Thin films of a-SiOx (0 < x < 2) were prepared by reactive r.f. magnetron sputtering from a polycrystalline-silicon target in an Ar/O-2 gas mixture. The oxygen partial pressure in the deposition chamber was varied so as to obtain films with different values of x. The plasma was monitored, during depositions, by optical emission spectroscopy (OES) system. Energy dispersive X-ray (EDX) measurements and infra-red (IR) spectroscopy were used to study the compositional and structural properties of the deposited layers. Structural modifications of SiOx thin films have been induced by UV photons' bombardment (wavelength of 248 nm) using a pulsed laser. IR spectroscopy and X-ray photoemission spectroscopy (XPS) were used to investigate the structural changes as a function of x value and incident energy. SiOx phase separation by spinodal decomposition was revealed. The IR peak position shifted towards high wavenumber values when the laser energy is increased. Values corresponding to the SiO2 material (only Si4+) have been found for laser irradiated samples, independently on the original x value. The phase separation process has a threshold energy that is in agreement with theoretical values calculated for the dissociation energy of the investigated material. For high values of the laser energy, crystalline silicon embedded in oxygen-rich silicon oxide was revealed by Raman spectroscopy. (c) 2006 Elsevier B.V. All rights reserved.