C60 submonolayers on the Si(1 1 1)-(7 × 7) surface: Does a mixture of physisorbed and chemisorbed states exist?

We have carried out a combined X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy(UPS), and scanning tunnelling microscopy (STM) study of the C60-Si(1 1 1) interaction where the XPS/UPS spectrometer and STM are integrated on a single UHV system. This enables a direct comparison of the XPS/UPS spectra with the STM data and eliminates any uncertainty in C60 coverage measurements. X-ray standing wave measurements and density functional theory calculations have been used to support and interpret the results of the XPS/UPS/STM experiments. Our data conclusively rule out models of C60 adsorption which involve a mixture of physisorbed and chemisorbed molecules [K. Sakamoto, et al., Phys. Rev. B 60 (1999) 2579]. Instead, we find that all molecules, up to 1 monolayer coverage, bond to the surface via Si–C bonds which are predominantly of covalent character.