The resistance R, spectral emissivity ∊, and power consumption of W and Re filaments heated to 2500 °C in mixtures of CH4 or C2H2 in H2 have been measured in a series of experiments focusing on the state of the filament activity, i.e., its ability to dissociate the reactant gases. It has been found that these properties of the filaments, as well as the partial pressures of CH4 and C2H2 in the reaction chamber, depend critically on both the filament temperature and the reactant ratio, e.g., C2H2/H2. Specifically, both W and Re filaments show sharp jumps in power consumption at essentially the same temperature, signaling strong increases in filament activity and, hence, production of atomic hydrogen. These results are proposed to be due to the removal of nonreactive carbon from the surface of the filament via etching by atomic hydrogen and are consistent with the predictions of our thermodynamic model for the C–H system. Evidence for gas phase reactions is presented and the role of thermal diffusion is discussed. The emissivities of the W and Re filaments are observed to have significantly different temperature dependences which are attributed to differences in the phase diagrams for the W–C and Re–C systems. The implications of these results for hot-filament diamond CVD are discussed.

The optical band gap, density, and hydrogen content of diamond-like carbon films have been controllably varied by rf biasing the substrate in an ECR discharge of pure methane. The optical band gap varied from 2.7 to 1.2 eV, the density from 1.4 to 2.2 g/cm3, and the atomic fraction of hydrogen from 50 to 5%. The range of measured values is in agreement with those predicted by both the random covalent network and defected graphite models.

Oxidation kinetics of microwave plasma assisted CVD diamond and diamond-like carbon (DLC) films in flowing oxygen were evaluated in the temperature range of 500 to 750 °C and were compared with those of graphite and natural diamond. The diamond and DLC films were prepared using CH4/H2 ratios of 0.1, 0.25, 0.5, 1.0, and 2.0%. The films deposited at 0.1% ratio had a faceted crystalline structure with high sp3 content and as the ratio increased toward 2%, the films contained more and more fine crystalline sp2 bonded carbon. The oxidation rates were determined by thermal gravimetric analysis (TGA), which shows that the films deposited at ratios of 2, 1, and 0.5% oxidized at high rates and lie between the rates of natural diamond and graphite. The oxidation rate decreased with lower CH4/H2 ratio and the films deposited at 0.25 and 0.1% exhibited the lowest oxidation rates associated with the highest activation energies in the range of 293–285 kJ/mol · K. The oxidation behavior of microwave plasma assisted diamond films was similar to that of DC plasma assisted CVD diamond films. The results suggest that the same mechanism of oxidation is operational in both DC and microwave plasma assisted diamond films and is probably related to the microstructure and preferred orientation of the crystallites.

Hard amorphous hydrocarbon films have been deposited by RF glow discharges in methane/hydrogen mixtures with different hydrogen isotopes. For CH4 + D2 and CD4 + H2 gas mixtures, the film growth rate, the density, the refractive index, and the isotopic hydrogen content are obtained as functions of the process gas composition. Further, the hydrogen loss induced by 15 keV helium ions is studied. The results are qualitatively interpreted in terms of different effects of ion bombardment during film deposition which influence the properties of the resulting films.

Raman spectra were taken of 48 polycrystalline diamond films grown by hot-filament and microwave-plasma chemical vapor deposition (CVD), and one gem-quality diamond, and characterized by fitting the spectra to a model line shape function. The line shape function contains three components: a narrow symmetric line at ∼1333 cm−1, the Raman line of diamond; a band centered at ∼1525 cm−1 ascribed to sp2-bonded carbon; and a broad background due to photoluminescence (PL). Four spectral parameters were observed to change from one specimen to another in an interrelated manner: (1) the linewidth of the diamond Raman line, which varies from ∼3 to ∼25 cm−1; (2) the intensity in the tails of the diamond Raman line, several halfwidths away from the peak; (3) the peak intensity ratio of the sp2-bonded carbon band to the diamond Raman line, which varies from ∼0 to ∼1; and (4) the intensity ratio of the PL background to the diamond Raman peak, which varies from ∼0.03 to ∼9. We suggest that the interrelated changes in the Raman spectra are due to changes in the abundance of sp2-bonded defect structures within the diamond crystallites. Polynuclear aromatic clusters are a possible model for these defect structures. Differences in film morphology, which were observed by SEM imaging, appear to be correlated with the changes in the Raman spectra. The peak position of the diamond Raman line is shifted to higher wave number in the CVD-grown films than in the gem, by as much as 3 cm−1, but this shift is not correlated with the other changes in the Raman spectra. As a function of deposition conditions, the defect-related features of the Raman spectra generally increase with increasing methane concentration or substrate temperature, and decrease with increasing oxygen concentration. A cyclic dependence of the defect-related features on deposition time is observed for one set of films grown by hot-filament CVD.

