Hot filament chemical vapour deposition and wear resistance of diamond films on WC-Co substrates coated using PVD-arc deposition technique

Different Cr- and Ti-base films were deposited using PVD-arc deposition onto WC-Co substrates, and multilayered coatings were obtained from the superimposition of diamond coatings, deposited on the PVD interlayer using hot filament chemical vapour deposition (HFCVD). The behaviour of PVD-arc deposited CrN and CrC interlayers between diamond and WC-Co substrates was studied and compared to TiN, TiC, and Ti(C,N) interlayers. Tribological tests with alternative sliding motion were carried out to check the multilayer (PVD + diamond) film adhesion on WC-Co substrate. Multilayer films obtained using PVD arc, characterised by large surface droplets, demonstrated good wear resistance, while diamond deposited on smooth PVD TiN films was not adherent. Multilayered Ti(C,N) + diamond film samples generally showed poor wear resistance.Diamond adhesion on Cr-based PVD coatings deposited on WC-Co substrate was good. In particular, CrN interlayers improved diamond film properties and 6 μm-thick diamond films deposited on CrN showed excellent wear behaviour characterised by the absence of measurable wear volume after sling tests. Good diamond adhesion on Cr-based PVD films has been attributed to chromium carbide formation on PVD film surfaces during the CVD process.     

Doping of vanadium to nanocrystalline diamond films by hot filament chemical vapor deposition

Doping an impure element with a larger atomic volume into crystalline structure of buck crystals is normally blocked because the rigid crystalline structure could not tolerate a larger distortion. However, this difficulty may be weakened for nanocrystalline structures. Diamonds, as well as many semiconductors, have a difficulty in effective doping. Theoretical calculations carried out by DFT indicate that vanadium (V) is a dopant element for the n-type diamond semiconductor, and their several donor state levels are distributed between the conduction band and middle bandgap position in the V-doped band structure of diamond. Experimental investigation of doping vanadium into nanocrystalline diamond films (NDFs) was first attempted by hot filament chemical vapor deposition technique. Acetone/H₂ gas mixtures and vanadium oxytripropoxide (VO(OCH₂CH₂CH₃)₃) solutions of acetone with V and C elemental ratios of 1:5,000, 1:2,000, and 1:1,000 were used as carbon and vanadium sources, respectively. The resistivity of the V-doped NDFs decreased two orders with the increasing V/C ratios.     

Synthesis of nanocrystalline diamond films by DC plasma-assisted argon-rich hot filament chemical vapor deposition

Continuous nanocrystalline diamond (NCD) films were grown in an argon-rich gas atmosphere with relatively high growth rates by sustaining a low power (5 W) DC plasma in a hot filament chemical vapor deposition system (HFCVD). The parameter window for the synthesis of NCD films was studied as a function of argon, methane and hydrogen concentrations, as well as substrate temperature and DC bias. The results are consistent with reports indicating that the DC plasma induces re-nucleation by ion bombardment during the initial growth step and helps to maintain the atomic H and hydrocarbon species near the growing surface. It was found that DC plasma-assisted HFCVD enables high NCD growth rates and expands the parameter window, rendering it unnecessary to heat the filament above 2800 K.     

Nucleation and growth of diamond films on aluminum nitride by hot filament chemical vapor deposition

Nucleation and growth of diamond films on aluminum nitride (ALN) coatings were investigated by scanning electron microscopy, Raman spectroscopy and scratch test. ALN films were grown in a magnetron sputtering deposition. The substrates were Si(111) and tungsten carbide (WC). Chemical vapor deposition (CVD) diamond films were deposited on ALN films by hot filament CVD. The nucleation density of diamond on ALN films was found to be approximately 10⁵ cm⁻², whereas over 10¹⁰ cm⁻² after negative bias pre-treatment for 35 min was −320 V, and 250 mA. The experimental studies have shown that the stresses were greatly minimized between diamond overlay and ALN films as compared with WC substrate. The results obtained have also confirmed that the ALN, as buffer layers, can notably enhance the adhesion force of diamond films on the WC.     

