镍改性层增强铜基底沉积金刚石膜的形核(英文)

在铜基底溅射约100nm厚的镍改性层,然后置入纳米金刚石悬浮液中超声震荡加载籽晶,随后在热丝化学气相沉积设备中制备出晶体颗粒接近热力学平衡形态的高质量金刚石膜,其中sp2碳相含量低于5.56%。分别采用激光拉曼光谱、扫描电镜与X射线衍射对金刚石膜的形核与生长进行研究。实验结果表明:在溅射有镍改性层的铜基底上,金刚石的形核密度比在无改性层的铜基底上的形核密度高10倍。镍改性层的增强机制主要来源于两个方面:镍改性层的纳米级粗糙表面增强金刚石籽晶颗粒的吸附;镍改性层的强催化效应加速铜基底上金刚石形核生长所需的石墨过渡层的形成,从而促进金刚石的快速形核。     

A study of diamond synthesis by hot filament chemical vapor deposition on Nc coatings

Deposition of diamond films onto various substrates can result in significant technological advantages in terms of functionality and improved life and performance of components. Diamond is hard, wear resistant, chemically inert, and biocompatible. It is considered to be the ideal material for surfaces of cutting tools and biomedical components. However, it is well known that diamond deposition onto technologically important substrates, such as co-cemented carbides and steels, is problematic due to carbon interaction with the substrate, low nucleation densities, and poor adhesion. Several papers previously published in the relevant literature have reported the application of interlayer materials such as metal nitrides and carbides to provide bonding between diamond and hostile substrates. In this study, the chemical vapor deposition (CVD) of polycrystalline diamond on TiN/SiN _x nc (nc) interlayers deposited at relatively low temperatures has been investigated for the first time. The nc layers were deposited at 70 or 400 °C on Si substrates using a dual ion beam deposition system. The results showed that a preliminary seeding pretreatment with diamond suspension was necessary to achieve large diamond nucleation densities and that diamond nucleation was larger on nc films than on bare sc-Si subjected to the same pretreatment and CVD process parameters. TiN/SiN _x layers synthesized at 70 or 400 °C underwent different nanostructure modifications during diamond CVD. The data also showed that TiN/SiN _x films obtained at 400 °C are preferable in so far as their use as interlayers between hostile substrates and CVD diamond is concerned. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.     

热丝辐射距离和W-C梯度过渡层对高速钢基体气相生长的影响

使用反应磁控溅射技术在W18Cr4V高速钢基体表面制备W-C梯度过渡层(WCGC),采用热丝化学沉积法(HFCVD),以甲烷和氢气为反应气体,在基体表面生长金刚石膜。采用场发射扫描电子显微镜(FE-SEM)、X射线衍射仪(XRD)和激光拉曼光谱(Raman)对W-C过渡层和金刚石膜进行检测分析,研究热丝辐射距离和沉积气压对WCGC与金刚石膜的的影响。结果表明:热丝辐射距离对金刚石薄膜和WCGC均有较大影响;WCGC过渡层能够在一定热丝辐射范围内降低Fe在金刚石膜沉积过程的负面影响,有效提高金刚石的形核率,在基体表面得到连续致密的金刚石膜。     

Effects of pre-treatments and interlayers on the nucleation and growth of diamond coatings on titanium substrates

During diamond deposition on titanium substrates, two processes exist: (1) diffusion of hydrogen into a titanium substrate and the formation of hydride thereby degrading the mechanical properties of the substrate; and (2) competition among the rapid diffusion of carbon atoms into substrates, the formation of carbide and the nucleation of diamond crystals (thereby affecting the nucleation and growth rate of the diamond coating). To increase the diamond nucleation rate and prevent the rapid diffusion of hydrogen and carbon into the substrate, different surface treatments and interlayers were studied in this paper. Results showed that polishing with diamond pastes and ultrasonic pre-treatment in diamond suspensions will significantly increase the nuclei density of diamond crystals. However, the diffusion of hydrogen into the substrate could not be prevented. Pre-etching of the titanium substrate using hydrogen plasma for a short time significantly increased the nuclei density of diamond crystals. Results showed that on a TiN interlayer, there was no significant improvement in diamond nucleation and growth, and the deposited diamond coatings showed poor adhesion. New diamond crystals were formed on the DLC interlayer in which DLC acted as the precursor for diamond nucleation. However, the so-formed diamond coating showed spallation. The plasma nitrided layer could prevent the rapid diffusion of hydrogen and carbon into the titanium substrate, but results showed a relatively low nucleation density of diamond crystals and poor adhesion. A graded interlayer combining plasma nitriding followed by plasma carbonitriding was effective in preventing the rapid diffusion of hydrogen and carbon into the substrate and improving the nucleation rate and adhesion of diamond coating.     

