Effects of CCl4 concentration on nanocrystalline diamond film deposition in a hot-filament chemical vapor deposition reactor

The effect of CCl₄ concentration on the nanocrystalline diamond (NCD) films deposition has been investigated in a hot-filament chemical vapor deposition (HFCVD) reactor. NCD films with a thickness of few-hundred nanometers have been synthesized on Si substrates from 2.0% and 2.5% CCl₄/H₂ at a substrate temperature of 610 °C. Polycrystalline diamond films and nanowall-like films with higher formation rates than those of the NCD films were deposited from lower and higher CCl₄ concentrations, respectively. The grain sizes of the diamond film grown using 2.0% CCl₄ increased with film thickness while a diamond film with uniform nanocrystalline structure all over a thickness of 1 μm can be deposited in the case of 2.5% CCl₄. We suggest that both the primary nucleation and the secondary nucleation processes are crucial for the growth of the NCD films on Si substrates.     

Nucleation and growth of diamond films on single crystal and polycrystalline tungsten substrates

Silicon has been the most widely studied substrate for the nucleation and growth of CVD diamond films. However, other substrates are of interest, and in this paper, we present the results of a study of the biased nucleation and growth of diamond films on bulk single and polycrystalline tungsten. Diamond films were nucleated and grown, using a range of bias and reactor conditions, and characterized by Raman spectroscopy and scanning electron microscopy (SEM). High-quality (100) textured films (Raman FWHM<4 cm⁻¹) could be grown on both single and polycrystalline forms of the tungsten substrate. On carefully prepared substrates, by varying the bias treatment, it was possible to determine the nucleation density over a 4–5 order range, up to ∼10⁹ cm⁻². Raman measurements indicated that the diamond films grown on bulk tungsten exhibited considerable thermal stress (∼1.1 GPa), which, together with a thin carbide layer, resulted in film delamination on cooling. The results of the study show that nucleation and growth conditions can be used to control the grain size, nucleation density, morphology and quality of CVD diamond films grown on tungsten.     

Deposition and characterization of nanocrystalline diamond films on Co-cemented tungsten carbide inserts

Nanocrystalline diamond films were deposited on Co-cemented tungsten carbides using bias-enhanced hot filament CVD system with a mixture of acetone, H₂ and Ar as the reactant gas. The effect of Ar concentration on the grain size of diamond films and diamond orientation was investigated. Nanocrystalline diamond films were characterized with field emission scan electron microscopy (FE-SEM), Atomic force microscopy (AFM), Raman spectroscopy and X-ray diffraction spectroscopy (XRD). Rockwell C indentation tests were conducted to evaluate the adhesion between diamond films and the substrates. The results demonstrated that when the Ar concentration was 90%, the diamond films exhibited rounded fine grains with an average grain size of approximately 60–80 nm. The Raman spectra showed broadened carbon peaks at 1350 cm^− 1 and 1580 cm^− 1 assigned to D and G bands and an intense broad Raman band near 1140 cm^− 1 attributed to trans-polyacetylene, which confirmed the presence of the nanocrystalline diamond phase. The full width at half maximum of the <111> diamond peak (0.8°) was far broader than that of conventional diamond film (0.28°–0.3°). The Ra and RMS surface roughness of the nanocrystalline diamond film were measured to be approximately 202 nm and 280 nm with 4 mm scanning length, respectively. The Ar concentration in the reactant gases played an important role in the control of grain size and surface roughness of the diamond films. Nanocrystalline diamond-coated cemented tungsten carbides with very smooth surface have excellent characteristics, which made them a promising material for the development of high performance cutting tools and wear resistance components.     

