Use of carbonitride film as buffer layer for CVD diamond nucleation

Enhanced nucleation of polycrystalline diamond has been achieved on Si(100) with an intermediate layer of carbonitride. The carbonitride film was formed by an ion beam assisted deposition method and was characterized by Rutherford backscattering, X-ray photoelectron and laser Raman spectroscopies. The diamond deposition was accomplished using a hot filament chemical vapor deposition technique. Diamond film quality was examined with the help of laser Raman spectroscopy and scanning electron microscopy.     

Nucleation enhancement of diamond by electric arcing

Enhancement of diamond nucleation by arcing on pre-existing diamond particles has been studied in the hot-filament CVD process. A positive bias of 400 volt was applied on a wire hanging over a grounded substrate. Electric arcing between the wire and the substrate occurred during heating the filament in the temperature range 900–2000 °C, and resulted in an enhancement of nucleation around the pre-existing diamonds. The nucleation behavior was different from that of the conventional bias-enhanced nucleation, but the maximum nucleation density was almost the same. Based on the observed microstructural features, the enhanced nucleation mechanism was proposed to be the fragmentation of diamond particles during arcing.     

Effect of bias enhanced nucleation on the nucleation density of diamond in microwave plasma CVD

The variation of diamond nucleation density as a function of the conditions of bias enhanced nucleation (BEN) were studied. The nucleation density increased with microwave power, but decreased with the substrate temperature. The nucleation density also increased with bias voltage above 60 V, and had a maximum around 100 V. The crystal growth of diamond took place when either the bias voltage was high or the deposition time was long. The shift of C_1s energy measured by X-ray photoelectron spectroscopy indicated that the ratio of carbon sp³ bonds in the amorphous carbon and/or SiC phases formed before the nucleation of diamond, increased around the bias voltage of 100 V, which seemed to be the reason for enhancement of diamond nucleation by bias voltage. A simple computer simulation was performed in order to understand the effect of BEN conditions on the nucleation of diamond. The simulation reproduced the experimentally observed changes of nucleation density and particle size.     

Enhanced performance of HFCVD nanocrystalline diamond self-mated tribosystems by plasma pretreatments on silicon nitride substrates

Nanocrystalline diamond (NCD) coatings were grown by the hot-filament chemical vapour deposition (HFCVD) method on hydrogen plasma pretreated silicon nitride (Si₃N₄) substrates. The friction and wear behaviour of self-mated NCD films, submitted to unlubricated sliding and high applied loads (up to 90 N), was assessed using an oscillating ball-on-flat configuration in ambient atmosphere. The reciprocating tests revealed an initially high friction coefficient peak, associated to the starting surface roughness of NCD coatings (R_q = 50 nm). Subsequently, a steady-state regime with low friction coefficient values (0.01–0.04) sets in, related to a smoother (R_q = 17 nm) tribologically modified surface. A polishing wear mechanism governing the material loss was responsible for mild wear coefficients (k  10^− 7 mm³ N^− 1 m^− 1). The hydrogen etching procedure notably increased the film adhesion with respect to untreated surfaces as demonstrated by the high threshold loads (60 N; 3.5 GPa) prior to film delamination.     

Growth rate improvements in the hot-filament CVD deposition of nanocrystalline diamond

The hot-filament CVD, a less used technique for NCD films growth using Ar/H₂/CH₄ gas mixtures, is optimized for the coating of silicon nitride ceramics. Parameters such as gas composition (Ar/H₂ and CH₄/H₂ ratios), total gas pressure, total mass flow and substrate and filament temperatures, are studied to assess their effect on NCD growth kinetics as well as on film quality and morphology. The smallest diamond crystallite sizes (8 nm) were recorded for the slowest growth rate of 0.1 μm h^− 1. A remarkable result is the very high growth rate of 1.6 μm h^− 1 of continuous NCD coatings with 28 nm of crystallite size, obtained in selected deposition conditions.     

Machining behaviour of silicon nitride tools coated with micro-, submicro- and nanometric HFCVD diamond crystallite sizes

Very smooth CVD diamond films are used as direct coatings on Si₃N₄ tool substrates. By adjusting deposition parameters, namely Ar/H₂ and CH₄/H₂ gas ratios, and substrate temperature, nano- (27 nm) and submicrometric (43 nm) crystallite sized grades were produced in a hot filament reactor. Also, a conventional 5 and 12 μm micrometric grain size types were produced for comparison. Normalized coated inserts were tested for dry turning of WC–25 wt.% Co hardmetal. All the CVD diamond grades endured the hardmetal turning showing slight cratering, having the flank wear as the main wear mode. Their turning performance was distinct, as a consequence of morphology and surface roughness characteristics. Among all the tested tools, the more even surface and the submicrometric grade presented the best behaviour regarding cutting forces, tool wear and workpiece surface finishing. For this coating, the depth-of-cut force attained the lowest value, 150 N, the best combination of wear types (KM = 30 μm, KT = 2 μm and VB = 110 μm) and workpiece surface finishing (Ra = 0.2 μm).     