Nucleation and growth of combustion flame deposited diamond on silicon nitride

The effect of substrate temperature (T_s) on the nucleation and growth of diamond on silicon nitride (Si₃N₄) based substrates deposited via the oxy-acetylene combustion flame technique was investigated. The diamond deposits were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The nucleation density of the resulting deposits, which was of the order 10⁵ nuclei/cm², was used to approximate the activation energy for heterogeneous nucleation of diamond as32 – 40 kcal/mol. An Arrhenius plot of particle growth rate was used to calculate the activation energy for diamond growth as9.4 and 8.3 kcal/mol in the center and outside annulus of the deposit, respectively. These results suggest that the heterogeneous nucleation of diamond is a highly energetic process and may in fact be responsible for the observed low nucleation density of diamond on Si₃N₄. Thermodynamic analysis of gas/substrate reactions under conventional process conditions predicted that SiC formation, which is known to be a necessary precursor to diamond nucleation on Si, is energetically forbidden. Via kinetic and thermodynamic considerations, a patented in situ multistage deposition technique was developed which yielded continuous diamond coatings on Si₃N₄ substrates without extensive substrate preparation.     

Effect of pretreatment, seeding and interlayer on nucleation and growth of HFCVD diamond films on cemented carbide tools

The direct deposition of diamond on carbide tools is difficult because formation of graphitization and thus leading to poor adhesion, due to presence of cobalt on the surface. Various methods were adopted to suppress the effect of cobalt during deposition. One of them was by putting an interlayer. In this study, carbide substrates with coatings of Ti, TiN and TiC were used. Ti coating has a strong tendency to form intermediate carbide leading to the highest nucleation density of diamond. A comparison was made on nucleation and growth of diamond crystals on various interlayers by hot filament CVD method. At the same time, the variations of diamond film growth morphology have been studied on unseeded and seeded carbide inserts. The SEM pictures revealed that among interlayer, Ti coating gave highest nucleation density compared to TiN and TiC coatings. At the same time, diamond seeded inserts, pretreated by Treat 1 [HCl + HNO₃ + H₂O (1:1:1)] for 15 min ultrasonically resulted in the highest nucleation density, compared to Treat 2 [K₃[Fe(CN)₆] + KOH + H₂O] solution in (1:1:10) for 15 min, at constant process parameters.     

预处理对金刚石薄膜质量及结合力的影响

目的改善硬质合金表面金刚石薄膜的结合力。方法采用热丝CVD法在硬质合金基体上制备金刚石薄膜,研究对比喷砂+一步法、喷砂+两步法、Al Cr N过渡层和传统两步法这四种预处理对金刚石薄膜质量及其结合性能的影响。对预处理后硬质合金基体表面的形貌和粗糙度进行分析,并通过扫描电子显微镜、X射线衍射、拉曼光谱及洛氏硬度计表征金刚石薄膜的形貌、结构及性能。结果喷砂有利于在基体表面获得均匀分布的凹坑,提高金刚石的形核密度及均匀性,尤其改善了金刚石颗粒的团聚现象。Al Cr N过渡层虽然表面粗糙度不高,但有大量的凸起颗粒,提供了极佳的形核点,也在一定程度上优于传统两步法的表面金刚石形核密度。在金刚石薄膜沉积参数不变的前提下,传统两步法预处理获得的涂层结合力为HF4级,喷砂结合一步法和两步法获得的结合力分别达到了HF3级和HF1级,但Al Cr N过渡层的结合力表现较差。结论 Al Cr N过渡层能阻挡Co的扩散,提高了金刚石的纯度,但金刚石膜的内应力较大,结合力差。喷砂和刻蚀复合预处理不仅能提高金刚石的结晶质量和纯度,金刚石薄膜的结合力也得到改善。     

