铁基触媒合成金刚石形成的金属包膜的组织结构

利用SEM，TEM和Raman光谱检测手段，研究了铁基触媒合成金刚石形成的金属包膜的组织结构。结果表明：包膜与合成后触媒的组织形貌不完全相同，包膜内无金刚石，在靠近金刚石的包膜内层没有石墨和无定型碳。据此并结合包膜所起的溶碳和催化作用分析，在高温高压下，金刚石成核和生长的碳来源于靠近金刚石的包膜层(Fe，Ni)3C的分解产物，分解后的(Fe，Ni)3C转变为γ—(Fe，Ni)，这时的γ—(Fe，Ni)与末分解的(Fe，Ni)3C保持晶面平行关系。     

铁基触媒中铁含量对合成金刚石形貌及氮含量的影响(英文)

利用3种铁基粉末触媒,在国产六面顶压机上进行了金刚石单晶的合成实验,研究了高压高温条件下,铁基粉末触媒随铁含量的改变,石墨碳–铁基触媒体系合成金刚石条件的变化规律以及金刚石单晶的形貌,并利用红外光谱对金刚石中的含氮量进行了检测。结果表明:随着铁基粉末触媒中铁含量的增加,合成金刚石的压力和温度逐渐升高,金刚石生长的"V形区"上移,晶体的透明度变差,所合成晶体的含氮量逐渐减少。     

氮对MPCVD单晶金刚石生长与含量研究进展

微波等离子体化学气相沉积(MPCVD)技术被认为是制备高纯单晶金刚石的首选方法。然而因为氮原子的半径与碳的原子半径相近,容易成为单晶金刚石生长层中的主要杂质,是阻碍MPCVD单晶金刚石推广应用的原因之一。经过国内外研究团队的对氮与MPCVD单晶金刚石的生长与氮杂质含量控制研究取得了一些结果。但是除此之外还需要解决氮掺杂提速与控制单晶金刚石生长层中氮杂质含量的控制统一问题,才能实现MPCVD单晶金刚石的高端领域应用。     

高温高压Fe-Ni-C-B系中含硼金刚石单晶合成机理研究(下)

采用现代材料分析测试方法,通过对高温高压Fe-Ni-C-B系合成出的含硼金刚石单晶及其金属包覆膜进行系统分析和表征,探寻含硼金刚石合成机理及生长机制。研究发现,添加在金属触媒中的硼以金属-碳-硼化合物的形式溶入金属包覆膜,作为含硼金刚石生长的直接碳/硼源,经金属中间相的催化,析出活性碳/硼原子(团)扩散至正在生长的金刚石单晶表面,促进金刚石的生长。而含硼金刚石则以一种层状生长的方式长大,这种层状生长的台阶来源前期以二维晶核为主,后期则以位错为主。活性碳/硼原子(团)扩散到达金刚石单晶表面,在生长台阶的前端被吸附,转变成为金刚石单晶的一部分。随着台阶的不断扩展,新的生长台阶在刚长成的晶面上继续形成,含硼金刚石单晶则以层状堆叠的方式完成长大过程。     

优质毫米级粗颗粒金刚石单晶的高温高压合成

粗颗粒工业金刚石的合成与普通工业金刚石相比,需要较长的生长时间,而且其合成条件相对于普通工业金刚石单晶更为苛刻.文章总结了在具有高精密化控制系统的国产SPD 6×1670T型六面顶压机上进行的优质粗颗粒金刚石单晶的合成研究.在粉末触媒合成金刚石工艺的基础上,提高了压力和温度控制系统的精密化程度,引入了旁热式组装,改良了合成工艺,通过精密地控制金刚石的成核量与生长速度,以及采用最佳粒度的触媒,在高温高压条件下(～5.4GPa,～1360℃)成功合成出尺寸达到1.0mm的(18目)粗颗粒金刚石单晶,并分析了晶体的形貌和表面特征.     