Nucleation and Growth of Diamond Films on Ni-Cemented Tungsten Carbide: Effects of Substrate Pretreatments

The nucleation and growth of diamond films on Nicemented carbide is investigated. Substrates made of WC with 6 wt% of Ni were submitted to grinding, and then to different pretreatments (scratching, etching, and/or decarburization) before diamond deposition. Diamond synthesis was carried out by hot-filament chemical vapor deposition (HFCVD) using a mixture of CH₄ (1% v/v) and H₂. Depositions were performed for different lengths of time with the substrates at various temperatures. The specimens were analyzed before and after deposition by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffractometry (XRD). Raman spectra showed that the phase purity of the diamond films was not affected by the presence of nickel on the substrate surface. After wet etching pretreatments, the nucleation of diamond was enhanced, mainly at the WC grain boundaries. Continuous films were obtained on scratched and etched substrates. The decarburizing treatment led to the formation of metallic tungsten and of brittle nicke–tungsten carbide phases. These phases reacted in the early stages of diamond film formation with gaseous carbon species with a parallel process which competes with stable diamond nucleus formation. The diamond film formed after long-term deposition on these samples was not continuous.     

Measurement of the adhesion of diamond films on tungsten and correlations with processing parameters

Adhesion between diamond films and tungsten substrates is reported as a function of the deposition processing parameters. Diamond films were grown by a hot filament method as a function of seven different processing parameters: substrate scratching prior to diamond deposition, substrate temperature, methane content of the input gas mixture, filament temperature, filament-substrate distance, system pressure, and total gas flow rate. Adhesion was measured by using a Sebastian Five A tensile pull tester. Testing was complicated by the non-uniformity of the film thickness, diamond quality, film cohesion, and surface preparation across the full substrate surface area. Various types of film failure mode were observed, which did not correlate with the film processing parameters. The measured adhesion values showed larger variations from point to point across the sample surface and from identically prepared samples than variations as a function of the film processing parameters. Weak correlations of adhesion with the processing parameters were found using statistical analysis of the results from multiple pulls on a large number of samples. The statistical results suggest that substrate preparation, gas flow rate, and gas pressure are the most important processing parameters affecting the film adhesion, while the temperature of the hot filament has little or no effect on the adhesion of the film. However, improvements in film processing and adhesion testing need to be made before true quantitative adhesion testing of high-quality diamond films can be accomplished.     

Cubic boron nitride films for industrial applications

The effects of kinetic energy, chemical nature of substrates and temperature on the synthesis of cBN films are explored to obtain cBN films with industrial quality. Carbon including amorphous carbon, nanocrystalline and polycrystalline diamond enables deposition of stable, thick and adherent cBN films with characteristic Raman signature. Although temperature has been designated as an unimportant parameter, the deposition at higher temperatures yields higher quality of cBN films. The higher temperature (800 °C) was also employed at cBN deposition on diamond coated tungsten carbide (WC) cutting inserts using plasma enhanced chemical vapor deposition (PECVD). The quality of cBN films grown by PECVD significantly overcomes that prepared by physical vapor deposition (PVD) which is affected in large extent by the lower kinetic energies of particles used in PECVD. The low kinetic energy of particles induces surface growth mechanism which differs from the growth models previously proposed.     

生长时间对纳米金刚石薄膜微结构的影响

文章研究了不同沉积时间下制备的不同厚度纳米金刚石薄膜的微观结构和相组成。采用热丝化学气相沉积法分别制备了沉积时间为52、67、97和127min的纳米金刚石薄膜。采用扫描电子显微镜和拉曼光谱表征薄膜的微观结构和相组成。结果表明,纳米金刚石薄膜表面颗粒尺寸大小无明显变化,约为50nm。随着生长时间增加,金刚石相含量保持稳定没有明显的增加或减小趋势,石墨相有序度以及石墨团簇尺寸随着生长时间增加而增加。     