CVD金刚石涂层硬质合金衬底预处理新方法研究

本文研究了甲醇预处理方法对硬质合金衬底表面抑制Co催石墨化作用。将甲醇预处理方法融入到传统的两步处理方法中,提出了新的两步预处理方法,通过电镜和EDX等手段对预处理后的衬底表面形貌、成分进行了分析。采用偏压增强热丝CVD(HFCVD)法,在预处理后的衬底表面成功沉积了金刚石薄膜。并以制做钻头为例,验证了两步法对复杂形状衬底的预处理及金刚石薄膜制备效果。研究结果表明:采用甲醇预处理方法能够有效抑制Co对金刚石薄膜的不利影响,新的两步预处理方法既能保证金刚石薄膜与衬底之间的附着强度,又非常适用于复杂形状整体式回转硬质合金刀具、拉拔模具等衬底,对于拓展金刚石涂层在涂层刀具领域的应用具有一定的参考作用。     

Effects of Ti- and Zr-based interlayer coatings on hot-filament chemical vapor deposition of diamond on high-speed steel

The prospect of obtaining good adhesion of diamond films onto steel substrates is highly exciting because the achievement of this objective will open up numerous new applications in industry. However, a major problem with depositing diamond onto steel is high diffusion of carbon into steel at chemical vapor deposition (CVD) temperatures leading to a very low nucleation density and cementite (Fe₃C) formation. Therefore, the study of the nucleation and growth processes is timely and will yield data that can be utilized to get a better understanding of how adhesion can be improved. This work focuses on the adhesion of thin diamond films onto high speed steel previously coated with various interlayers such as ZrN, ZrC, TiC, and TiC/Ti(C,N)/TiN. The role of seeding on nucleation density and the effect of diamond film thickness on stress development and adhesion has been investigated using scanning electron microscopy (SEM), x-ray diffraction (XRD), and Raman spectroscopy (RS). The main emphasis in this study lies with TiC, which for the first time proved to be a suitable layer for diamond CVD on high-speed steel (HSS). In fact, different from other interlayer materials investigated, no delamination was observed after 3 h of CVD at 650 °C when TiC was used. Nevertheless, the increase of diamond film thickness on TiC-coated HSS substrates led to delamination of small areas. This occurrence suggests that there was a distribution of adhesive toughness values at the diamond/TiC interface with the stress development being dependent on film thickness. This paper was presented at the fourth International Surface Engineering Congress and Exposition held August 1–3, 2005 in St. Paul, MN.     

CVD金刚石薄膜及膜-基界面形态

采用直流等离子体财流CVD法在硬质合金基体上沉积了多晶金刚石薄膜,借助XRD、Raman光谱、SEM和EPMA等对金刚石薄膜及膜-基界面的结构、形貌和成分进行了研究.结果表明,结晶度高的刻面型金刚石薄膜质量、纯度较好,膜-基界面处较致密,机械锚固作用明显,结合性能较好沉积前后基体表面形貌变化很大,存在数十微米厚的脱钴-等离子体刻蚀层,等离子体刻蚀导致脱钻表面更加凹凸不平,为金刚石形核提供了有利条件.     

