US and ZnS semiconducting colloid nanoparticles were deposited as thin films using the technique of electrostatic self-assembly. The process of alternative deposition of Poly-allylamine Hydrochloride (PAH) and CdS (or ZnS) layers were monitored with a novel optical method of total internal reflection ellipsometry (TIRE). The fitting of TIRE spectra allowed the evaluation of the parameter (thickness, refractive index and extinction coefficients) of all consecutively deposited layers. 1-V characteristics of the films obtained were studied in sandwich structures on Indium Tin Oxide (ITO) conductive electrodes using the mercury probe technique. The presence of US (or ZnS) nanoparticles in the polyelectrolyte films leads to a switching behaviour, which may be attributed to the resonance electron tunneling via semiconducting nanoparticles. (c) 2008 Elsevier B.V. All rights reserved.