H atom production in a hot filament chemical vapour deposition reactor

Multiphoton ionisation spectroscopy of atomic hydrogen, resonance enhanced at the two photon energy by the 2s¹;²S_1/2 state, and subsequent analysis of the resulting Doppler broadened lineshapes, has been used to provide direct, spatially resolved relative H atom number densities and gas temperature profiles in the vicinity of a coiled Ta hot filament (HF) in a reactor used for diamond chemical vapour deposition. The effects of filament temperature and H₂ pressure on the relative H atom number densities and the gas temperature profiles have been investigated, as have the effects of small amounts of added CH₄. The effective activation energy for H atom production so obtained (E_a=237±22 kJ mol⁻¹) suggests that the HF provides a particularly efficient means of heating (and thus promoting the dissociation of) H₂ molecules that adsorb onto its surface.     

Negative-biased diamond nucleation on silicon at a wide range of methane concentrations in hot filament chemical vapour deposition

In order to enhance the production of hydrocarbon ions for bias-induced diamond nucleation, high CH₄ fractions up to 16% were applied in a hot filament chemical vapour deposition process. Filament temperatures between 2900 and 3000°C were used, at which the filament was kept clean throughout the process. On a negatively biased silicon substrate, diamond nucleation was observed to increase from 2×10⁷ to 10¹⁰ cm⁻² when the CH₄ fraction was increased from 2% to 8%. Diamond film grown on bias-induced nuclei exhibited a preferred orientation along [001], which is believed to be growth on the nuclei with the same orientation. By calculation, the production rate of hydrogen atoms is not pronounced by plasma chemistry compared with the supply of hydrogen atoms from a clean filament. This indicates further the importance of keeping the filament clean during the biasing.     

Electron microscopy of interfaces in chemical vapour deposition diamond films on silicon

The structure of interfaces in diamond films grown on Si(100) has been investigated by transmission electron microscopy for the early stages of microwave-assisted chemical vapour deposition. Using conditions optimized for achieving so-called highly-oriented diamond films the depositions were performed in two steps, a bias-enhanced nucleation step and a subsequent growth step. Characteristic for the early deposition stages is the self-organized formation of regular arrays of predominantly {111}-facetted Si substrate surface grooves and islands elongated along [1̄10] and [110] directions. Subsequently, an interlayer of nanocrystalline β-silicon carbide islands forms, followed by the formation of epitaxially oriented diamond nanocrystals with high fractions of {111} interfaces. High-resolution electron microscopy of the interface regions depicts arrays of terminating {111} diamond planes at an average ratio of five diamond to four SiC lattice planes which corresponds to a remaining lattice mismatch of 2.3%. The orientation relationships between the lattices may be described by a coincidence site lattice model if the elastic lattice distortions are taken into account. Only small fractions of amorphous inclusions are present near interfaces, essentially consisting of amorphous carbon as could be deduced from analyses of the C K edge fine structure in electron energy loss spectra. The observations are compared with cases for which diamond nucleation directly on silicon has been obtained.     

Heteroepitaxial nucleation of diamond on Si(100) via double bias-assisted hot filament chemical vapor deposition

A new process has been developed to obtain high density epitaxial diamond nucleation via a double bias-assisted hot filament chemical vapor deposition (HFCVD). In the process, a negative bias voltage is applied to the Si substrate and a positive bias voltage is applied to a steel grid placed on top of the hot filaments. With this arrangement, a stable plasma can be generated between the grid and the hot filaments. Ions in the plasma are then drawn to the substrate by a negative substrate bias voltage. The impinging rate of these ions can be easily controlled by adjusting the grid current, and the ion energy can be independently controlled by adjusting the substrate bias voltage. Hence, the energy and dosage of ion bombardment onto the Si(100) substrate can be controlled easily and independently. With the controlled ion bombardment, high density and heteroepitaxial nucleation can be achieved routinely. After the nucleation process, highly textured diamond films were grown by either the HFCVD or the microwave plasma chemical vapor deposition process (MPCVD).     

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.     

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.     

Analysis of diamond nucleation on molybdenum by biased hot filament chemical vapor deposition

The nucleation and initial growth of diamond on molybdenum using biased hot filament chemical vapor deposition were investigated by scanning electron microscopy, Raman spectroscopy and adhesion force tests. The studies showed that the negative biased pre-treatment greatly enhanced the nucleation density and adhesion force of diamond films on molybdenum. The experimental evidence was confirmed that there is large stress near the interface between the diamond and the Mo substrate, which were originated from the disordered graphite phases and molybdenum carbide near the interface. This may play an important role during nucleation stage. However, larger stress can cause the degradation of the adhesion force of diamond films on Mo substrate. However, the adhesion force was enhanced with increasing bias voltage. The theoretical relationship between the adhesion force and the bias voltage is given by theoretical calculation.     

