Selective growth of diamond and carbon nanostructures by hot filament chemical vapor deposition

Diamond and carbon nanostructures have been synthesized selectively on differently pretreated silicon substrates by hot filament chemical vapor deposition in a CH₄/H₂ gas mixture. Under typical conditions for CVD diamond deposition, carbon nanotube and diamond films have been selectively grown on nickel coated and diamond powder scratched silicon surface, respectively. By initiating a DC glow discharge between the filament and the substrate holder (cathode), well aligned carbon nanotube and nanocone films have been selectively synthesized on nickel coated and uncoated silicon substrates, respectively. By patterning the nickel film on silicon substrate, pattern growth of diamond and nanotubes has been successfully achieved.     

Friction force microscopy study of diamond films modified by a glow discharge treatment

A glow discharge treatment technique has been developed which enables control of the surface roughness and morphology of diamond films for applications in optical and electrical components. A conventional hot filament chemical vapour deposition (CVD) system was used to deposit the diamond films onto silicon substrates via a three-step sequential process: (i) deposition under normal conditions; (ii) exposure to either a pure hydrogen plasma or 3% methane in an excess of hydrogen using DC-bias; and (iii) diamond deposition for a further 2 h under standard conditions. The frictional characteristics and roughness of the film surfaces were investigated by atomic force microscopy (AFM) and the morphology and the growth rates determined from scanning electron microscope images. Lateral force microscopy (LFM) has revealed significant differences in frictional behaviour between the high quality diamond films and those modified by a glow discharge treatment. Friction forces on the diamond films were very low, with coefficients ∼0.01 against silicon nitride probe tips in air. However, friction forces and coefficients were significantly greater on the DC-biased films indicating the presence of a mechanically weaker material such as an amorphous carbon layer. A combination of growth rate and frictional data indicated that the exposure to the H₂ plasma etched the diamond surface whereas exposure to CH₄/H₂ plasma resulted in film growth. Re-Nucleation of diamond was possible (stage iii) after exposure to either plasma treatment. The resultant friction forces on these films were as low as on the standard diamond film.     

Characterization of diamond fluorinated by glow discharge plasma treatment

The surface fluorination of diamond by treatment in glow discharge plasmas of CF₄ for different times has been investigated. High quality diamond films were deposited onto silicon substrates using hot filament chemical vapor deposition (HFCVD). Subsequently, the films were exposed to a radiofrequency glow discharge plasma of CF₄ for times ranging from 5 min to 1 h. The effects of the plasma treatment on the surface morphology, diamond quality and elemental composition were investigated using atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. Differences in film roughness caused by the plasma treatment were detected by AFM and confirmed by scanning electron microscopy (SEM). Raman spectroscopic analyses showed that the original diamond was of high quality and that the bulk of each film was unchanged by the plasma treatment. Analyses using XPS revealed increased surface fluorination of the films at longer treatment times. In addition, the density of free radicals in the films was probed using electron paramagnetic resonance spectroscopy (EPRS), revealing that untreated diamond possesses an appreciable density of free radicals (6×10¹² g⁻¹) which initially falls with treatment time in the CF₄ plasma but increases for long treatment times.     

Synthesis of diamond films and nanotips through graphite etching

A hot filament CVD process based on hydrogen etching of graphite has been developed to synthesize diamond films and nanotips. The graphite sheet was placed close to the substrate and only hydrogen was supplied during deposition. No hydrocarbon feed gases are required for this process. High quality diamond films were synthesized with high growth rate on P-type (1 0 0)-oriented silicon wafers without discharge or bias. The diamond growth rate is approximately five times higher than that through conventional hot filament chemical vapor deposition using a gas mixture of methane and hydrogen (1 vol.% methane) under similar deposition conditions. The diamond films synthesized in this process exhibit smaller crystallites and contain smaller amount of non-diamond carbon phases. Synthesis of well-aligned diamond nanotips with various orientation angles was achieved on the CVD diamond-coated Si substrate when the substrate holder was negatively biased in a DC glow discharge. The nanotips grown at locations far enough from the sample edges are aligned vertically, while those around the sample edges are tilted and point away from the sample center. The alignment orientation of the nanotips appears to be determined by the direction of the local electric field lines on the sample surfaces.     

