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 thesp2andsp3hybridization state, with increasing boron concentration the film structure becomes increasinglysp3dominated. This is evidenced by decreasing HREELS loss intensities of the vibrational modes related to graphitic hydrogenated carbon, i.e., C=C,sp2CH stretches, and aromatic CH deformations, but enhanced C–C andsp3CHnstretch 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 asp3‐dominated network upon B doping. The &pgr;‐plasmon energy was found to shift toward lower energies at C/B:H films which also is in line with a decrease of the carbonsp2concentration, 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 thesp3configuration. 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 H2desorbing from the films between 500 and 1100 K upon thermal decomposition of the films. Although hydrogen originating fromsp3CH groups increased significantly, the amount of chemically eroded species, monitored by CnHmproduction 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.