金刚石单晶/镍基金属包膜界面的相结构和形貌

利用透射电镜和原子力显微镜(atomic force microscope,AFM)研究了高温高压合成金刚石过程中金刚石单晶/镍基金属包膜的界面结构和形貌.分析表明:金刚石/金属包膜界面包膜一侧由Ni3C,Mn23C,γ-(Ni,Mn)和纳米级金刚石颗粒组成,未发现石墨结构;金刚石晶面的AFM形貌与所对应的包膜表面形貌相近,但又不互为负形;金刚石(100)晶面为细小的颗粒状表面,而(111)晶面呈现出有台阶的平直表面.结果表明:金刚石的生长不是源于石墨结构的直接转变.在高温高压下,金刚石/包膜界面至包膜熔体的温度梯度差异导致了金刚石晶面形貌的不同.     

铁触媒表面的氧化铁包覆层对金刚石成核的影响

在国产SPD 6×1200型六面顶压机上,研究了高温高压条件下铁触媒表面的氧化铁包覆层对金刚石成核的影响.研究发现,在5.7GPa和1600℃的条件下,铁触媒表面的氧化铁包覆层与石墨碳源发生氧化还原反应而生成了Fe3O4和FeO,同时包覆层内部的铁熔融渗出,并与石墨碳源接触,促使了金刚石的成核生长.与纯铁触媒相比,氧化铁包覆层对金刚石成核具有明显的抑制作用,而且随着包覆层厚度的增加,抑制作用更明显.文中同时还借助穆斯堡尔谱、X-ray衍射和扫描电镜测试手段,对上述实验机理进行了深入的探讨.     

含硼金属包覆膜的物相结构与含硼金刚石的生成

使用以FeB为硼源的含硼粉末冶金铁基触媒,在六面顶压机上高温高压合成含硼金刚石单晶.金相观察发现,金刚石金属包覆膜由粗大的板条状渗碳体和细密的莱氏体共晶组织构成.X射线衍射(XRD)发现,金属包覆膜的物相组成为(Fe,Ni)3C、(Fe,Ni)3(C,B)、石墨(Gr)以及γ-(Fe,Ni)(A).使用透射电镜(TEM)在包覆膜中发现了颗粒状的Fe3(C,B),条状的γ-(Fe,Ni) 和颗粒状的Fe23(C,B)6.电子探针分析(EPMA)结果表明,硼元素在包覆膜中存在浓度梯度,越接近含硼金刚石,硼元素的含量越高.分析认为,高温高压下硼是以铁-碳-硼化合物的形式通过金属包覆膜向金刚石晶体扩散的,Fe3(C,B)或(Fe,Ni)3(C,B)极有可能是含硼金刚石生长的直接碳源和硼源.     

"柱状"金刚石晶体的高温高压合成

利用普通触媒和自行研制的新型触媒A,在国产六面顶压机上分别进行了合成金刚石单晶的实验.研究表明,普通粉末触媒合成出的金刚石单晶呈黄色,晶形完整,晶形是六-八面体,晶体透明度较好,并且合成出晶体的粒度比较集中,大约为0.3 mm.用新型触媒A合成的金刚石单晶呈绿色,并且晶形以长条晶体出现,长度集中在(0.5～0.7)mm.用SEM电镜观察到,前一种晶体晶形完整,表面光滑,后一种晶体表面也比较平整,存在"V"形缺陷.含氮量分析结果表明,用普通粉末触媒合成的金刚石的含氮量较低.     

合成后的触媒组织结构对立方氮化硼单晶合成效果的影响

以氮化锂(Li_3N)为触媒和六方氮化硼(hBN)为原料,在静态高温高压条件下加入籽晶批量合成出了≥50目的立方氮化硼(cBN)单晶。通过X射线衍射仪(XRD)和红外线光谱仪(FTIR)对合成后的触媒层内物相组成进行了分层表征;采用K值法、绝热法和RIR值等理论方法,计算出了触媒层内各物相的质量分数,分析了各物相在触媒层中的变化规律。采用扫描电子显微镜(SEM)对cBN单晶形貌和cBN单晶/触媒的界面形貌进行了观察,分析了触媒层的形貌对cBN单晶合成效果的影响。结果表明,触媒层内主要存在不规则的cBN微晶、hBN和Li3BN2等物相。触媒层的中间层是hBN发生固相直接转变生成cBN微晶的主要区域,触媒层中Li3BN2和cBN微晶的含量直接影响cBN单晶的合成效果。     