Early Stages of Diamond-Film Formation on Cobalt-Cemented Tungsten Carbide

The surface composition of cemented tungsten carbide (WC-5.8 wt% Co) was studied by X-ray photoelectron spectroscopy (XPS), during the early stages of diamond-film deposition, by hot-filament chemical vapor deposition (HFCVD). The nucleated diamond films were analyzed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and automatic image analysis (AIA). The evolution of the surface composition of cemented tungsten carbide during the early stages of diamond-film deposition was strongly dependent on the substrate temperature. At relatively low temperature (750°C), cobalt-rich particles started to segregate at the substrate surface after a few minutes of diamond deposition. The conspicuous segregation of the binder partly inhibited the formation of stable diamond nuclei, through intense carbon dissolution or carbon segregation at the binder surface, but did not affect nucleic growth. At higher temperatures (940°C), no cobalt-rich particles formed at the substrate surface, even after 2 h of deposition. However, XPS results demonstrated the presence of cobalt in a surface layer, although in a lower amount than at 750°C. Nevertheless, the nucleation density of diamond at 940°C was much lower than at 750°C. Gaps between WC grains formed within 10 mins. Therefore, intergranular cobalt was removed at 940°C, a finding attributed to the etching performed by monohydrogen, rather than to binder evaporation. The time evolution of the substrate area fraction covered by diamond islands, S ( t ), was well described by Avrami kinetics for two-dimensional phase transformations, suggesting that diamond formation took place via a heterogeneous nucleation process. The S ( t ) functions exhibited a similar trend at 750° and 940°C, because the higher growth rate of diamond crystallites at higher temperature counteracted the slower nucleation rate at the higher temperature.     

Diamond growth by hollow cathode arc chemical vapor deposition at low pressure range of 0.02–2 mbar

An attempt was made to synthesize diamond films on (001) silicon substrates by means of a graphite or tungsten hollow cathode arc chemical vapor deposition at a lower pressure range of 0.02–2 mbar. The hollow cathode arc provides the advantage of the generation of a large area, high-flux electron beam, a very high-density plasma, and the high kinetic reaction species due to relatively low pressure operation. Diamond films have been characterized by scanning electron microscopy and Raman spectroscopy. The quality of diamond films deposited using the graphite hollow cathode was better than that using the tungsten hollow cathode at 2 mbar pressure. With further decreasing the deposition pressure, the evaporation and sputtering of the graphite hollow cathode are increased and the film quality was deteriorated. The growth rate of diamond films decreased and the nucleation density increased with decreasing deposition pressure.     

Epitaxial Ir layers on SrTiO3 as substrates for diamond nucleation: deposition of the films and modification in the CVD environment

Iridium films on SrTiO₃(001) have recently proven to be a superior substrate material for the heteroepitaxy of diamond thin films by chemical vapour deposition in the effort towards the realization of single crystal diamond films. In this paper we report on the growth and structural properties of iridium (Ir) films deposited by electron-beam evaporation on SrTiO₃(001) surfaces varying the deposition temperature between 280 and 950°C. The films were studied by scanning electron microscopy, atomic force microscopy and X-ray diffraction. At the highest temperature film growth proceeds via three-dimensional nucleation, coalescence and subsequent layer-by-layer growth. The resulting films show a cube-on-cube orientation relationship with the substrate and a minimum mosaic spread of 0.15°. Towards lower deposition temperatures the orientation spread increases only slightly down to ∼500°C while the surface roughness, after passing through a maximum at ∼860°C, decreases significantly. For the lowest temperatures (below 500°C) the mosaic spread rises accompanied by the occurrence of twins until the epitaxial order is lost. Plasma treatment in the diamond deposition reactor at high temperature (920°C) yields low nucleation densities and modifies the Ir surface. At the same time {111} facets show a significantly higher structural stability as compared with {001} facets. Nucleation at 700°C results in highly aligned diamond grains with low mosaic spread and a vanishing fraction of randomly oriented grains, proving the superior properties of Ir films on SrTiO₃ for diamond nucleation as compared with pure silicon substrates.     

Partially stabilized zirconia substrate for chemical vapor deposition of free-standing diamond films

In this work we investigated the use of partially stabilized zirconia (PSZ) as the substrate for deposition of CVD diamond films. The polycrystalline PSZ substrates were sintered at high temperatures and the results showed that this material has unique properties which are very appropriated for the growth of free-standing diamond films. The diamond nucleation density on PSZ is high, even without seeding, and the CVD diamond film was totally released from the substrate after the deposition process, without cracking. Micro-Raman analysis revealed that the free-standing diamond film had a good crystallinity on both surfaces with practically no stress in the structure. The same PSZ substrate can be reutilized for the deposition of a large number of diamond films. The average growth rate is about 5–6 μm/h in a microwave plasma reactor at 2.5 kW. The deposition process causes the reduction of ZrO₂, producing ZrC. The high mobility of oxygen in the zirconia matrix at high temperature would probably help to etch the interface region between the substrate surface and the diamond film, decreasing the adhesion strength and eliminating some defects in the film structure related to non-diamond carbon phases.     