Bilayer diamond films were deposited on Si substrates by microwave-plasma chemical-vapor deposition (CVD) using a methane-hydrogen gas mixture. The first layer was deposited for 3 h using a reaction gas which was composed of 2.5 vol. % methane and 97.5 vol.% hydrogen. The deposited film consisted of very weakly (110)-oriented microcrystalline diamonds as well as amorphous carbon and graphite. In order to remove non-diamond carbons from the film surface, the specimen was treated in hydrogen plasma for 1 h. Finally, a second layer was deposited on the first layer for 14 h using a methane concentration of between 0.2 and 1.6 vol.%. It was found that the x-ray intensity of the (220) diffraction of the bilayer films was much greater than that of the (111) diffraction, indicating that the diamond grains in the second layer were strongly oriented with their crystallographic (110) planes parallel to the substrate surface. X-ray diffraction spectra of bilayer films in which the second layer was deposited for 7, 14, 21, and 35 h using two different methane concentrations, 0.3 and 1.2 vol.%, showed that within periods of up to 21 h, the (220) intensity increased with the deposition time much more quickly than the (111) intensity, indicating that the degree of (110) orientation was further enhanced as the second layer thickness increased. However, the (220) intensity decreased after 21 h, presumably due to thermal randomization. Results of scanning electron microscopy, electron diffraction, and Raman spectroscopy of the bilayer films are also presented.

Oxidation of polycrystalline diamond films on (111) Si wafers in air at temperatures up to 1073 K was investigated by thermogravimetry. The diamond films before and after partial oxidation were characterized by optical and scanning electron microscopy, x-ray, infrared, and Raman spectroscopy. The oxidation of synthetic diamond films started at a lower temperature than that for natural diamond. The rates of oxidation of the diamond films synthesized by the hot filament and the microwave plasma methods were intermediate between the rates of oxidation of the 111 and 100 planes of natural diamond crystals. The apparent activation energy for the oxidation of the synthetic diamond films agreed well with that for the oxidation of natural diamond via diamond to graphite transition at low oxygen pressures.

Thin C:N films were prepared by rf diode sputtering of a graphite target in a mixed argon/nitrogen plasma. We have observed a systematic variation of the properties of these C:N films with an increase in the nitrogen partial pressure. XPS, AES, and TEM studies show that nitrogen will stabilize the diamond sp3 bonding. From XPS studies, we found that the density of our C:N films is increased from 1.37 × 1023 atoms/cm3 to 1.63 × 1023 atoms/cm3 using a 100% nitrogen plasma. The energy gap of our nitrogen carbon also shows an increase from 1.1 eV to 1.4 eV using a 100% nitrogen plasma. The mechanical properties also are shown to be enhanced for certain applications. By using the same method, we can also show that it can produce 100% amorphous C:N films which are more diamond-like as compared with other methods.

Schottky diodes were formed with free-standing polycrystalline thin film diamond base as well as with polycrystalline diamond films grown on crystalline silicon. Current-voltage and internal photoemission measurements were used to characterize the Schottky diodes and the diamond film. Internal photoemission measurements yielded a barrier height of 1.15 eV. A comparison of experimental data for metal contacts to free-standing diamond films and those on silicon substrates indicates that both rectification and internal photoemission originate at the metal/diamond interface.

The photoluminescence spectra of polycrystalline diamond films prepared by filament assisted chemical vapor deposition are dominated by a defect band with a strong zero phonon line near 1.68 eV and weak phonon replicas at lower energies. The 1.68 eV line is blucshifted from the 1.675 eV zero phonon line associated with the neutral vacancy in bulk diamond. The line shape and position of the 1.68 eV line are shown to depend on substrate material (Si, Mo, Ni). The 1.68 eV emission for Ni and Mo substrates is interpreted in terms of the stress shifted and broadened neutral vacancy emission. The broader 1.68 eV line observed for Si substrates may indicate the additional effects of Si absorption by the diamond films. Films prepared by an oxygen-acetylene flame technique exhibit two additional luminescence bands with zero phonon lines at 1.95 and 2.16 eV. These lines have been tentatively assigned to nitrogen-vacancy complexes. The temperature dependence (6 K–300 K) of the luminescence of a free-standing diamond film, which had been deposited on a molybdenum substrate, is comparable to similar observations reported for bulk diamond. We have also observed a strong dependence of the PL spectra radially across a given combustion film and associated this with details of the flame chemistry.