Characterization of boron-doped micro- and nanocrystalline diamond films deposited by wafer-scale hot filament chemical vapor deposition for MEMS applications

Micro- and nanocrystalline diamond (MCD and NCD) films are deposited on 4-inch silicon substrates by a large-area multi-wafer-scale hot filament chemical vapor deposition (HFCVD) system. The films are in-situ doped by boron. The chemical and crystalline structures are studied by electron probe microanalysis (EPMA), Raman spectroscopy and X-ray diffraction (XRD). The microcrystalline films have a preferred (111) texture, while the nanocrystalline films exhibit (220) texture. Strain gauges and cantilever beam arrays are micro-fabricated by surface micro-machining techniques to characterize the residual strain and strain gradient of the diamond films. Both micro- and nanocrystalline films have small compressive strains of − 0.052% and − 0.040% respectively, with the strain gradient of about 10^− 5 μm^− 1. These values are low enough to enable the realization of many MEMS devices.     

Nucleation of diamond over nanotube coated Si substrate using hot filament chemical vapor deposition (CVD) system

We studied the use of carbon nanotubes as a seeding layer for the nucleation of diamond on Si (100) substrate by using a hot filament chemical vapor deposition (HFCVD) system. Prior to deposition, substrates were seeded with multi-wall carbon nanotube (MWCNT) powder which was prepared separately. MWCNTs were used as nucleation precursors. The diamond grains grew essentially over the nanotubes with a higher growth density in comparison with the un-seeded substrates. The scanning electron microscopy (SEM) image of surface morphology shows crystallites of cauliflower shaped grains. The micro Raman spectroscopic results show a sharp peak at 1,332 cm^-1 corresponding to diamond phase. X-ray photoelectron spectroscopic study show the presence of carbon (C_1s) phase. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

A new polarised hot filament chemical vapor deposition process for homogeneous diamond nucleation on Si(100)

A new hot filament chemical vapor deposition with direct current plasma assistance (DC HFCVD) chamber has been designed for an intense nucleation and subsequent growth of diamond films on Si(100). Growth process as well as the I=f(V) characteristics of the DC discharge are reported. Gas phase constituents activation was obtained by a stable glow discharge between two grid electrodes coupled with two sets of parallel hot filaments settled in-between and polarised at the corresponding plasma potential. The sample is negatively biased with a small 10–15 V extraction potential with respect to the cathode grid. Such design allows to create a high density of both ions and radicals that are extracted and focussed onto the surface of the sample. The current density onto the sample can be finely tuned independently of the primary plasma. A homogeneous plasma fully covering the sample surface is visualized. Consequently, a high-density nucleation (⩾10¹⁰ cm⁻²) occurs.     

Effects of cobalt and cobalt oxide buffer layers on nucleation and growth of hot filament chemical vapor deposition diamond films on silicon (100)

An initial study on the nucleation and growth of diamond, using hot filament chemical vapor deposition (HFCVD) technique, was carried out on Co and CoO thin buffer layers on non-carbon substrates (Si (100)), and the results were compared with conventional scratching method. The substrate temperature during the growth was maintained at 750±50 °C. A mixture of CH₄ and H₂ (1: 100 volume %) was used for deposition. The total pressure during the two hour deposition was 30±2 Torr. X-ray photoelectron spectroscopy (XPS) study showed the diamond nucleation at different time periods on the Co and CoO seed layers. It is observed that Co helps in nucleation of diamond even though it is known to degrade the quality of diamond film on W-C substrate. The reason for improvement in our study is attributed to (i) the low content of Co (~0.01%) compared to W-C substrate (~5–6%), (ii) formation of CoSi₂ phase at elevated temperature, which might work as nucleation sites for diamond. SEM analysis reveals a change in the morphology of diamond film grown on cobalt oxide and a significant reduction in the size of densely packed crystallites. Raman spectroscopic analysis further suggests an improvement in the quality of the film grown on CoO buffer layer.     

Carbon nanowall growth on carbon paper by hot filament chemical vapour deposition and its microstructure

Carbon nanowall films were synthesized by plasma enhanced hot filament chemical vapour deposition on carbon paper, a three dimensionally structured material. The micro-structured nature of the carbon paper, which is composed of an irregular and open mesh of carbon fibres, allowed one to determine the microstructure of the carbon nanowalls both at the tip and at the fibre–nanowall base interface. The number of graphenes which pile up to form the structure of a single nanowall ranges from 1 to 2 at the tip up to several 10s at the base, making this material suitable to study and eventually exploit the electronic properties of graphenes on a macroscopic scale. Such material is promising for electrochemical applications.     

