Tribological behaviour of diamond and diamondlike carbon films: status and prospects

Abstract

Diamond and diamondlike carbon films possess several unique characteristics that govern their tribological properties, in particular their high hardness and lubricity nature. In this paper, the influence of the deposition methods on the adhesion of the films and on their wear resistance and frictional properties is summarised. It is observed that the deposition technique contributes greatly to the variation in microstructure of the diamond or diamondlike carbon film. The multitude of tribotesters (pin-on-disc, reciprocating ball-on-plate, ball-on-three flat, etc.) used to evaluate these films also complicate the interpretation of the tribological performance and confuse direct comparisons of the deposition techniques. Also, the effect of non-diamond carbons and hydrogen in the film is elucidated in relation to the friction coefficient. The application of these films to rolling and sliding components in various industries is highlighted, together with their limitations. The hard brittle nature of the film makes it an excellent candidate in abrasive and erosive applications, but less desirable in rolling contact. Choice of substrate material is critical in order to support the film under high contact stresses.

MST/1692     

Niederenergie-IBAD: Zusammenhang zwischen Prozeßparametern und Schichteigenschaften bei ionenstrahlunterstützten Aufdampf-und Sputtertechniken

Low energy IBAD: correlation between process parameters ans film properties for ion beam assisted evaporation and sputter deposition Binary nitride films with Al, Cr and Ti as metal components have been deposited with ion beam assisted evaporation and sputtering (IBAD) and the film properties are investigated in terms of the individual deposition parameters. In the case of ion beam assisted evaporation the flux ratio between the film forming metal atoms and the nitrogen ions from the ion source was shown to enable a quantitative control of the composition and the chemical phases of the films. Detailed studies for TiN reveal the possibilities to manipulate texture and stress, the average grain size and the morphology of the films. Such results are discussed with an extended structure zone model, introducing the energy input per film forming particle as the relevant parameter. Also, the structural film properties and the deposition parameters are quantitatively correlated with the hardness and the beginning of TiN deposition on stainless steel resulted in distinctly improved adhesion properties. For the deposition of TiN with a dual ion beam arrangement in which one beam bundle was directed onto a Ti-target and an other onto the substrate with the growing film, a strong influence of the particle energies and the incidence angles on the film texture and its directional orientation was found. Such effects are quantitatively related to the minimization of the free energy of the films and the influence of preferential re-sputtering effects. For ion beam sputter deposition without simultaneous ion bombardment of the growing film, the texture and the film stress are found to be controlled by energetic particles resulting from elastic backscattering at the target surface.     

A review of crystallographic textures in chemical vapor-deposited diamond films

Diamond is one of the most important functional materials for film applications due to its extreme physical and mechanical properties, many of which depend on the crystallographic texture. The influence of various deposition parameters matters to the texture formation and evolution during chemical vapor deposition (CVD) of diamond films. In this overview, the texture evolutions are presented in terms of both simulations and experimental observations. The crystallographic textures in diamond are simulated based on the van der Drift growth selection mechanism. The film morphology and textures associated with the growth parameters α (proportional to the ratio of the growth rate along the 〈100〉 direction to that along the 〈111〉 direction) are presented and determined by applying the fastest growth directions. Thick films with variations in substrate temperature, methane concentration, film thickness, and nitrogen addition were analyzed using high-resolution electron back-scattering diffraction (HR-EBSD) as well as X-ray diffraction (XRD), and the fraction variations of fiber textures with these deposition parameters were explained. In conjunction with the focused ion beam (FIB) technique for specimen preparation, the grain orientations in the beginning nucleation zones were studied using HR-EBSD (50 nm step size) in another two sets of thin films deposited with variations in methane concentration and substrate material. The microstructures, textures, and grain boundary character were characterized. Based on the combination of an FIB unit for serial sectioning and HR-EBSD, diamond growth dynamics was observed using a 3D EBSD technique, with which individual diamond grains were investigated in 3D. Microscopic defects were observed in the vicinity of the high-angle grain boundaries by using the transmission electron microscopy (TEM) technique, and the advances of TEM orientation microscopy make it possible to identify the grain orientations in nano-crystalline diamond.     