CVD金属石薄膜及膜——基界面形态

采用直流等离子体射流ＣＶＤ法在硬质合金基体上沉积了多晶金刚石薄膜,借助ＸＲＤ,Ｒａｍａｎ,光谱、ＳＥＭ和ＥＰＭＡ等对金刚石薄膜及膜－基界面的结构、形貌和成分进行了研究,结果表明,结晶度高的刻面型金刚石薄膜质量、纯主较好,膜－基界面处较致密,机械锚固作用明显,结合性能较好,沉积前后基体表面形貌变化很大,存在数十数米厚的脱钴－等离子体刻蚀层,等离子体刻蚀导致脱钴表面更加凹凸不平,为金刚石形核提供了有利     

溶媒表面夹杂物对金刚石形核的影响

本文在对Ｔｉ７０－Ｍｎ２５－Ｃｏ５合金溶媒片进行表面夹杂物的观察与分析之后，向溶媒片表面添加了与这些夹杂物或类似的粉末粒子，以研究其对金刚石形核的影响作用。结果发现，在原始ＮｉＭｎＣｏ合金溶煤片表面本身就存在着许多夹杂物粒子，而向溶媒片表面添加与之相似的粉末粒子，将导致金刚石形核密度的明显增加。在金刚石合成中，溶媒片表面夹杂物的存在对金刚石形核密度的控制的影响作用是不可忽视的。     

Effect of mechanical pretreatment on nucleation and growth of HFCVD diamond films on cemented carbide tools with a complex shape

To enhance the mechanical pretreatment efficiency for WC-Co complex-shaped cutting tools, a self-made vibrating grinding equipment and mixed abrasives made up of walnut shell and diamond particles are proposed. The technique can abrade the dozens of tools simultaneously, modify surface properties of tools, and maintain sharpness of the cutting edges. Several experiments are performed to explore effects of the different types and proportions of walnut shell and diamond powders on the properties of nucleation, growth, and adhesion of diamond films deposited via a chemical vapor deposition method. Subsequently, Field Emission Scanning Electron Microscopy (FE-SEM), Atomic Force Microscopy (AFM,), Laser scanning micro-gauge, Micro-Raman Spectroscopy, Stylus Profiler, and Rockwell hardness tester are adopted to characterize the as-pretreated substrates and as-deposited diamond films. According to the results, a low residual cobalt content around 0.2 wt% and a markedly increased surface defects are detected on the pretreated milling tools when the preferred types and proportions of mixed abrasives are applied, which can help to significantly enhance the nucleation density and growth rate of diamond films, and strengthen the adhesion between the films and substrates.     

Nucleation of highly oriented diamond on silicon

Highly oriented diamond particles were deposited on the mirror-polished (100) silicon substrates in the belljar type microwave plasma deposition system. The diamond films were deposited by a three-step process consisting of carburization, bias-enhanced nucleation and growth. The bias-enhanced nucleation was performed under the deposition conditions such as 2-3% of methane concentration in hydrogen, 1333-2666 Pa of total pressure, the negative bias voltage below 200V and the substrate temperature of 1073 K. By adjusting the geometry of the substrate and substrate holder, very dense disc-shaped plasma was formed on the substrate when the bias voltage was below 200V. As characterized by transmission electron microscopy (TEM), almost perfectly oriented diamond particles were obtained only in this dense plasma. From the results of the optical emission spectra of disc-shaped dense plasma, it was found that the concentrations of atomic hydrogen and hydrocarbon radicals were increased with negative bias voltage. As a result, it was suggested that the highly oriented diamonds were obtained by the combination of the high dose of hydrocarbon radicals and the increased hydrogen etching effects.     

静压法合成金刚石的成核研究

针对静高压合成技术中片状样品的组装工艺特点,分析了在高温（约1500K)高压（约5GPa）下石墨与触媒之间的相互扩散过程和金刚石在合成腔中的成核几率。根据外界提供给石墨的能量大小,判断出纳米石墨微晶是形成金刚石晶核的基本单元。金刚石成核很可能是纳米石墨微晶转化为金刚石晶核的结构相变过程。讨论了在触媒的参与下金刚石的成核率与温度压力变化的关系,证明了压力是控制金刚石成核的有效参数,而温度不宜作为金刚石成核的控制参数。     

沉积参数对Mo-Re合金基体上沉积金刚石薄膜的影响

采用热丝化学气相沉积法(HFCVD),以甲烷和氢气为反应气体,在综合性能良好的Mo-40%Re(摩尔分数)合金基体上沉积金刚石薄膜.采用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)和显微激光拉曼光谱仪(Raman)分别对金刚石薄膜相组成、表面形貌、晶粒大小和质量等进行检测分析,研究CVD沉积参数,如基体温度(θs)、碳源浓度(R,Cn4的体积分数)和沉积压强(p),对金刚石形核、生长和金刚石成膜的影响.结果表明在合适的基体预处理条件下,当θs=750℃,R=-3%,p=3.5kPa时,薄膜平均线生长速率高达1μm/h,得到的金刚石膜完整致密,晶粒大小均匀,纯度较高,具有明显的(111)织构.     