Filament metal contamination and Raman spectra of hot filament chemical vapor deposited diamond films

Chemical vapor deposited diamond films grown in a hot filament reactor using three filament metals (tungsten, tantalum, and rhenium) have been analyzed for their metal impurity content. This is the first report wherein all three common CVD filament metals have been examined and a single technique used for diamond film analysis. Tungsten carbide filaments yielded the lowest impurity level (few ppm by mass), whereas rhenium yielded the highest (parts per thousand). The effects of filament temperature and addition of ammonia or oxygen to the reactant gas mixture were examined. A correlation was observed between the metal content of the product films and their quality, as judged using Raman spectroscopy. Films with the highest metal content yielded Raman spectra showing the lowest fluorescence background, the smallest sp² carbon contribution, and the narrowest 1332 cm⁻¹ diamond line.     

Mechanism of diamond nucleation enhancement by electron emission via hot filament chemical vapor deposition

The mechanism of diamond nucleation enhancement by electron emission in the hot filament chemical vapor deposition process has been investigated by scanning electron microscopy, Raman spectroscopy and infrared (IR) absorption spectroscopy. The maximum value of the nucleation density was found to be 10¹¹ cm⁻² with a −300 V and 250 mA bias. The electron emission from the diamond coating on the electrode excites a plasma, and greatly increases the chemical species, as we have seen by in situ IR absorption. The experimental studies showed that the diamond and chemical species were transported and scattered from the diamond coating on the electrode and through the plasma towards the substrate surface, where they caused enhanced nucleation.     

Gradual transitions in morphology of diamond films grown by using N2 admixtures of CH4+H2 gas in a hot filament assisted chemical vapour deposition system

A study of the evolution of morphology of diamond films grown as a function of N₂ gas additions to the CH₄+H₂ precursor in an HF-CVD system is presented. With the increase of admixture of N₂ fraction, in contrast to earlier studies, the morphology was observed first to gradually change from {111}-faceted crystallites texture to that of an intermediate cubo-octahedral crystallite texture and then gradually but finally to transform completely into that of {100}-faceted crystallites. The threshold nitrogen concentration, [N₂]^thr, required to bring about the said transition in morphology was much larger than it was reported previously. Moreover, the morphology transition required a larger [N₂]^thr when a large fraction of methane was employed. Further additions of nitrogen, that just exceeded the [N₂]^thr, resulted in growth of films containing slightly bigger {100}-multi-layered grains or isolated planar {100}-platelets. For extremely large nitrogen additions, the growth of nanocrystalline or amorphous carbon films was observed. The N₂ additions more than 50 vol.% did not yield any deposition. Raman scattering and photoluminescence measurements were used respectively for characterizing the quality and nitrogen doping in the films. These results are attributed to the possible catalytic role of atomic nitrogen at the growing surface.     

Thermal chemical vapor deposition of fluorocarbon polymer thin films in a hot filament reactor

Formation of fluorocarbon polymer films with a linear (CF₂-CF₂)_n molecular structure similar to polytetrafluoroethylene, PTFE is described by a hot filament chemical vapor deposition method. Growth process is analyzed by infrared absorption and C(1s), O(1s) and F(1s) core level electron spectroscopy of films deposited at −5 and +70 °C. Absorption doublet at 1220 and 1160 cm⁻¹ assigned to C-F₂ asymmetric and symmetric stretches, rock at 518 cm⁻¹ and wag at 637 cm⁻¹ indicate formation of linearly organized CF₂ groups with minimum hindrance to molecular vibration modes in CVD grown films. Absorption bands at 1660 and 3389 cm⁻¹ show O and OH groups in the films which diminish on annealing. The C(1s) components, CF₃, CF and C-CF bonding show branching, cross-liking and defects sites which increase as substrate temperature is increased. The O(1s) line analysis shows O₂ in fluorocarbon films is chemically bonded as C-O and F₂CO with relative ratio depending on the film growth temperature. Both O₂ and OH are the result of additional reaction pathways involving the species generated from fragmentation of CF₃C(O)F. Molecular structure of fluorocarbon polymer films involving these species are discussed which are in conformity with the XPS and IR absorption data.