Study of CrNx and NbC interlayers for HFCVD diamond deposition onto WC–Co substrates

Chromium nitride (CrN_x) and niobium carbide (NbC) films were deposited by magnetron sputtering on Co-cemented tungsten carbide (WC–Co) substrates and diamond deposition was performed by using hot-filament chemical vapor deposition (HFCVD) technique. The CrN_x and NbC interlayers have been deposited at different substrate temperatures (T_S = 400, 550 and 700 °C). The stability of these interlayers for diamond deposition has been studied by a heat treatment in H₂ atmosphere for 60 h at a temperature of 765 °C in the HFCVD reactor. X-ray diffraction (XRD), scanning electron microscopy (SEM) and glow discharge optical emission spectroscopy (GDOES) confirmed that due to this heat treatment the CrN_x films transformed into porous films composed of CrN_x, Cr₃C₂, Cr₇C₃ and Co phases, accompanied by a dramatic loss of nitrogen which is replaced by carbon. It was observed that higher nitrogen contents in the CrN_x films reduce the Co diffusion through the CrN_x layer. For NbC films, deposited by non-reactive magnetron sputtering from an NbC compound target, the heat treatment in the HFCVD reactor revealed that the films are absolutely stable during the heat treatment with some relaxation of residual stresses up to a factor of about 3. Furthermore it was found that Co diffuses through the NbC films with a T_S-dependant accumulation on the NbC film surface. By HFCVD it was possible to deposit adherent diamond coatings on the CrN_x and NbC interlayers. However, a reasonable adhesion of diamond on NbC was only obtained after different pre-treatments of the WC–Co substrates. The adhesion seems to be mainly governed by the topography of the WC–Co substrates.     

Influence of cathode temperature on gas discharge and growth of diamond films in DC-PCVD processing

In this paper, a novel direct current glow discharge plasma chemical vapor deposition (DC-PCVD) process, i.e., hot cathode DC-PCVD, is employed to deposit diamond films on molybdenum substrate. Compared with the conventional DC-PCVD method, the hot cathode DC-PCVD process is distinctive for its hot cathode with the temperature ranging from 700 to 1600 °C. Detailed experiments and analyses showed that the cathode temperature plays a key role in the stabilization of gas discharge and growth of diamond films.     

Diamond nucleation on Ni3Al substrate using bias enhanced nucleation method

Diamond deposition with positive and negative bias enhanced nucleation (BEN) pretreatments on mirror-polished polycrystalline Ni₃Al substrates has been investigated, respectively. It was found that diamond deposition on the substrates under both biasing exhibited significant variations among grains of different orientations. The substrate surface was found to be rough in the case of negative biasing, whereas it was smooth in the case of positive biasing. Thus, the correlation of the crystallographic orientation of grains on the samples with the diamond nucleation behavior was systematically characterized for the case of positive biasing by electron backscattered diffraction method with scanning electron microscopy. Diamond deposition on Ni₃Al grains near (111) orientation results in higher nucleation densities, while the densities are low on (110) and (100) oriented grains. Also, the interfacial microstructure between diamond deposited and Ni₃Al was characterized by cross-sectional transmission electron microscopy.     