Pulsed ion beam characterization of CVD diamond surfaces under thin film deposition conditions

Diamond and diamond-like carbon have properties which in principle make them ideally suited to a wide variety of thin-film applications. The widespread use of diamond thin films, however, has been limited for a number of reasons related largely to the lack of understanding and control of the nucleation and growth processes. Real-time, in-situ studies of the surface of the growing diamond film are experimentally difficult because these films are normally grown under a relatively high pressure of hydrogen, and conventional surface analytical methods require an ultrahigh vacuum environment. Pulsed ion beam based analytical methods with differentially pumped ion sources and particle detectors are able to characterize the uppermost atomic layer of a film during growth at ambient pressures in the range 0.7–27 Pa (4–6 orders of magnitude higher than other surface-specific analytical methods). We describe here a system which has been developed for the purpose of determining the hydrogen concentration and bonding sites on diamond surfaces as a function of sample temperature and ambient hydrogen pressure under hot-filament chemical vapor deposition (CVD) growth conditions. It is demonstrated that as the hydrogen partial pressure increases the saturation hydrogen coverage of the surface of a CVD diamond film increases, but that the saturation level depends on the atomic hydrogen concentration and substrate temperature. At the highest temperatures studied (700 °C), it was found that the surface hydrogen concentration did not exceed 1/4 monolayer.     

A review of crystallographic textures in chemical vapor-deposited diamond films

Diamond is one of the most important functional materials for film applications due to its extreme physical and mechanical properties, many of which depend on the crystallographic texture. The influence of various deposition parameters matters to the texture formation and evolution during chemical vapor deposition (CVD) of diamond films. In this overview, the texture evolutions are presented in terms of both simulations and experimental observations. The crystallographic textures in diamond are simulated based on the van der Drift growth selection mechanism. The film morphology and textures associated with the growth parameters α (proportional to the ratio of the growth rate along the〈100〉direction to that along the 〈111〉direction) are presented and determined by applying the fastest growth directions. Thick films with variations in substrate temperature, methane concentration, film thickness, and nitrogen addition were analyzed using high-resolution electron back-scattering diffraction (HR-EBSD) as well as X-ray diffraction (XRD), and the fraction variations of fiber textures with these deposition parameters were explained. In conjunction with the focused ion beam (FIB) technique for specimen preparation, the grain orientations in the beginning nucleation zones were studied using HR-EBSD (50nm step size) in another two sets of thin films deposited with variations in methane concentration and substrate material. The microstructures, textures, and grain boundary character were characterized. Based on the combination of an FIB unit for serial sectioning and HR-EBSD, diamond growth dynamics was observed using a 3D EBSD technique, with which individual diamond grains were investigated in 3D. Microscopic defects were observed in the vicinity of the high-angle grain boundaries by using the transmission electron microscopy (TEM) technique, and the advances of TEM orientation microscopy make it possible to identify the grain orientations in nano-crystalline diamond.     

Deposition of Diamond Films in a Closed Hot Filament CVD System

A closed system hot filament chemical vapor deposition (CVD) reactor has been used to deposit diamond films on silicon substrates. A fixed charge of hydrogen gas is fed into the deposition system until the desired deposition pressure level is reached. A solid graphite cylindrical rod held above the tungsten filament was the carbon source. System parameters for diamond film growth have been determined. The diamond structure of the films has been verified by x-ray diffraction (XRD). Morphology typical of CVD diamond films has been observed in scanning electron microscopy (SEM). The quality of the diamond films has been evaluated by micro-Raman spectroscopy.     

离子束增强沉积制备TiB_2薄膜及其性能研究

用离子束增强沉积法（IBED）在硅及铜基体上沉积了TiB2薄膜，研究了轰击离子束能量和束流对薄膜的微结构及力学性能的影响。用俄歇电子谱（AES）分析了膜的成分及其界面状况，用X射线衍射（XRD）研究了膜的微结构，并测定了膜的硬度及进行了膜的高温氧化试验。结果指出：（1）离子束轰击使薄膜晶化，从而影响到膜的硬度及抗高温氧化性能；（2）离子束增强沉积的二硼化钛薄膜是一种耐高温氧化的高硬膜。     

Precursor gas effect on the mechanical and optical properties of ion beam deposited diamond-like carbon films

The effect of precursor gases on the diamond-like carbon (DLC) film deposition was investigated by the direct ion beam deposition method. DLC films were deposited using methane and benzene as the precursor gases. Ion energies for the deposition range from 100 to 700 eV were achieved by adjusting the beam voltage. The residual stresses, refractive indices and optical band gaps were compared at the same ion energy. We observed significant differences in residual stress and optical properties between these films. As in r.f. plasma-assisted CVD, the residual stresses of the films deposited from benzene show a characteristic behaviour of lower ion energy deposition than those deposited from methane. The present observations are discussed in terms of the difference in ion energy per carbon atom at the growth surface. We also observed that the Ar addition effect on the residual stress is strongly dependent on the precursor gases.     