Nucleation of nanocrystalline diamond on masked/unmasked Si3N4 ceramics with different mechanical pretreatments

Results are presented concerning different mechanical pretreatments performed on silicon nitride substrates and their influence on the nucleation and growth of nanocrystalline diamond (NCD). All substrates were equally sintered and finished, but differently pretreated. Then, they were diamond coated in a microwave chemical vapor deposition system (MPCVD) for relatively short periods, using Ar/H₂/CH₄ gas mixtures. The main objective was to identify the best pretreatment among those proposed, while verifying how it correlates with film uniformity and surface roughness after post-growth. The effect of a molybdenum mask during growth is investigated.The top surface analysis revealed major differences in the nucleation morphology of diamond nuclei on the pretreated samples, two different nucleation types having been identified. For all pretreatments, samples exhibited a very smooth and uniform underlayer of very fine grain particles before the formation of larger aggregates, suggesting a bi-phase nucleation mechanism. When no mask is used considerable changes in the nucleation concentration are found, the resulting films showing grain enlargement near the edges, where the morphology assumes microcrystalline nature. This effect is suppressed by the use of a mask that allowed obtaining very uniform smooth films (R_rms∼ 30 nm, thickness ∼ 1.3 μm, MUS pretreatment), indicating a strong edge effect for the unmasked case. This fact can be attributed both to increased local temperature, plasma density and gas turbulence.     

Tribological properties and cutting performance of boron and silicon doped diamond films on Co-cemented tungsten carbide inserts

Boron and silicon doped diamond films are deposited on the cobalt cemented tungsten carbide (WC-Co) substrate by using a bias-enhanced hot filament chemical vapor deposition (HFCVD) apparatus. Acetone, hydrogen gas, trimethyl borate (C₃H₉BO₃) and tetraethoxysilane (C₈H₂₀O₄Si) are used as source materials. The tribological properties of boron-doped (B-doped), silicon-doped (Si-doped) diamond films are examined by using a ball-on-plate type rotating tribometer with silicon nitride ceramic as the counterpart in ambient air. To evaluate the cutting performance, comparative cutting tests are conducted using as-received WC-Co, undoped and doped diamond coated inserts, with high silicon aluminum alloy materials as the workpiece. Friction tests suggest that the Si-doped diamond films present the lowest friction coefficient and wear rate among all tested diamond films because of its diamond grain refinement effect. The B-doped diamond films exhibit a larger grain size and a rougher surface but a lower friction coefficient than that of undoped ones. The average friction coefficient of Si-doped, B-doped and undoped diamond films in stable regime is 0.143, 0.193 and 0.233, respectively. The cutting results demonstrate that boron doping can improve the wear resistance of diamond films and the adhesive strength of diamond films to the substrates. Si-doped diamond coated inserts show relatively poor cutting performance than undoped ones due to its thinner film thickness. B-doped and Si-doped diamond films may have tremendous potential for mechanical application.     

Free-standing diamond films prepared by a dc-plasma method above the ethylene glycol solution

Free-standing diamond films were prepared using a plasma chemical vapor deposition method above the liquid surface through two routes. Diamond was deposited on the surface of a tungsten anode under a dc-plasma regime. The electric field near the anode surface was flattened by placing a sub-electrode and it brought uniform film deposition. The growth rate was 5 μm h^− 1 and the thickness increased with the deposition time up to 12 μm. A free-standing film removed from the tungsten anode showed translucency. A glassy carbon layer with a thickness of 100 nm existed between the diamond film and the anode surface, and it partly remained on the back side of the removed diamond film. Under a plasma-jet regime, diamond was deposited on a silicon substrate brown with a plasma jet expelled from a nozzle exit. A high growth rate of 100 μm h^− 1 was attained at the maximum with increasing discharge power and carbon concentration, but the thickness profile was quite uneven. The removed film was elliptical and was larger than the nozzle size. A 3C–SiC layer was formed on the back side of the removed film.     