Interfacial oxide and carbide phases in the deposition of diamond films on beryllium metal

We have investigated beryllium metal as a substrate for the microwave plasma chemical vapor deposition of diamond films. The dependence of oxide and carbide interfacial phase formation with temperature and their influence on diamond nucleation and growth behavior were studied by thin film X-ray diffraction. Although a native oxide (BeO with the hexagonal wurtzite structure) remains for the range of substrate temperatures studied (700–800°C), the formation of a carbide (Be₂C with the cubic antifluorite structure) is found only above a critical substrate temperature of approximately 750°C. Without the formation of Be₂C, the diamond growth rate is low and a significant amorphous carbon component is observed. Just above the critical temperature, films exhibited high growth rates with high phase-purity diamond. Thick films (>30 μm) grown above the critical temperature were observed to fracture completely within the Be₂C layer, suggesting this to be the weak structural link.     

Duplex DLC coatings fabricated on the inner surface of a tube using plasma immersion ion implantation and deposition

A duplex plasma immersion ion implantation and deposition (PIIID) process, involving carbon ion implantation and diamond-like carbon (DLC) deposition, is proposed to modify the inner surface of a tube. In the research, samples of GCr15 bearing steel were placed inside a tube in the vacuum chamber. After the vacuum chamber was evacuated to a base pressure of 6 × 10^− 3 Pa, C₂H₂ gas was introduced into the chamber, and the tube was biased by a negative pulsed bias. Since a pulsed glow discharge (PGD) plasma can be formed by the bias, carbon ion implantation and DLC film deposition process can be obtained by biasing the tube with a high and low bias, respectively. To synthesize different DLC films, single PIIID processes employing a low voltage (several kV) PGD method and duplex PIIID processes combining the high (several tens kV) and low voltage PGD techniques were carried out. The as-synthesized films were characterized by Raman spectrum, nano-indentation, scratch, tribological and electrochemical tests. Raman results show that duplex DLC films were synthesized by this duplex PIIID process. In addition, compared with the single DLC film synthesized by the low voltage PGD process, the duplex DLC films can obtain a high wear and corrosion resistances. Furthermore, using this duplex PIIID method, batch treatment of outer-rings of the bearing was realized.     

Selective deposition of diamond films on insulators by selective seeding with a double-layer mask

Polycrystalline diamond films have been patterned on Si₃N₄/Si and SiO₂/Si substrates by selective seeding with a double-layer mask via hot-filament chemical vapor deposition. High quality in the patterned diamond films and high selectivity were obtained by the process. The diamond films deposited on the insulators at different CH₄/H₂ concentrations were studied by scanning electron microscopy and Raman spectroscopy. The process proved to be far less damaging to the substrates, and yet effective in developing patterns of diamond films on a large and different substrate.     

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.     

Influence of bias voltage on diamond like carbon (DLC) film deposited on polyethylene terephthalate (PET) film surfaces using PECVD and its blood compatibility

In this paper, diamond like carbon (DLC) films were coated on polyethylene terephthalate (PET) film substrate as a function of biasing voltage using plasma enhanced chemical vapour deposition. The surface morphology of the DLC films was analyzed by scanning electron microscopy and atomic force microscopy. The chemical state and structure of the films were analyzed by X-ray photoelectrons spectroscopy and Raman spectroscopy. The micro hardness of the DLC films was also studied. The surface energy of interfacial tension between the DLC and blood protein was investigated using contact angle measurements. In addition, the blood compatibility of the films was examined by in vitro tests. For a higher fraction of sp³ content, maximum hardness and surface smoothness of the DLC films were obtained at an optimized biasing potential of ? 300 V. The in vitro results showed that the blood compatibility of the DLC coated PET film surfaces got enhanced significantly.     

