An essential prerequisite for the successful application of Si/SiO 2 nanostructures in photovoltaics is the realization of well-defined and abrupt interfaces with low densities of interface gap states. Here, a complete in situ process from preparation and hydrogen passivation to interface gap state analysis by near-UV photoelectron spectroscopy without breaking ultrahigh vacuum (UHV) conditions is introduced. It is demonstrated that by RF plasma oxidation of Si(111) substrates with thermalized neutral oxygen atoms, ultrathin SiO2 layers can be realized with compositionally and structurally abrupt Si/SiO2 interfaces and a minimal amount of intermediate oxidation states bridging the transition from Si to SiO 2. Plasma oxidized samples have significantly lower interface gap states than samples oxidized by thermal oxidation at 850°C. Interface gap state densities were further reduced by in situ hydrogen plasma passivation with nearly thermalized H atoms. The resulting reduction of interface recombination velocity and the increase of effective majority and minority carrier lifetimes are revealed by constant photocurrent measurements and quasi-steady-state photoconductance, respectively. © IOP Publishing Ltd.