Absorption and cathodoluminescence spectra have been recorded for single crystals of diamond and polycrystalline films of diamond, grown by microwave-assisted chemical vapor deposition (CVD) using methane and hydrogen. The investigation has been carried out to see to what extent the properties of CVD diamond are similar to those of conventional diamond, and to what extent they are unique. Studies have been made of the as-grown material, which has not been intentionally doped, and also samples that have been subjected to radiation damage and thermal annealing. The single crystals grown using methane concentrations of 0.5 to 1.0% exhibit bright blue “band A” emission and also intense edge emission, similar to the cathodoluminescence spectra of some natural type IIa diamonds. This implies that the crystals are relatively free from structural and chemical defects, a conclusion which is reinforced by the absence of any zero-phonon lines in the absorption spectra of crystals which have been subjected to radiation damage and annealing at 800 °C. Before radiation damage the spectrum does, however, reveal an absorption which increases progressively to higher energies, and which may be associated with sp2-bonded carbon. The Cathodoluminescence spectra after radiation damage indicate that the crystals contain some isolated nitrogen, and the detection of H3 luminescence, following thermal annealing at 800 °C, demonstrates for the first time that these samples contain small concentrations of nitrogen pairs. All of the polycrystalline films, grown using methane concentrations between 0.3 and 1.5%, have an absorption which increases progressively to higher energies, and which again is attributed to sp2-bonded carbon. This absorption is stronger in the films grown using higher methane concentrations. Films grown at a methane concentration of 0.3% also exhibit bright blue cathodoluminescence, although the edge emission is undetectably weak. The use of higher methane concentrations produces films with evidence in the cathodoluminescence spectra of nitrogen + vacancy and nitrogen + interstitial complexes, as well as optical centers unique to CVD diamond. One particular defect produces an emission and absorption line at 1.681 eV. By implanting conventional diamonds with 29Si ions it has been confirmed that this center involves silicon, and it has been shown that the 1.681 eV luminescence is relatively more intense in implanted diamonds which have a high concentration of isolated nitrogen.

The adhesion of diamond films deposited by microwave plasma-enhanced CVD on various substrates can be quantitatively determined by an indentation method. The friction behaviors of diamond-coated cemented carbides sliding against a brass ring were studied. The wear resistance of the diamond-coated cemented carbide inserts and the commercial inserts with the other ceramic coatings were compared and directly evaluated by turning tests. Effects of the coating conditions, the substrate materials, and the surface pretreatments of the substrate on adhesion, friction, and wear properties are discussed.

Using an are-discharge method, we deposited a diamond-like carbon film 600 nm thick on hardened steel. Characterization of the film was carried out with Raman spectroscopy. In dry sliding wear and friction tests, with a hardened steel pin as a counterpart, we obtained a friction coefficient between 10000 and 20000 cycles, with the maximum value of 0.18. The value decreased to 0.12 after about 100000 cycles. We obtained a wear coefficient of 7 × 10−17 m3/mN. A transfer layer formed on the pin during sliding and probably had the dominating effect on the tribological behavior. We observed in nanoindentation measurements that the film softened in a wear track during the first 20000 cycles. Although fracture pits on the wear track occurred, fracture is not the dominant failure mechanism of these films. Degradation of good tribological properties was caused mainly by partial wear-through of the film after 370000 cycles and by a subsequent redeposition of the transfer film on the wear track during prolonged sliding.

Diamond-like carbon, or DLC, films, prepared by the rf plasma decomposition of acetylene, have been deposited at substrate temperatures of 100 to 250 °C, with the substrate at a negative bias of 80 V dc. The DLC films have been annealed in vaccum at temperatures up to 600 °C for 3–4 h. The optical properties of the as-deposited and annealed films have been characterized by ellipsometry and Fourier transform infrared spectroscopy. The wear resistance of the thin DLC films and their friction coefficients have been characterized by a specially designed tribotester. The stresses in the films have also been determined. No significant differences were found between the index of refraction and IR absorption spectra of the as-deposited films, or films annealed at up to 390 °C. The DLC films begin losing hydrogen after annealing above 390 °C and only sp2 bond carbon is observed after annealing at 590 °C. The wear behavior of the as-deposited films was identical for all deposition temperatures. DLC films deposited at 250 °C were more stable and could withstand higher annealing temperature than films deposited at lower temperatures, and remained wear resistant after anneling at 390 °C.

Amorphous carbon films were deposited on glass by dc magnetron sputtering from a graphite target in mixtures of argon and hydrogen. Hydrogen flow and other parameters affected the optical and mechanical properties of these films. Increasing hydrogen content caused the average visible transmittance to vary from 16% to 86% for 500-Å thick films. Maximum compressive stress and hardness occur between 0 and 1% hydrogen flow, resulting in rapid delamination. Low sputtering power moderately increases transmittance and hardness while relieving stress. Transparency is induced in both the high-hydrogen and low-power films by formation of sp3 C–C bonds. In the case of the hydrogenated films, however, a softer polymeric structure is formed.

