ALBERT

Notes: Hydrogen containing carbon (C:H) films have been prepared by ion beam deposition of 160 eV ethane ions on a carrier consisting of a Pt(111) single crystal surface covered with a monolayer of graphite. Several monolayers thick films deposited at 350 K contain hydrogen bound to sp, sp2, and sp3 hybridized carbon. Vibrational spectroscopy reveals that thermal D(H) atoms directed to the C:H film surface hydrogenate unsaturated CH groups at the surface and transform sp and sp2 hybridized carbon to sp3. The observed reaction mechanism explains the microscopic processes in chemical erosion of graphite by hydrogen atoms which is a crucial reaction step in the low pressure synthesis of diamondlike carbon.

Notes: Several monolayers thick hydrogenated carbon films, C:H, were prepared by ion beam deposition from hydrocarbon process gases onto Pt and monolayer C covered Pt single crystal surfaces and investigated with Auger electron and thermal desorption spectroscopies in an UHV environment. Efficient deposition was achieved at ion energies in the 160–300 eV range. The deposited thickness and H/C ratio of the films depend on both, target temperature and H/C ratio of the process gas. It is shown that the C monolayer is crucial for efficient on-top deposition. Irrespective of the process gas used for deposition, the films grow as a C network and assume a constant H/C ratio at thicknesses greater than ∼ 3 monolayers. The H/C ratio of the films scale with the H content of the hydrocarbon process gas, a H/C ratio of 0.4 was obtained for ethane at 350 K substrate temperature. Upon thermally activated decomposition the films release molecular hydrogen as the major gaseous species and various hydrocarbons as minority species. The latter products signal chemical erosion of the film. It is shown that the rate determining step towards erosion via methane is a C–C bond breaking event which releases methyl radicals from the C network in the film. The activation energies for this step are determined as a 10 kcal/mol wide Gaussian distribution centered at 56 kcal/mol. Transport through the film is found to be so fast that it does not contribute to the observed gas release rates. © 1995 American Institute of Physics.

Notes: Few monolayers thick hydrogenated carbon films doped with boron (C/B:H) were prepared and investigated in an ultrahigh-vacuum environment by high-resolution electron energy loss, Auger electron, electron energy loss, and thermal desorption/decomposition spectroscopies with specific emphasis on their chemical erosion behavior as compared to their undoped C:H counterparts. Films of thicknesses ranging from 1 to about 10 monolayers, with a maximum B/C ratio of 0.5, were grown by ion-beam deposition at room temperature on a carrier consisting of a Pt(100) single-crystal surface covered with a graphite monolayer. The process gas used was a mixture of ethane and trimethylboron of varied compositions. While at zero boron concentration the films exhibit a graphiticlike structure with about equal amounts of carbon atoms in the sp2 and sp3 hybridization state, with increasing boron concentration the film structure becomes increasingly sp3 dominated. This is evidenced by decreasing HREELS loss intensities of the vibrational modes related to graphitic hydrogenated carbon, i.e., C=C, sp2 CH stretches, and aromatic CH deformations, but enhanced C–C and sp3 CHn stretch mode intensities. No BH vibrational modes have been observed at any doping level. In accordance with these observations, the C-272 eV Auger peak line shape underwent a change characteristic for a sp3-dominated network upon B doping. The π-plasmon energy was found to shift toward lower energies at C/B:H films which also is in line with a decrease of the carbon sp2 concentration, giving further support for a change to a less graphitic structure. The observed enhanced capacity for hydrogen in the films was found to correlate in a linear fashion with the increase of the fraction of carbon atoms in the sp3 configuration. The relative hydrogen content of the films, H/C, starting at 0.4 at zero boron content, was observed to increase, saturating at 0.75 for boron concentrations greater than 10%.This in turn coincides with a substantial growth of the film hydrogen capacity, as judged from the amount of H2 desorbing from the films between 500 and 1100 K upon thermal decomposition of the films. Although hydrogen originating from sp3 CH groups increased significantly, the amount of chemically eroded species, monitored by CnHm production in the thermal decomposition spectra, was unaffected by boron doping. However, the desorption maxima for either species, hydrogen and hydrocarbons, shift to lower temperatures at boron doped films. As reasons for the effect of B doping on the chemical constitution of C/B:H films and the resulting chemical erosion behavior, the capability of B to block the formation of aromatic structures is proposed. © 1995 American Institute of Physics.

Notes: The mechanism of thermally activated chemical erosion of sputter-deposited C:H films of a few atomic layer thickness is investigated using thermal desorption spectroscopy. Methane, CH3 radicals, and various C2Hj species of molecular and radical nature desorb as gaseous products above 600 K competitively to H2. C-CiHj bond breaking is determined to be the rate limiting step of hydrocarbon production. The reaction is of first order with respect to CiHj precursors in the films with a distribution of activation energies, 56±5 kcal/mol for methane production. CH3 radical desorption occurs predominantly from the very surface of the C:H films.

Notes: Benzene and (1,4)-dimethyl-cyclohexane monolayers were physisorbed on graphite covered Pt(111) surfaces. Exposure of benzene monolayers at 125 K to D atoms (1700 K) initially hydrogenates sp2 hybridized C atoms with a cross section of ca. 8 A(ring)2 producing C6H6D intermediates. Additional D atom reactions either transform this intermediate via a second hydrogenation reaction to cyclohexadiene-d2, C6H6D2, or restore benzene, C6H5D, via H abstraction. Once the aromaticity is broken, successive hydrogenation of the diene occurs rapidly generating the saturated cyclohexane-d6, C6H6D6. The C6H5D reaction product can undergo further H/D exchange reactions and, at any level of deuteration, the benzene species might get hydrogenated. Monolayers of the saturated hydrocarbon (1,4)-dimethyl-cyclohexane (DMCH) that are exposed to D atoms produce deuterated DMCH via successive abstraction/hydrogenation reactions. Thermal desorption mass spectra revealed that H atoms at the ring were exchanged with an apparent cross section of 1.7 A(ring)2. Methyl groups H atoms were exchanged much more slowly than ring H atoms. It was also observed that D exposed molecules/radicals exhibit a tendency to desorb from the surface, which is ascribed to the exothermicity of the reactions which lead to these species. © 1996 American Institute of Physics.