A kinetic model of diamond nucleation and silicon carbide interlayer formation during chemical vapor deposition

The presence of thin silicon carbide intermediate layers on silicon substrates during nucleation and the early stages of diamond deposition have been frequently reported. It is generally accepted that the intermediate layer is formed by the bulk diffusion of carbon atoms into the silicon carbide layer and the morphology and orientation of the diamond film subsequently grown on the intermediate layer are strongly affected by that layer. While there have been considerable attempts to explain the mechanism for intermediate layer formation, limited quantitative data are available for the layer formation under the operating conditions conducive to diamond nucleation.This study employs a kinetic model to predict the time evolution of a β-SiC intermediate layer under the operating conditions typical of diamond nucleation in hot filament chemical vapor deposition reactors. The evolution of the layer is calculated by accounting for gas-phase and surface reactions, surface and bulk diffusions, the mechanism for intermediate layer formation, and heterogeneous diamond nucleation kinetics and of its dependence on the operating conditions such as substrate temperature and inlet gas composition. A comparison between the time scales for intermediate layer growth and diamond nuclei growth is also performed. Discrepancies in published adsorption energies of gaseous hydrocarbon precursors on the intermediate layer—ranging from 1.43 to 4.61 eV—are examined to determine the most reasonable value of the adsorption energy consistent with observed saturated thicknesses, 1–10 nm, of the intermediate layer reported in the literature. The operating conditions that lead to intermediate layer growth followed by diamond deposition vs. those that yield heteroepitaxial diamond nucleation without intermediate layer formation are discerned quantitatively. The calculations show that higher adsorption energies, 3.45 and 4.61 eV, lead to larger surface number densities of carbon atoms, lower saturated nucleation densities, and larger intermediate layer thicknesses. The observed saturated thicknesses of the intermediate layer may be reproduced if the true adsorption energy is in the range of 3.7–4.5 eV. The intermediate layer thickness increases by increasing substrate temperature and inlet hydrocarbon concentration and the dependence of the thickness on substrate temperature is especially significant. Heteroepitaxial diamond nucleation without intermediate layer formation reported in experimental results can be readily explained by the significant decrease of the intermediate layer thickness at lower substrate temperatures and at higher diamond nucleation densities. Further, the present model results indicate that the intermediate layer thickness becomes saturated when growing diamond nuclei cover a very small surface area of that layer.     

Heteroepitaxy of Diamond on Cubic Boron Nitride

The epitaxial growth process of diamond from the gas phase on a cubic boron nitride (c-BN) {111} surface has been investigated. At the initial growth stage, carbon adsorption progressed on a boron-terminated surface of c-BN ({111}_B). The coordination of the carbon atoms was found to be the same as that observed in diamond, as confirmed by electron energy loss spectroscopy (EELS). The epitaxial growth of diamond particles has been observed after formation of the carbon layer. On the other hand, on the nitrogen-terminated surface ({111}_N), neither stable adsorption of carbon nor nucleation of diamond has been observed. The stability of adsorbed carbon atoms in the chemical vapor deposition (CVD) ambient, in which large amounts of atomic hydrogen are supplied to the substrate heated at high temperature, is quite important for the nucleation of diamond. Using cross-sectional transmission electron microscopy (TEM), numerous crystal defects were observed, both in c-BN and diamond. Formation of the epitaxial diamond particles has been observed especially at defect sites on c-BN. The misfit dislocation has been observed near the interface with the diamond particle. Even though there exist misfit dislocations that relieve the stress caused by the lattice mismatch between diamond and c-BN, the epitaxial film involved retains a tensile strain of about 0.29% for a film thickness of about 200 nm.     

