Plasma-enhanced chemical vapour deposition has been applied to the fabrication of high-quality SiO2/Si interfaces and to the functionalization of the silicon dioxide surfaces for organic thin film transistor applications. The advantage of the method herein reported resides in the possibility of activating the substrate, depositing and functionalizing high-quality SiO2 films in a single-run process, at low temperature. The structural properties of silicon dioxide samples have been studied by infrared spectroscopy, angle resolved and depth profiling X-ray photoelectron spectroscopy. The electronic properties have been retrieved from the leakage current values and the Fowler-Nordheim current plots. (c) 2007 Elsevier B.V. All rights reserved.