The initial nucleation stages during deposition of SiO2 by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO2 thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO2 grows in the form of islands. When the SiO2 particles reach heights close to10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO2 particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.