Zinc peroxide and zinc oxide nanoparticles were prepared and self-assembled hybrid nanolayers were built up using layer-by-layer (LbL) technique on the surface of glass substrate using the layer silicate hectorite and an anionic polyelectrolyte, sodium polystyrene sulfonate (PSS). Light absorption, interference and morphological properties of the hybrid films were studied to determine their thickness and refractive index. The influence of layer silicates and polymers on the self-organizing properties of ZnO2 and ZnO nanoparticles was examined. X-ray diffraction revealed that ZnO2 powders decomposed to ZnO (zincite phase) at relatively low temperatures (less than 200 degrees C). The optical thickness of the films ranged from 190 to 750 nm and increased linearly with the number of layers. Band gap energies of the ZnO2/hectorite films were independent from the layer thickness and were larger than that of pure ZnO2 nanodispersion. Decomposition of ZnO2 to ZnO and O-2 at 400 degrees C resulted in the decrease of the band gap energy from 3.75 to 3.3 eV. Concomitantly, the refractive index increased in correlation with the formation of the zincite ZnO phase. In contrast, the band gap energies of the ZnO2/PSS hybrid films decreased with the thickness of the nanohybrid layers. We ascribe this phenomenon to the steric stabilization of primary ZnO2 particles present in the confined space between adjacent layers of hectorite sheets. (c) 2009 Elsevier B.V. All rights reserved.