介质保护膜制备参数对AC PDP放电特性的影响

以ＭｇＯ为例,对ＡＣ　ＰＤＰ中电子束蒸发介质保护膜制备的工艺参数,如成膜时基板温度、沉积速率、成膜后的热处理条件等对ＡＣＰＤＰ工作特性的影响进行了系统的研究和分析,讨论了保护膜成分、结构、形貌等对发射特性和ＡＣＰＤＰ工作特性的影响,探讨了成膜的最佳工艺,并根据在放电过程中,由离子轰击产生的 ＭｇＯ膜表面特性的变化和假设氧对 ＭｇＯ膜表面特性的作用,对观测到的放电特性对 ＡＣＰＤＰ板各种制造工艺参数的依赖性进行了解释。     

The effect of the ion beam energy on the properties of indium tin oxide thin films prepared by ion beam assisted deposition

Indium tin oxide (ITO) thin films have been deposited onto polycarbonate substrates by ion beam assisted deposition technique at room temperature. The structural, optical and electrical properties of the films have been characterized by X-ray diffraction, atomic force microscopy, optical transmittance, ellipsometric and Hall effect measurements. The effect of the ion beam energy on the properties of the films has been studied. The optical parameters have been obtained by fitting the ellipsometric spectra. It has been found that high quality ITO film (low electrical resistivity and high optical transmittance) can be obtained at low ion beam energy. In addition, the ITO film prepared at low ion beam energy gives a high reflectance in IR region that is useful for some electromagnetic wave shielding applications.     

用压痕试验法研究CVD金刚石膜的粘附性能

在观察与分析压入过程中CVD金刚石膜开裂方式的基础上,初步探讨了用压痕试验法评定CVD金刚石膜粘附性能的可行性．采用反映膜／基粘附性能的临界开裂或剥落载荷P_er和抗裂性参数dP／dX两指标评定了硬质合金基体表面经不同预处理方法和沉积工艺参数合成的金刚石膜的粘附性能;研究了粘附性能指标与沉积工艺参数（如甲烷浓度、沉积气压、沉积功率）之间的关系．适当的表面预处理、适中的甲烷浓度、较低的沉积气压、较高的沉积功率均有利于改善金刚石膜的粘附性能．     

生长温度对CVD金刚石薄膜的影响

系统研究了ＣＶＤ金刚石薄膜成膜过程中生长温度对薄膜质量、生长率和力学性能的影响。研究结果表明：在典型沉积条件下，生长温度愈高、薄膜的晶体质量愈好；但薄膜的应力状况和附着性能变坏；在８００℃时，金刚石薄膜的生长速率最大。讨论了ＣＶＤ金刚石薄膜作为机械工具涂层的最佳生长温度。     

Diamond and diamond-like carbon films

Polycrystalline diamond films are grown from low pressure gas mixtures, the deposition techniques are Microwave Plasma Chemical Vapour Deposition and Hot filament Chemical Vapour Deposition, in both techniques the deposition temperature is close to 900°C. The film growth process is strongly dominated by the initial nucleation stage, after this stage, the film grows at a rate of one micron per hour. The carbon atoms in the diamond film are fully fourfold (sp³) co-ordinated and the film properties are close to those of single crystalline diamond: extremely hard, resistant and transparent from UV to IR.Diamond-like carbon (DLC) films are amorphous and contain a variable amount of hydrogen in their structure, the carbon atoms are partially threefold (sp²) co-ordinated. Films are obtained at temperatures below 250°C and deposited on almost any substrate. Film composition, structure and functional properties are strongly dependent on the level of ionic bombardment of the film during growth. DLC films are very hard, have a low friction coefficient and good wear resistance, are chemically inert and are transparent in the IR.     

