Alkyl-modified silicon nanocrystallites are efficient fluorophores which are of interest for fundamental spectroscopic studies and as luminescent probes in biology because of their stability in aqueous media. In this work we have investigated these particles using scanning tunneling microscopy, synchrotron-radiation excited photoemission, and x-ray excited optical luminescence (XEOL). During the course of illumination with 145-eV photons we have monitored the evolution of the Si2p core level and, in samples which have suffered prolonged atmospheric exposure, observed in real time the growth of an extra Si2p component attributed to in situ photoinduced oxidation of the Si nanocrystallites. XEOL reveals that two emission bands are active upon soft-x-ray photon excitation and that photoluminescence intensity decreases with photon exposure, which is attributed to charge trapping within the film. (c) 2005 American Institute of Physics.