Tribological studies of electroless nickel/diamond composite coatings on steels

In this study, a commercially available process of electroless nickel plating with co-deposited diamond powders was applied to a steel substrate as an intermediate layer prior to diamond deposition by MPECVD. The diamond films show excellent adherence, since they are strongly bounded to the diamond particles, deeply anchored into the electroless plated nickel matrix. A synergism effect of electroless nickel plating and MPECVD diamond growth are discussed. The electroless nickel plate which can be hardened itself by the precipitated phosphide phases after the heat treatment is an efficient diffusion barrier against the inter-diffusion of iron from the steel substrate and carbon from CH₄. A more continuous and smoother diamond film can be formed on the outermost surface. The results of tribotesting indicated that each step in the process of composite formation significantly lowers the friction coefficient (μ), especially the secondary layer of electroless nickel plate (~ 1 μm) is particularly effective and possesses a steadily low value of μ, which has promise for tribological applications. The secondary nickel layer could enhance the adherence of diamonds in the metal matrix, and be responsible for the better continuity of the top diamond film.     

Growth and Adhesion Enhancement of Diamond Films Deposited on Steel Substrates by a Cr–N Interlayer

Diamond film deposition onto iron-based substrates by chemical vapor deposition methods is complicated by the formation of black carbon or graphitic soot on the substrate surface prior to diamond nucleation and growth, by fast diffusion of carbon into the iron substrate, and by poor adhesion of the deposited film. These complications suggested the use of a buffer layer between the deposited diamond film and the iron-based substrate. We review different methods used to improve the adhesion of diamond film to steel substrates. In particular we describe in detail our own studies which involve the use of a Cr-N interlayer. The use of a chromium nitride interlayer has been found to improve significantly the adhesion of diamond films deposited on ferrous substrates. This is achieved by hindering diffusion processes of carbon and iron, very stable mechanical and chemical bonding between the interlayer and the diamond film, and good adhesion of the interlayer to the steel substrate. We also report on our studies related to residual stress present in the films, as well as a correlation between the interlayer properties and adhesion strength of deposited films.     

Effect of titanium metal in the prenucleation of ultrananocrystalline diamond film growth at low substrate temperature

Ultrananocrystalline diamond (UNCD) film is usually grown in methane–argon plasma unlike methane–hydrogen plasma conventionally used to deposit microcrystalline diamond film. The prenucleation and growth mechanism of these two types of diamond films are different as well. The present study introduces titanium metal powder during ultrasonication of silicon substrate to enhance the nucleation density of UNCD. A titanium thin film was also used at the interface to find the effect of metal on the growth of diamond film. The nucleation density of as-grown film was estimated from the FE-SEM images. After 20 min of growth, nucleation density reaches to 10¹¹/cm² on a surface pretreated by titanium mixed nanodiamond powder. Raman study was carried out for qualitative analysis of different carbon phase present in the UNCD films. X-ray photoelectron spectroscopy (XPS) was used to understand the growth mechanism by detecting the formation of carbon phase and metal carbide formation at the surface after stopping the growth at different time intervals.     

Planarizing CVD diamond films by using hydrogen plasma etching enhanced carbon diffusion process

Polycrystalline diamond films, deposited by microwave plasma chemical vapor deposition (MPCVD), were planarized in hydrogen plasma under the graphitization of iron film obtained by reduction of iron chloride under hydrogen plasma ambient. For this process, the free-standing diamond films were dipped in a saturated iron chloride solution and dried horizontally in atmospheric ambient. Then the diamond samples were heated by hydrogen plasma in the same MPCVD reactor. Under the effect of hydrogen reduction, iron thin film was formed on the surface of diamond films. Under ca. 800 °C, the carbon diffusion process was carried out under the graphitization effect of iron thin film. Since the iron film used in this process is very thin, the diffused carbon will diffuse from the diamond side to the hydrogen plasma side and then etched away by the plasma. Therefore, the etching rate of diamond film can be kept consistent. After etching the growth surface of a free-standing diamond film, we investigated the surface morphologies and the carbon phases on the etched surfaces of diamond films. Finally, compared with the result of mechanical lapping experiments, we suggest that the hydrogen plasma etching enhanced carbon diffusion process can serve as a new planarization method for rough diamond film surface. A mechanism for this enhanced etching effect is also presented and discussed.     

