Grain boundaries and grain size distributions in nanocrystalline diamond films derived from fullerene precursors

Film growth from C{sub 60}/Ar mixtures results in very pure diamond. Diamond films grown using C{sub 60} as a carbon source have been shown to be nanocrystalline with average grain sizes of 15 nm and standard deviations of 13 nm. The measured grain size distribution for two separate films, each based on measurements of over 400 grains, were found to be very similar and well approximated by a gamma distribution. Unlike typical CVD grown diamond films, these nanocrystalline films do not exhibit columnar growth. From the measured grain size distributions, it is estimated that 2% of the carbon atoms are located in the grain boundaries. The structure of the carbon in the grain boundaries is not known, but the films survive extended wear tests and hold together when the substrate is removed, indicating that the grains are strongly bound. The grain boundary carbon may give rise to additional features in the Raman spectrum and result in absorption and scattering of light in the films. We also expect that the grain boundary carbon may affect film properties, such as electrical and thermal conductivity

Diamond films grown from fullerene precursors

Transmission Electron Microscope (TEM) techniques are applied to study the microstructure of diamond films grown from fullerene precursors. Electron diffraction and electron energy loss spectra (EELS) collected from the diamond films correspond to that of bulk diamond. Microdiffraction, high resolution images and EELS help determine that the first diamond grains that nucleate from fullerene precursors generally form on a thin amorphous carbon interlayer and seldom directly on the silicon substrate. Grain size measurements reveal nanocrystalline diamond grains. Cross section TEM images show that the nanocrystalline diamond grains are equiaxed and not columnar nor dendritic. The microstructure of small equiaxed grains throughout the film thickness is believed responsible for the very smooth surfaces of diamond films grown from fullerene precursors

Friction and wear properties of smooth diamond films grown in fullerene-argon plasmas

In this study, we describe the growth mechanism and the ultralow friction and wear properties of smooth (20-50 nm rms) diamond films grown in a microwave plasma consisting of Ar and fullerene (the carbon source). The sliding friction coefficients of these films against Si{sub 3}N{sub 4} balls are 0.04 and 0.1 in dry N{sub 2} and air, which are comparable to that of natural diamond sliding against the same pin material, but is lower by factors of 5 to 10 than that afforded by rough diamond films grown in conventional H{sub 2}-CH{sub 4} plasmas. Furthermore, the smooth diamond films produced in this work afforded wear rates to Si{sub 3}N{sub 4} balls that were two to three orders of magnitude lower than those of H{sub 2}-CH{sub 4} grown films. Mechanistically, the ultralow friction and wear properties of the fullerene-derived diamond films correlate well with their initially smooth surface finish and their ability to polish even further during sliding. The wear tracks reach an ultrasmooth (3-6 nm rms) surface finish that results in very little abrasion and ploughing. The nanocrystalline microstructure and exceptionally pure sp{sup 3} bonding in these smooth diamond films were verified by numerous surface and structure analytical methods, including x-ray diffraction, high-resolution AF-S, EELS, NEXAFS, SEM, and TEM. An AFM instrument was used to characterize the topography of the films and rubbing surfaces

Growth of (110) Diamond using pure Dicarbon

We use a density-functional based tight-binding method to study diamond growth steps by depositing dicarbon species onto a hydrogen-free diamond (110) surface. Subsequent C_2 molecules are deposited on an initially clean surface, in the vicinity of a growing adsorbate cluster, and finally, near vacancies just before completion of a full new monolayer. The preferred growth stages arise from C_2n clusters in near ideal lattice positions forming zigzag chains running along the [-110] direction parallel to the surface. The adsorption energies are consistently exothermic by 8--10 eV per C_2, depending on the size of the cluster. The deposition barriers for these processes are in the range of 0.0--0.6 eV. For deposition sites above C_2n clusters the adsorption energies are smaller by 3 eV, but diffusion to more stable positions is feasible. We also perform simulations of the diffusion of C_2 molecules on the surface in the vicinity of existing adsorbate clusters using an augmented Lagrangian penalty method. We find migration barriers in excess of 3 eV on the clean surface, and 0.6--1.0 eV on top of graphene-like adsorbates. The barrier heights and pathways indicate that the growth from gaseous dicarbons proceeds either by direct adsorption onto clean sites or after migration on top of the existing C_2n chains.Comment: 8 Pages, 7 figure