Thin films of amorphous carbon (a–C) and amorphous hydrogenated carbon (a–C:H) were prepared using magnetron sputtering of a graphite target. The chemical structures of the films were characterized using electron energy loss spectroscopy (EELS) and Raman spectroscopy. The mass density, hardness, residual stress, optical band gap, and electrical resistivity were determined, and their relation to the film's chemical structure are discussed. It was found that the graphitic component increases with increasing sputtering power density. This is accompanied by a decrease in the electrical resistivity, optical band gap, mass density, and hardness. Increasing the hydrogen content in the sputtering gas mixture results in decreasing hardness (14 GPa to 3 GPa) and mass density, and increasing optical band gap and electrical resistivity. The variation in the physical properties and chemical structures of these films can be explained in terms of the changes in the volume of sp2-bonded clusters in the a–C films and changes in the termination of the graphitic clusters and sp3-bonded networks by hydrogen in the a–C:H films.

Diamond films, ranging in thickness to approximately 35 μm, were grown on Si(100) substrates using hot-filament-assisted CVD. Two different CH4:H2 ratios were employed during deposition, and the effects on the film morphology and ultralow-load indentation hardness and modulus were investigated. Films deposited from a single, linear filament exhibited a nonuniform deposition thickness profile that can be described by a simple exponential function. Films deposited at lower methane concentrations, 0.11% CH4 in H2, had larger crystallite sizes of ∼5–8 μm, an average hardness of 31 GPa, and an average modulus of 541 GPa. A higher CH4 concentration of 0.99% in H2 resulted in the formation of finer crystallites of approximately 0.5 μm, an average hardness of 65 GPa, and an average modulus of 875 GPa. While these values lie on the low end or outside of the range reported for single crystal diamond, this study has demonstrated that CVD diamond films can be synthesized with ultrahigh or near ultrahigh hardness.

A study has been made of the correlation between wear resistance and crystalline structure of ion implanted glassy carbon. Nitrogen ions were implanted in glassy carbon with fluences ranging from 5 × 1014 to 5 × 1016 ions/cm2 at an energy of 150 keV. The target temperature during ion implantation was maintained constantly at −70, 25, and 200 °C. Wear tests were carried out with the system of glassy carbon and polishing silk disk on which water including diamond slurry was poured, using a conventional polishing machine. The surface layer structure was investigated by means of laser Raman spectroscopy. Nitrogen implantation causes the wear resistance to improve, and the reduction of wear rate is dependent on the ion fluence and the target temperature during ion implantation. As the fluence increases and the target temperature is lower than room temperature, the wear rate decreases drastically. Raman spectra show that the structure of ion implanted layers becomes what is called amorphous-like as the fluence increases and the target temperature is lowered. In conclusion, the wear resistance of glassy carbon is improved owing to the change in structure followed by nitrogen implantation at a relatively high fluence and low target temperature.

Amorphous carbon-silicon (a–C–Si) coatings with smooth surface and adhesion to steel substrate were deposited at 550°C by a dc glow discharge method from reactant gases of CH4, SiCl4, H2, and Ar at a deposition rate of 1–3 μm h−1. Diamond-like carbon was detected by laser Raman spectroscopy in the coatings with high hardness of Hv 2000 and more than 70 at. % carbon. Ball-on-disk type and Ohgoshi-type apparatuses were used to measure the tribological properties. Ball-on-disk tests revealed that the a–C–Si coatings showed a friction coefficient as low as 0.04 against steel with no lubricant in an ambient atmosphere of 70% relative humidity, which was one-third that of an i–C coating. The wear rate of the steel ball against the coated disk was an order and three orders of magnitude smaller than that against i–C coated and uncoated disks, respectively. Both types of tests showed that the wear rate of the a–C–Si coating itself was also very small.

Polycrystalline diamond films of several thicknesses have been fractured by manual bending and examined by scanning electron microscopy. These films have been deposited in controlled environments at low pressures by chemical vapor deposition and in ambient atmosphere with an oxygen-acetylene torch. Fracture surfaces in the low pressure depositions exhibit cleavage steps across the grains. These surfaces, independent of thickness, are primarily transgranular, attesting to the inherent strength of the deposits. However, the ambient deposited diamond has primarily intergranular fracture indicative of weak grain boundaries. Internal defects, observed with transmission electron microscopy, such as twins, stacking faults, and dislocations, occur generally in both types of deposition with no apparent preference for location or type of deposition.