In this work polysilazane based silica thin films grown on multilayer structures of different ultra-thin barriers (UTBs) on silicon substrates were studied. The silica thin films were obtained by polysilazane spin coating deposition (also called SOD, spin-on dielectrics) upon different UTB liners (silicon nitride or silicon dioxide). By curing the SOD with thermal treatments the polysilazane is converted into silica thin films. The degree of conversion to SiO2 was analyzed and the oxide local structure was studied in terms of Si-O-Si bridges by FTIR spectroscopy. Steady state and time resolved luminescence were applied to further characterize the oxide structure, the substrate-silica interfaces and the presence of defects. The analysis revealed the presence of dioxasilirane, =Si(O-2), and silylene, =Si:, defect centers in the samples grown on silicon nitride UTB, while these defects are not observed in samples grown on silicon oxide UTB. (C) 2012 Elsevier B.V. All rights reserved.