A Low Energy Cluster Beam Deposition apparatus is employed to produce cluster assembled silicon thin films (1-500 nm thick) by using a laser vaporization source. The generated clusters are studied since their formation through time of flight mass spectra and the calculated size in the gas phase are compared with those of the deposited aggregates obtained through Dynamic Scanning Force Microscopy. The deposited material is also studied "in situ" by Raman and infrared spectroscopy. The spectra reveal that the as deposited clusters are hydrogenated with negligible amount of oxide. A comparison of the film properties before and after their air exposure shows that the exposition induces a consistent oxidation, leading to a near-infrared luminescent silicon nanoparticles surrounded by SiOx shells. (c) 2005 Elsevier B.V. All rights reserved.