In situ surface roughness measurement during PECVD diamond film growth

To investigate the development of surface morphology and bulk optical attenuation in diamond films, we have followed diamond film growth on silicon by in-situ laser reflection interferometry in a microwave plasma chemical vapor deposition system. A model for the interpretation of the reflectivity data in terms of film thickness, rms surface roughness and bulk losses due to scattering and absorption is presented. Results are compared with ex situ measurements of these quantities and found to be in good agreement

TEM study of diamond films grown from fullerene precursors

Transmission Electron Microscope (TEM) techniques are applied to study the microstructure of diamond films grown from fullerene precursors. Electron diffraction and electron energy loss spectra (EELS) collected from the diamond films correspond to that of bulk diamond. Microdiffraction, high resolution images and EELS help determine that the first diamond grains that nucleate from fullerene precursors generally form on a thin amorphous carbon interlayer and seldom directly on the silicon substrate. Grain size measurements reveal nanocrystalline diamond grains. Cross section TEM images show that the nanocrystalline diamond grains are equiaxed and not columnar nor dendritic. The microstructure of small equiaxed grains throughout the film thickness is believed responsible for the very smooth surfaces of diamond films grown from fullerene precursors

Physical and tribological properties of diamond films grown in argon-carbon plasmas

Nanocrystalline diamond films have been deposited using a microwave plasma consisting of argon, 2--10% hydrogen and a carbon precursor such as C{sub 60} or CH{sub 4}. It was found that it is possible to grow the diamond phase with both carbon precursors, although the hydrogen concentration in the plasma was 1--2 orders of magnitude lower than normally required in the absence of the argon. Auger electron spectroscopy, x-ray diffraction measurements and transmission electron microscopy indicate the films are predominantly composed of diamond. Surface roughness, as determined by atomic force microscopy and scanning electron microscopy indicate the nanocrystalline films grown in low hydrogen content plasmas grow exceptionally smooth (30--50 nm) to thicknesses of 10 {mu}m. The smooth nanocrystalline films result in low friction coefficients ({mu}=0.04--0.06) and low average wear rates as determined by pin-on-disk measurements

Pulsed ion beam methods for in situ characterization of diamond film deposition processes

Diamond and diamond-like carbon (DLC) have properties which in principle make them ideally suited to a wide variety of thin-film applications. Their widespread use as thin films, however, has been limited for a number of reasons related largely to the lack of understanding and control of the nucleation and growth processes. Real-time, in situ studies of the surface of the growing diamond film are experimentally difficult because these films are normally grown under a relatively high pressure of hydrogen, and conventional surface analytical methods require an ultrahigh vacuum environment. It is believed, however, that the presence of hydrogen during growth is necessary to stabilize the corrugated diamond surface structure and thereby prevent the formation of the graphitic phase. Pulsed ion beam-based analytical methods with differentially pumped ion sources and particle detectors are able to characterize the uppermost atomic layer of a film during, growth at ambient pressures 5-7 orders of magnitude higher than other surface-specific analytical methods. We describe here a system which has been developed for the purpose of determining the hydrogen concentration and bonding sites on diamond surfaces as a function of sample temperature and ambient hydrogen pressure under hot filament CVD growth conditions. It is demonstrated that as the hydrogen partial pressure increases, the saturation hydrogen coverage of the surface of a CVD diamond film increases, but that the saturation level depends on the atomic hydrogen concentration and substrate temperature