Analysis of size distribution functions of diamond crystallites formed in the early stages of chemical vapour deposition

Size distribution functions of diamond particles formed in the early stages of chemical vapour deposition (CVD) can be used to distinguish between seeding and heterogeneous nucleation on the basis of their shape and of the d_max/d_min ratio, d_max and d_min being the maximum and the minimum diameters, respectively. A monomodal size distribution function with a d_max/d_min ratio much greater than 1.2–1.3 indicates diamond formation to occur via heterogeneous nucleation. In this case the nucleation kinetics can be calculated once the growth law of the crystallites has been established. The nucleation kinetics at copper substrates have been derived from distribution functions and described by a new kinetic model which includes the generation of nucleation sites.     

Control of abnormal grain inclusions in the nanocrystalline diamond film deposited by hot filament CVD

Formation of abnormal grain inclusions in nanocrystalline diamond films deposited by hot filament CVD (HFCVD) was investigated. The phenomenon was attributed to two different origins: an intrinsic and an extrinsic one. The inclusions due to the intrinsic origin could be either avoided or weakened by controlling chamber pressure, CH₄/N₂ concentrations in H₂, and by positive substrate bias. The extrinsic origin for the abnormal grains was found to be the contamination from the alumina insulation tubes for the thermocouple placed near the substrate, which were degraded by the extended exposure to the high temperature and strongly reducing atmosphere.     

A study of diamond film deposition on WC–Co inserts for graphite machining: Effectiveness of SiC interlayers prepared by HFCVD

Thin silicon carbide (SiC) films were deposited from tetramethylsilane/hydrogen gas mixture on Co-cemented tungsten carbide (WC–Co) inserts by using Hot-Filament Chemical Vapour Deposition (HFCVD) technique. Grazing incidence X-Ray Diffraction (XRD) confirmed that the films were composed of cubic silicon carbide (β-SiC) and that small amounts of dicobalt silicide (Co₂Si) were formed. These films were used as interlayers for subsequent CVD of diamond films. XRD and combined Scanning and Transmission Electron Microscopies showed that the binder phase reacted during CVD to form cobalt silicides. However, these intermetallic compounds did not have bad effects on diamond adhesion. Dry turning of graphite was chosen to check the multilayer (SiC + diamond) film performance. For the sake of comparison, machining tests were also carried out under identical conditions using commercial sintered diamond (PCD) inserts and WC–Co diamond coated inserts with no interlayer. The wear mechanism of the tools has been identified and correlated with the criterion used to evaluate the tool life. The results showed that multilayer (SiC + diamond) coatings exhibited the longest tool lives. Therefore, thin SiC interlayers proved to be a new viable alternative and a suitable option for adherent diamond coatings on cemented carbide components and cutting tools.     

Thickness controlled and smooth polycrystalline CVD diamond film deposition on SiO2 with electrostatic self assembly seeding process

Sub micrometer thick continuous CVD diamond film was synthesized on thermally grown SiO₂ film employing the electrostatic self assembly seeding with nano-meter sized ultra dispersed diamond particles. Hot filament CVD system was used to deposit diamond film. Formation of mono-dispersed and mono-layered nano diamond seeding layer by well-known Electrostatic Self-Assembly method was effective to increase density and homogeneity of seeding particles. Because of high density of uniformed seeding particles, the nm controlled continuous CVD films with the surface roughness of less than 13 nm on silicon oxide without any mechanical damage were obtained. Linear growth rate with short incubation time was also observed. Depending on the film thickness, coloring effect was observed ranging from blue to yellow and orange. There was no visible fringe on the coated surface which affirms the good thickness uniformity.     

Influence of the silicon surface treatment by plasma etching and scratching on the nucleation of diamond grown in HFCVD - a comparative study

A comparative study for the nucleation of diamond was carried out using surface treatment like (i) surface scratching with 1 μm diamond paste and (ii) surface etching using chlorine plasma at different RF powers (50, 100 and 150 W). Atomic force microscopic study shows variation in roughness from 31 nm to 110 nm. Scratching results in random scratches, whereas plasma etches a surface uniformly. Scanning electron microscopic observations show well faceted crystallites with a predominance of angular shaped grains corresponding to 〈100〉 and 〈110〉 crystallite surfaces for the scratched as well as plasma etched substrate. Surface etching at 150 W plasma power results in a better growth in comparison with 50 and 100 W plasma powers. Chlorine-radical is found responsible for the changes in the growth morphology. Raman spectroscopy shows a sharp peak at 1,332 cm⁻¹ and a peak at ∼1,580 cm⁻¹ for both samples.     

Stochastic and deterministic models for nucleation and growth in non-isothermal and/or non-isobaric powder transformations

The calculation of fractional conversion can be very difficult in certain cases of nucleation and growth transformations (Mampel assumptions): it has only been developed for a few shapes of grains (spheres, cylinders) and only in isobaric and isothermal conditions. Here, a stochastic model which is intrinsically independent on geometry and which stands for non-isobaric and/or non-isothermal reactions is presented. The numerical evaluation of this model can be carried out in two different ways. First a slow Monte Carlo approach which is valid for all kinds of shapes and external conditions is presented, then, a faster, more classical approach is given which allows changing external conditions but only for well-known shapes.