Chemical and structural transformations of silicon submitted to H2 or H2/CH4 microwave plasmas

Silicon substrates are often used to synthesize polycrystalline diamond films by microwave plasma assisted chemical vapour deposition technique (MPCVD). In the case of highly oriented diamond films, several steps are employed to carefully prepare the silicon surface (pre-treatment steps), to nucleate diamond crystals (nucleation step) and to thick the film (growth step). In this study, we characterize {100} silicon substrates and diamond released from its silicon substrate by electronic microscopies (TEM and SEM), by Atomic Force Microscopy (AFM) and by X-ray photoelectron spectroscopy (XPS), to follow the substrate transformations after each step, particularly the formation and the evolution of the silicon carbide and to characterise the diamond films grown on the carburised silicon. We show that according to the experimental conditions and the level of surface/gas contamination by carbon and silicon species, isolated islands or continuous β-SiC compound are formed over the silicon surface and can generate defects such as voids or strip structures that influence the subsequent diamond nucleation and growth.     

Diamond films with preferred <110> texture by hot filament CVD at low pressure

The effects of gas pressure on the textured growth of diamond films were investigated in a hot filament chemical vapor deposition (HFCVD) system. Diamond thin film with the growth rate of 1.3 μm/h and with high <110> texture was obtained at 5 Torr when lowering the gas pressure from 40 Torr to 1 Torr. The formation of high density nanocrystalline diamond nuclei elongated along the <110> direction in the nucleation stage and its consequent growth at lower pressure were considered to be responsible for the formation of <110> textured diamond thin film.     

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.     

Analysis of optical emission spectroscopy in diamond chemical vapor deposition

We used optical emission spectroscopy (OES) to study the gas phase chemistry in hot filament chemical vapor deposition (HFCVD) diamond processes. The results show that the methane concentration strongly influenced the intensity ratios of CH, CH⁺ and H_γ to H_β, and the effects of the pressure and filament temperature on the relative concentrations of the species were also analyzed. Spatially resolved OES implied that a relative high concentration of atomic H existed near the substrate surface, which is favorable for diamond film growth. Although the relatively high concentrations of CH and CH⁺ to atomic H are beneficial to increasing diamond nucleation density, they are very harmful to the growth of diamond films.     

Effect of metallic seed layers on the properties of nanocrystalline diamond films

Three metallic films (Mo, Ti and W) were sputtered on Si substrates and ultrasonically seeded in diamond powder suspension. Nanocrystalline diamond (NCD) films were deposited using a dc arc plasma jet CVD system on the seeded metallic layers and, for comparison, a seeded Si without any metallic layer. The effect of metallic seed layers on the nucleation, microstructure, composition and mechanical properties of NCD films was investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and nanoindentation. We found that the metallic seed layers were transformed into metallic carbide or/and metallic silicide during the deposition of NCD films at high temperature. Adding metallic seed layers had no obvious effect on the bonding structure of the NCD films but significantly improved their surface roughness and mechanical properties. The NCD film deposited on W seed layer displays the lowest root-mean-square roughness of 19 nm while that on Ti seed layer has the highest compactness, hardness and elastic modulus.     

Low temperature growth of highly transparent nanocrystalline diamond films on quartz glass by hot filament chemical vapor deposition

Highly transparent and hard nanocrystalline diamond (NCD) films were prepared on quartz glass by hot filament chemical vapor deposition (HFCVD). The effects of total gas pressure, substrate's temperature, and concentration of CH₄ on the grain size, surface's roughness and hardness, growth rate, as well as the optical properties of NCD films were investigated. The results indicated that with a low total gas pressure and high CH₄ concentration, high frequency of secondary nucleation can be obtained. In addition, low substrate temperature can increase the rate of the hydrogen atom etched sp² graphite carbon in the film, yielding a smooth surface of NCD films and very high sp³ content. Under optimized conditions, the hardness can be enhanced up to 65 Gpa, with 80% maximum transmittance in the visible light region. The aforementioned reaction platform outcomes a 1.2 μm thickness of NCD coating with a low root-mean-square (r.m.s.) surface roughness around 12–13 nm and a high growth rate around 1 μm/h. The influences of the total gas pressure, substrate's temperature, and CH₄ concentration for growing NCD films were also discussed in this paper.