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 。     

甲烷浓度对于金刚石膜二次形核的影响

采用实验室研制的石英钟罩式MPCVD装置,在低功率(950 W)条件下,以H2-CH4为反应气源,在不同甲烷浓度下沉积了金刚石膜。利用扫描电子显微镜、激光拉曼光谱及X射线衍射仪等对金刚石膜二次形核现象进行了分析。实验结果表明:甲烷浓度变化对金刚石膜沉积过程中二次形核有不同程度的影响。甲烷浓度由1.0%上升到2.5%时,薄膜中二次形核现象逐渐增加,晶粒尺寸逐渐减小,金刚石相含量下降,晶面取向由(111)面转变为(220)面以及(311)面。     

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。     

钢渗铬沉积金刚石膜的研究

用热解CVD装置研究了甲烷浓度、基底温度、室压对钢渗铬沉积金刚石膜的影响.结果表明,甲烷浓度越低,沉积得到的金刚石膜的晶形越好,甲烷浓度超过0.8%后,金刚石的形貌呈"菜花状";基体温度高时,难于在渗铬层上形成连续的金刚石膜,但基体温度高所得的晶形较好;室压越高,金刚石的形核密度越高,但随室压的升高,金刚石的形貌变差.菜花状金刚石膜是由大量二次晶核长大的微晶金刚石晶粒组成,含有较多的非金刚石碳相.     

一种提高金刚石薄膜形核密度的新方法

报导了一种提高火焰法合成高质量金刚石薄膜形核密度的新方法-化学腐蚀法;研究了在化学腐蚀试样表面上金刚石的形核与生长行为、晶粒度与形核密度之间的关系。试验表明:经腐蚀后的样品,金刚石形核均匀致密,2min内便能形成连续的膜。金刚石形核密度随晶粒度的增加而增大。初步分析了化学腐蚀法提高形核密度的原因,认为晶界对金刚石的形核起重要作用。     

杆状氧化铍表面金刚石薄膜的生长

利用一种新型线形微波等离子体源以甲烷和氢气为反应气体在135 mm×1 mm×0.5 mm杆状氧化铍表面沉积金刚石膜。研究了氧化铍基底预处理对金刚石形核密度和膜的连续性,以及基底温度对金刚石质量的影响。通过扫描电镜、拉曼光谱对沉积的金刚石膜表面形貌以及质量进行表征。实验结果表明:600#砂纸与金刚石粉混合预处理可以大大提高氧化铍表面金刚石的形核密度,得到连续性较好的金刚石薄膜;同时,基底温度不仅影响着金刚石膜的表面形貌,也影响着金刚石膜的质量。基底温度较低时,金刚石膜在沉积过程中二次形核增强,非金刚石相含量较高;提高沉积温度后,等离子体中H原子浓度增加,有利于金刚石质量的提高。     

用于X射线光刻掩模的纳米金刚石膜成核研究

介绍了金刚石膜在下一代X射线光刻掩模中应用的必要性;通过调节衬底温度,改变生长时间、控制甲烷浓度等工艺措施,实验研究了不同参数对成核密度及成核质量的影响,获得了高密度形核的样品;对形核后的预生长期进行了工艺优化,有效地控制了核岛的优势生长,总结出了一套优化的形核方案,即甲烷浓度4％,衬底温度700℃,形核时间14min;这套工艺不仅改善了自支撑金刚石薄膜窗口的光学性能,还有效地降低了膜的内应力。     

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.     

金刚石厚膜的晶界对耐磨性的影响

用直流辉光等离子体化学气相沉积制备金刚石厚膜,用氢的微波等离子体对其抛光截面进行刻蚀,研究了晶界对金刚石厚膜耐磨性的影响.结果表明：在金刚石膜的生长过程中,随着甲烷流量的增加,金刚石膜的晶界从纵向排列为主过渡到网状结构,晶粒内部缺陷逐渐增加,杂质、空洞主要分布于晶界处．金刚石膜的磨耗比随着晶界密度、宽度、杂质含量及晶粒内部缺陷的增加而下降．晶界是杂质、空洞主要富集区,是影响金刚石厚膜耐磨性的主要因素．     

形核工艺对金刚石膜形貌和电阻率的影响

金刚石薄膜电阻率的高低是薄膜绝缘性能优劣的直观反映,也是影响辐射剂量计器件性能的重要因素.针对目前形核工艺与电阻率的关系还不十分清楚的问题.本文研究了微波等离子体形核阶段工艺参数如基片位置、微波功率、甲烷浓度的变化对金刚石薄膜的表面形貌和电阻率的影响.结果表明微波等离子体形核工艺参数对金刚石薄膜的电阻率和表面形貌有显著影响.获得的最佳成核工艺条件:基体温度960℃、甲烷浓度0.72%、压力5.3 kPa、微波功率1300 W.在此工艺条件下制得的金刚石薄膜的电阻率值达到1011 Ω·cm数量级.     

Adherent diamond coating on copper using an interlayer

With a titanium interlayer, adherent diamond coating on copper is obtained. The diamond nucleation density is enhanced significantly by scratching the substrate with diamond powder and is influenced by the deposition conditions. It is found that the diamond growth rate increases with microwave power, gas pressure and methane concentration. However, a higher methane concentration results in increased growth defects and non-diamond phases. Under typical deposition conditions, the diamond crystals exhibit a (111) face dominating. The coating adhesion is accessed by pull-off tests and scratch tests. The former indicates that the coating adhesion is better than the strength of the adhesive, at ca 13 MPa. The latter shows a critical load about 8 N.     