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。     

Hydrogen induced microstructural variation in diamond and diamond like carbon thin films

Hydrogen plays a crucial role in the growth of micro-crystalline diamond (MCD) and diamond like carbon (DLC) thin films grown by plasma assisted chemical vapour deposition (PACVD) processes. It selectively etches graphite phase and helps in stabilizing the diamond phase. The presence of various hydrocarbon species in the plasma and their reaction with atomic, excited or molecular hydrogen on the substrate surface decide the mechanism of diamond nucleation and growth. Several mechanisms have been proposed but the process is still not well understood. Control of hydrogen and other deposition parameters in the PACVD process leads to deposition of yet another class of materials called diamond like carbon. By varying the concentration of hydrogen it is possible to produce purely amorphous carbon films on the one hand and amorphous hydrogenated carbon films (with as high as 60% hydrogen) on the other. Very hard, optically transparent and electrically insulating films characterize the diamond like behaviour. The proportion of hydrogen and its bonding with carbon or hydrogen in the film can be varied to obtain very hard to very soft films which could be optically transparent or opaque. The microstructure of these films have been investigated by a large number of techniques. The results show interesting situations. This paper reviews the work on the role of hydrogen on the growth, structure and properties of MCD and DLC thin films.     

镍铬合金薄膜的研究进展

镍铬合金薄膜是重要的精密电阻和应变电阻薄膜材料.简述了镍铬合金薄膜的3种制备方法:真空蒸发沉积、磁控溅射沉积和离子束沉积;讨论了基底、工作气压、沉积时间等薄膜制备工艺参数以及退火工艺对薄膜性能的影响.重点叙述了镍铬合金薄膜、改良型镍铬合金膜、含氮镍铬合金膜、镍铬合金多层膜和纳米镍铬合金薄膜等膜系的特征.阐明了制备具有高电阻率、低电阻温度系数、高应变灵敏系数、良好的热稳定性等优异综合性能的镍铬合金薄膜的新工艺发展趋势.     

Electrical properties of diamond films grown at low temperature

The unique electronic properties of diamond, associated with the emergence of chemical vapour deposition (CVD) methods for the growth of thin films on non-diamond substrates, have led to considerable interest in electronic devices fabricated from this material. In our previous work, we found that polycrystalline diamond films can be deposited at 250 °C using CH₄---CO₂ gas mixtures. Studying the electrical properties and the upcoming problems of applications of low-temperature diamond films are relevant concerns.

In this work, the electrical properties of diamond films grown at low temperatures were studied and compared with those of conventional diamond films. Platinum was used as the upper electrode. The resistivity of low-temperature diamond was around three orders of magnititude lower than that of conventional diamond. However, both the low temperature and conventional growth diamond exihibited rectifying behavior when platinum was used as the upper electrode.     

fabrication of diamond membranes for MEMS using reactive ion etching of silicon

Polycrystalline diamond thin film has been grown on a silicon substrate using high pressure microwave plasma-assisted chemical vapor deposition from a gas mixture of methane and hydrogen at a substrate temperature of 950°C. A simple process flow has been developed to fabricate optically transparent polycrystalline synthetic diamond membranes/windows employing reactive ion etching (RIE) of a single crystal silicon substrate using an electron beam evaporated aluminum thin film mask pattern formed by photolithography. Scanning electron microscopy has been used to study the morphology of as-grown diamond thin films.     

New developments in ionized-cluster beam and reactive ionized-cluster beam deposition techniques

Ionized-cluster beam (ICB) and reactive ionized-cluster beam (R-ICB) deposition techniques are described from the standpoint of the ion-based technique, as applied to the production of thin film devices. In ICB deposition, clusters (macroparticles consisting of approximately 10³ atoms loosely coupled together) instead of atomic or molecular particles are used after ionization, resulting in a remarkable improvement of epitaxial film growth and of the quality of deposited films with strong adhesion. This paper describes in detail the influences of the ion content and the acceleration voltage on nucleation and film properties. MnBi films as magneto-optical memories and ZnO epitaxial films as optical devices are discussed as practical applications of the ICB and R-ICB deposition techniques.     

Study of the moderate-temperature growth process of optical quality synthetic diamond films on quartz substrates

Growth of undoped and boron-doped diamond films on quartz substrates at moderate temperature of 500 °C by microwave plasma chemical vapor deposition method was studied in terms of growth rate, surface roughness and optical transmittance. Similar density of diamond seed particles on quartz surfaces seeded mechanically before the deposition process and diamond grains within diamond films grown on those substrates is observed. The growth rate is found similar to that reported for diamond deposited on silicon substrates in the same plasma deposition system, although with substantially higher activation energy. Furthermore, increased level of dopant concentration in the gas mixture resulted in a decrease of the growth rate, while a gradual reduction of the surface roughness occurred at high dopant levels. Overall, the highest measured regular optical transmittance of the undoped diamond film on quartz was 45% at 1100 nm (including quartz absorption), whereas that of boron-doped diamond peaked 5% at 700 nm (tail absorption of boron centers).