Cobalt diffusion in different microstructured WC-Co substrates during diamond chemical vapor deposition

Our investigation on diamond deposition using cemented tungsten carbide (WC-Co) has shown that diamond particles deposit at different rates onto micrograin and coarse-grain WC-Co substrates. Diamond deposition was carried out using a parallel-plate plasma-enhanced chemical vapor deposition system, which utilized the bias-enhanced growth (BEG) process. BEG was performed at four different times: 15, 20, 25, and 30 min. The resultant diamond-based deposits were characterized for morphology, microstructure, and crystallinity using scanning electron microscopy. It was found that diamond nucleation initiated at the grain boundaries of the substrates. The present article discusses the possible reasons that can potentially explain our key findings. In particular, the CO diffusion from the bulk material through the grain boundaries and onto the substrate surface using a theoretical approach.     

脱钴处理对YG8硬质合金刀片上金刚石形核的影响

对比分析了经金刚石磨盘研磨、脱铅、未脱钻YG8硬质合金上蒸镀非晶碳膜对金刚石形核的影响．结果表明未脱钴YG8硬质含金上沉积金刚石膜时,即使蒸镀非晶碳膜,金刚石的形核密度仍相当低．金刚石结晶质量差．颗粒呈“菜花状”。在长时间沉积金刚石过程中,基体内的Co会扩散或蒸发到刀片表面,产生明显的钴颗粒聚集、长大。而脱钴、蒸镀非晶碳膜YG8硬质含金上沉积金刚石膜时．成核密度可达108cm-2．金刚石结晶质量好,刻面轮廓分明．表面已基本成膜。     

梯度基体温度法和反应溅射TiC过渡层对钛合金基体沉积金刚石薄膜的影响

以H2和CH4作为反应气体,采用热丝化学气相沉积法(HFCVD)在钛合金(Ti6Al4V)平板基体上制备金刚石薄膜,利用扫描电镜(SEM)、X射线衍射仪(XRD)、激光拉曼光谱(Raman)和洛氏硬度仪分析薄膜的表面形貌、结构、成分和附着性能,研究了高温形核-低温生长的梯度降温法对原始钛合金和反应磁控溅射TiC过渡层的钛合金表面沉积金刚石薄膜的影响。结果表明:原始基体区和TiC过渡层区沉积的金刚石薄膜平均尺寸分别为0.77μm和0.75μm,薄膜内应力分别为-5.85GPa和-4.14GPa,TiC层的引入可以有效提高金刚石的形核密度和晶粒尺寸的均匀性,并减少薄膜残余应力;高温形核-低温生长的梯度降温法可以有效提高金刚石的形核密度和质量,并提高原始基体上沉积金刚石薄膜的附着性能。     

MPCVD中双基片台结构对单晶金刚石生长的影响

在波导耦合的微波等离子体化学气相沉积制备金刚石的装置中引入双基片台结构,用光谱仪测量等离子体的发射光谱,用Raman光谱仪和SEM分析生长的单晶金刚石的Raman位移和表面形貌,对比研究双基片台结构对等离子体发射光谱和单晶金刚石生长的影响。研究表明:双基片台结构可以提高等离子体的功率密度。在相同的沉积参数下,双基片台结构有利于提高等离子体发射光谱的强度,从而显著提高单晶金刚石的生长速率,最快可达到24 μm/h。生长的单晶金刚石具有金刚石Raman特征峰的偏移度更小,Raman特征峰的半高宽更窄,非金刚石相含量更少的特点。