Temperature influence on the interlayer and surface morphology of diamond coating on 3D porous titanium substrates

Nanocrystalline (NCD) and/or microcrystalline (MCD) diamond films grown on three-dimensional porous titanium (Ti) substrate were obtained by hot filament chemical vapor deposition (HFCVD) technique. The morphology variation of diamond films grown on porous three-dimensional titanium substrate was studied at four different deposition temperatures to investigate their influence on nucleation density. Scanning electron microscopy images depicted the continuous change from microcrystalline diamond grains with a random crystallographic orientation, at 500 °C and 600 °C, to a cauliflower-like structure for deposits at 700 °C and 800 °C. Visible Raman spectroscopy confirmed the good quality of diamond films and revealed that the amount of amorphous carbon increased associated to the film morphology changes from MCD to NCD. X-ray diffraction analyses, performed both through θ–2θ scans and at grazing incidence angle, allowed the investigation of the crystallographic properties and structural evolution of the different film/substrate interface phases, such as TiC(111), TiC(200) and TiH₂. The results revealed that the temperature enhanced the nucleation sites for diamond growth.     

Influence of substrate nature on the d.c.-glow discharge induced nucleation of diamond

The nature of the nucleation centers, formed during the so called bias enhanced nucleation (BEN) of chemical vapor deposition (CVD) diamond is still an open question. We address this question by investigating the chemical composition and structure of the material deposited during the “nucleation” stage on various substrates by near edge X-ray absorption fine structure technique (NEXAFS) and Raman spectroscopy.The key step of the BEN of diamond in hot filament CVD systems is the generation of a stable d.c.-glow discharge between the grounded substrate and a positively biased electrode. This process results in the deposition of a carbon based film which contains the diamond nucleation and growth centers. Different materials, such as Si(100), CVD diamond films, and Si(100) onto which thin films of Ni were evaporated were used as substrates.It was found that the structure of the material deposited during the d.c.-glow discharge process is affected by the nature of the substrate. The d.c.-glow discharge process applied to the Si substrate resulted in the formation of a graphite-like film in the earlier stages (5 min), which after prolonged treatment time (30 min) was predominantly composed of nanosized diamond. The CVD diamond film, used as a substrate, promoted the formation of nanosized diamond particles even after 5 min of the d.c.-glow discharge process. However, C-13 labeling experiments have shown that microcrystalline diamond does not grow on the pre-existing CVD diamond substrate under the d.c.-glow discharge conditions. In the case of the Ni modified Si, the deposited film was graphitic in nature both after short and prolonged d.c.-glow discharge treatment times.     

Influence of substrate material and ion bombardment on plasma-deposited fluorocarbon thin films

The influence of substrate material and ion bombardment on fluorocarbon thin films deposited using a C₂F₆ glow discharge in an rf, parallel plate reactor was investigated. Monitoring of the plasma process by optical emission spectroscopy indicated that the dominant species in the glow discharge was CF₂. Studies of bulk polytetrafluoroethylene (PTFE) and plasma-polymerized fluorocarbon thin-film samples in an XPS system demonstrated that the formation of non-CF₂ species can be induced by ion bombardment of CF₂ molecules. Characterization of the deposited fluorocarbon films by XPS found that the F/C ratio and CF_x distribution (0 < x < 3) in the films were dependent on processing conditions. Fluorocarbon films deposited simultaneously onto Al, glass, steel, and PTFE substrates using a C₂F₆ plasma and a graphite sputter target had measurably different F/C ratios, with the F/C ratio of the films deposited onto the Al substrates consistently lower than the F/C ratios of the films deposited onto the other substrates. When a C₂F₆ plasma was used without a graphite target, the F/C ratio in the film was constant, but the CF_x distribution was different for each of the substrate materials. Analysis of the plasma-polymerized films by TEM revealed that localized growth of fluorocarbon particles occurred during the initial stages of deposition, consistent with an activated growth mechanism. Differences in the F/C ratio for films deposited onto the various substrate materials were attributed to the interaction of the fluorocarbon plasma with the exposed surface of the substrate prior to complete coverage by the polymeric film. © 1994 John Wiley & Sons, Inc.     

Effect of substrate temperature on the selective deposition of diamond films

Selective diamond films on roughened Si(100) substrates with patternings have been achieved by microwave plasma chemical vapor deposition (MP-CVD). The films have been characterized by scanning electron microscopy (SEM) and Raman spectra. The influence of substrate temperature on the selective deposition of diamond films has been discussed in detail: the diamond nucleation density on the SiO₂ mask increased with substrate temperature while the effect of the selective deposition of diamond films deteriorated; the optimized deposition temperature conditions have been concluded.     