Effect of crystal structure on the electrochemical behaviour of synthetic semiconductor diamond: Comparison of growth and a nucleation surfaces of a coarse-grained polycrystalline film

Comparative studies of the electrochemical behaviour of the growth and nucleation surfaces of a free-standing boron-doped polycrystalline diamond film grown in a microwave plasma CVD reactor are performed. The uncompensated acceptor concentration in diamond is determined from the electrochemical impedance (Mott–Schottky plots), uncompensated boron acceptor concentration from infrared absorption measurements, and the total boron concentration, by the SIMS method. In the diamond bulk adjacent to the nucleation surface, constituted from submicrometre-sized crystallites, both the boron concentration and the total acceptor concentration are found to be significantly higher than near the growth surface, where the film crystallinity is more perfect. This difference is tentatively attributed to the increased concentration of crystal lattice defects near the nucleation surface. These defects, in addition to boron atoms, play the role of acceptors in diamond.     

The diffusion behavior of carbon in sputtered tungsten film and sintered tungsten block and its effect on diamond nucleation and growth

Diamond was done on sintered tungsten block with or without sputtered tungsten films. The effects of various depositing conditions, including methane concentration, temperature, pressure, the diamond seeding step and reaction time, on diamond growth were investigated in detail. The results show that the sputtered tungsten film has a dual effect on diamond growth. Firstly, after ultrasonication with diamond slurry, the tungsten film will adsorb a large number of diamond nanoparticles. Therefore, the nucleation density of diamond will be substantially improved. Secondly, the film will be carbonized during the deposition process and the carbon on the surface of the film will decrease. Methane concentration generally does not affect the carbonization level of the tungsten film but higher temperature will lead to a higher level of carbonization. The carbonization process of sputtered tungsten films during deposition is made up of two steps. Also, the nucleation surface of diamond was revealed. The nucleation surface was a layer of ultrasmooth and seamless nanocrystalline diamond film with high-quality and special surface architecture (tiny peaks arrays), which is potential to be applied in MEMS and field-emission devices. A potential method to prepare ultrasmooth nanocrystalline diamond films is proposed.     

Ru-doped nanostructured carbon films

Pure and Ru-doped carbon films are deposited on Si (100) substrates by electron cyclotron resonance chemical vapor deposition. The films are characterized by transmission electron microscopy, electron energy loss spectroscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. In both the pure and Ru-doped samples, diamond nanocrystallites are formed in amorphous carbon matrices. The Ru-doped film contains much smaller diamond nanocrystallites (approx. 3 nm) than the pure samples (approx. 11 nm). Lower surface roughnesses are observed in both pure and Ru-doped samples as compared to other reported nanocrystalline diamond films. The conductivity of the Ru-doped film is significantly higher than that of the pure film. The results show that Ru-doped nanocrystalline diamond films have unique structures and properties as compared to pure nanocrystalline diamond films or metal doped diamond-like carbon films, which may offer advantages for electrochemical, optical-window, field emission or tribological applications.     

Diamond nucleation on iridium: Local variations of structure and density within the BEN layer

The diamond nuclei generated by the bias enhanced nucleation (BEN) on iridium are gathered in well defined areas (“domains”). In atomic force microscopy (AFM) measurements they become manifest in a 1 nm downward step. The fine structure of the carbon layer inside and outside these domains has been studied by small spot Auger electron spectroscopy (AES), high resolution transmission electron microscopy (HRTEM), AFM and lateral force microscopy (LFM). The Auger spectra of the carbon KLL peak taken in an ultra high vacuum setup revealed diamond features inside and more graphitic features outside the domains. The comparison with the intensity of the Auger signal originating from the underlying Ir film indicates a carbon coverage inside the domains which is only by about 20% lower than outside. Cross section HRTEM images after BEN and after a short growth step, as well as AFM measurements after softly etching off the carbon layer, give no indication that the Ir had experienced a major modification by the domain formation process. Combining the information deduced from these experiments we conclude a significantly higher density of the carbon matrix within the domains. The lower friction forces measured in these regions by LFM confirm the interpretation of a material with higher elastic modulus. The present results allow to refine our understanding of structure and formation of the BEN layer on Ir.