Microwave plasma enhanced chemical vapor deposition diamond synthesis from high carbon content source

To synthesize diamond films by microwave plasma enhanced chemical vapor deposition (MPECVD), the methane concentration (CH₄/H₂)plays a crucial role. It is well-known that there always exists a critical methane concentration (≤0.6%) only below which a good quality diamond film can be obtained. In this study, however, the phenomena of diamond synthesis resulting from high carbon concentration conditions were observed. The molten metals, e.g., Ag, Cu, were used as the deposition substrates on which crystalline diamonds can be achieved from a methane content of CH₄/H₂≥6% or even from solid carbon sources. These results suggest that there may exist a low methane content boundary layer (<0.6%) in the proximity of molten metal surface on which suitable species, CH, CH⁺, H_α and H_β are composed for the diamond nucleation and growth similar to the condition as in the conventional low methane contents. The molten metal inclines to dissolve other forms of carbonaceous materials other than diamond, and thus keeps a much higher steady supply of carbon atoms that enhances the quality as well as the growth rate of the forming diamonds. Received: 23 June 2001 / Accepted: 23 July 2001     

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.     

Effects of enhanced nucleation on the growth and thermal performance of diamond films deposited on BeO by hot filament CVD technique

A method of controlling the feeding concentration of methane was applied in a hot-filament chemical vapor deposition (HFCVD) in order to improve the nucleation of diamond on the beryllium oxide substrates. The nucleation density and the morphologies of diamond were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) while the thermal conductivities of substrates and the composites were detected by laser-diathermometer. The results show that the diamond thin film is in larger grain size with lower roughness when CH₄ and H₂ enter the chamber, respectively, rather than as a mixture, and the composites’ conductivity soared by 21%–31% compared with BeO substrates. At the conditions of separated gas entry, several projects with changes of the CH₄ flux during depositing were designed to discuss the influence of CH₄ concentration on diamond nucleation. The uniform and compact diamond thin films were acquired when the ratio of CH₄:H₂ at nucleation stage was in the range of 4%–8%.     

CVD nanocrystalline diamond coatings on Ti alloy: A synchrotron-assisted interfacial investigation

Diamond coating on Ti-6Al-4V alloy was carried out using microwave plasma enhanced CVD with a super high CH₄ concentration, and at a moderate deposition temperature close to 500 °C. The nucleation, growth, adhesion behaviors of the diamond coating and the interfacial structures were investigated using Raman, XRD, SEM/TEM, synchrotron radiation and indentation test. Nanocrystalline diamond coatings have been produced and the nucleation density, nucleation rate and adhesion strength of diamond coatings on Ti alloy substrate are significantly enhanced. An intermediate layer of TiC is formed between the diamond coating and the alloy substrate, while diamond coating debonding occurs both at the diamond-TiC interface and TiC-substrate interface. The simultaneous hydrogenation and carburization also cause complex micro-structural and microhardness changes on the alloy substrates. The low deposition temperature and extremely high methane concentration demonstrate beneficial to enhance coating adhesion strength and reduce substrate damage.     

Effect of reaction pressure on the nucleation behaviour of diamond synthesized by hot-filament chemical vapour deposition

Synthetic diamond particles were deposited on a Si (1 0 0) substrate using a hot-filament chemical-vapour-deposition method in order to study the effect of the reaction pressure on the nucleation behaviour. The reaction pressure was controlled, as an experimental variable, from 2 to 50 torr under the following conditions: a filament temperature of 2200 °C, a substrate temperature of 850 °C, a total flow rate of 200 s.c.c.m. and a methane concentration of 0.8 vol%. Diamond deposits on the Si wafer were characterized by micro-Raman spectroscopy, scanning electron microscopy (SEM) and optical microscopy.The maximum nucleation density of diamond particles on the unscratched Si substrate is shown at the reaction pressure of 5 torr. These phenomena can be explained by the competition effect between -SiC formation, which increases the diamond nucleation density, and atomic-hydrogen etching which decreases the nucleation sites.A new fabrication method for a high-quality diamond film without any surface pretreatments is introduced using a combination process between diamond nucleation at low pressure (5 torr) and growth at high pressure (30 torr).     

Effects of enhanced nucleation on the growth and thermal performance of diamond films deposited on BeO by hot filament CVD technique

A method of controlling the feeding concentration of methane was applied in a hot-filament chemical vapor deposition (HFCVD) in order to improve the nucleation of diamond on the beryllium oxide substrates. The nucleation density and the morphologies of diamond were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) while the thermal conductivities of substrates and the composites were detected by laser-diathermometer. The results show that the diamond thin film is in larger grain size with lower roughness when CH₄ and H₂ enter the chamber, respectively, rather than as a mixture, and the composites’ conductivity soared by 21%–31% compared with BeO substrates. At the conditions of separated gas entry, several projects with changes of the CH₄ flux during depositing were designed to discuss the influence of CH₄ concentration on diamond nucleation. The uniform and compact diamond thin films were acquired when the ratio of CH₄:H₂ at nucleation stage was in the range of 4%–8%.     

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.