Low surface temperature synthesis and characterization of diamond thin films

Polycrystalline diamond films are deposited on p-type Si(100) and n-type SiC(6H) substrates at low surface deposition temperatures of 370–530 °C using a microwave plasma enhanced chemical vapor deposition (MPECVD) system. The surface temperature during deposition is monitored by an IR pyrometer capable of measuring temperature between 250 and 600 °C in a microwave environment. The lower deposition temperature is achieved by using an especially designed cooling stage. The influence of the deposition conditions on the growth rate and structure of the diamond film is investigated. A very high growth rate up to 1.3 μm/h on SiC substrate at 530 °C surface temperature is attributed to an optimized Ar-rich Ar/H₂/CH₄ gas composition, deposition pressure, and microwave power. The structure and microstructure of the films are characterized by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. A detailed stress analysis of the deposited diamond films of grain sizes between 2 and 7 μm showed a net tensile residual stress and predominantly sp³-bonded carbon in the deposited films.     

Diamond coating of coloured Si3N4 ceramics

The effect of Si₃N₄ secondary phases on chemical vapour deposition (CVD) diamond film growth was analyzed. Silicon nitride substrates were obtained by pressureless sintering, placing the green samples inside a powder bed of Si₃N₄/BN. Local variations in the sintering atmosphere led to samples with different grey colouration as well as chemical and physical characteristics, determined by X-ray diffraction and thermal conductivity tests, which affected the diamond film growth. A complete characterization of the films, including thickness, average crystal size, surface roughness, texture and adhesion, was done. The Si₃N₄ substrate with glassier phase gave thicker diamond films, with smaller crystal sizes and better film adhesion to the substrate than the diamond films grown on ceramic substrates with less vitreous phase.     

Fretting wear and electrochemical corrosion of well-adhered CVD diamond films deposited on steel substrates with a WC–Co interlayer

Diamond films have been grown on carbon steel substrates by hot-filament chemical vapour deposition methods. A Co-containing tungsten-carbide (WC–Co) coating prepared by high velocity oxy-fuel spraying was used as an intermediate layer on the steel substrates to minimize the early formation of graphite (and thus growth of low quality diamond films) and to enhance the diamond film adhesion. The effects of the WC–Co interlayer on nucleation, quality, adhesion, tribological behaviour and electrochemical corrosion of the diamond film were investigated. The diamond films exhibit excellent adhesion under Rockwell indentation testing (1500 N load) and when subjected to high-speed, high-load, long-time reciprocating dry sliding ball-on-flat wear tests against a Si₃N₄ counterface in ambient air (500 rpm, 200 N, 300,000 cycles). A WC–Co interlayer with appropriate chemical pretreatment is shown to play an important role in improving the nucleation, quality and adhesion of the diamond film, relative to that shown by substrates without such pretreatment.     

Comparative study of diamond films grown on silicon substrate using microwave plasma chemical vapor deposition and hot-filament chemical vapor deposition technique

Diamond films on the p-type Si(111) and p-type(100) substrates were prepared by microwave plasma chemical vapor deposition (MWCVD) and hot-filament chemical vapor deposition (HFCVD) by using a mixture of methane CH₄ and hydrogen H₂ as gas feed. The structure and composition of the films have been investigated by X-ray Diffraction, Raman Spectroscopy and Scanning Electron Microscopy methods. A high quality diamond crystalline structure of the obtained films by using HFCVD method was confirmed by clear XRD-pattern. SEM images show that the prepared films are poly crystalline diamond films consisting of diamond single crystallites (111)-orientation perpendicular to the substrate. Diamond films grown on silicon substrates by using HFCVD show good quality diamond and fewer non-diamond components.