X-ray photoelectron spectra (XPS) of thin SiO2 layers grown by pulsed Nd:YAG laser at a substrate temperature of 748 K are presented, The peak decomposition technique combined with depth profiling is employed to identify the composition and chemical states of the film structure. It is established that the oxide is non-stoichiometric, and contains all oxidation states of Si in different amounts throughout the film. The interface Si/laser-grown oxide is not abrupt, and the coexistence of Si2O3 and Si2O suboxides in a relatively wide interfacial region is found. It is concluded that post-oxidation annealing is necessary in order to improve the microstructure of both oxide and near interface region. (c) 2006 Elsevier B.V. All rights reserved.