浓度、影响金刚石相的转变和晶粒取向和尺寸,进而影响金刚石薄膜的光,力,热,电学性能。还讨论了目前研究工作中存在的一些不足,如偏压作用的机理仍不清晰,对电子浓度变化,氢原子刻蚀的作用尚缺少明确的解释等。最后展望了偏压技术在金刚石制备领域未来的研究和应用方向。     

Two-step growth of high-quality nano-diamond films using CH4/H2 gas mixture

Diamond films with fine grain size and good quality were successfully deposited on pure titanium substrate using a novel two-step growth technique in microwave plasma-assisted chemical vapor deposition (MWPCVD) system. The films were grown with varying the methane (CH₄) concentration at the stage of bias-enhanced nucleation (BEN) and nano-diamond film deposition. It was found that nano-diamond nuclei were formed at a relatively high methane concentration, causing a secondary nucleation at the accompanying growth step. Nano-diamond film deposition on pure titanium was always very hard due to the high diffusion coefficient of carbon in Ti, the big difference between thermal expansion coefficients of diamond and Ti, the complex nature of the interlayer created during diamond deposition, and the difficulty in achieving very high nucleation density. A smooth and well-adhered nano-diamond film was successfully obtained on pure Ti substrate. Detailed experimental results on the synthesis, characterization and successful deposition of the nano-diamond film on pure Ti are discussed.     

Nucleation behaviour of diamond particles on silicon substrates in a hot-filament chemical vapour deposition

Diamond films and particles have been deposited on a silicon substrate using a hot-filament chemical vapour deposition (CVD) method in order to study the effect of hydrogen on the behaviour of diamond nucleation. The nucleation density of diamond was affected by both hydrogen treatment prior to deposition and filament temperature,T _f. The nucleation density was decreased markedly with increasing hydrogen-treatment time. The nucleation density also changed with increasingT _f, which increased initially and then reached a maximum at 2100°C and decreased thereafter. Etching of the substrate surface was observed and enhanced with both increasing hydrogen-treatment time and increasingT _f. The changes in nucleation behaviour were related closely to the etching of substrate surface. These results are explained in terms of the etching of nucleation sites.     

大面积长生金刚石相关物理参量的空间分布

研究了在热丝化学气相生长金刚石的过程中,衬底温度、衬底表面附近的气体温度以及气流的质量流密度分布对金刚石膜的形核和生长的影响。模拟计算结果表明,这三个参量是空间位置的参数,在某些区域,这三个参量均匀分布。当热丝阵列面与衬底间距离超过７ｍｍ之后,这三个参量在衬底上有一个较大的均匀区域,在该区域的两侧,各参量值显著变化。在衬底中心的均匀区域,金刚石膜晶形清楚而致密;偏离该区域,这三个参量数值明显下降,形核密度和生长速度较低,三个参量均匀的区域可作为金刚石大面积均匀的形核和生长的位置。