The aim of this paper is to investigate the structural and optical stability of porous silicon layers (PSLs) planned to be used in silicon solar cells technology. The PSLs were prepared by a HNO3/HF vapor etching (VE) based method. Fourier transform infrared (FT-IR) spectroscopy shows that fresh VE-based PSLs contain N-H and Si-F bonds related to a ammonium hexafluorosilicate (NH4)(2)SiF6 minor phase, and conventional Si-H-x and Si-O-x bonds. Free air exposures of PSLs without and with UV irradiation lead to oxidation or photo-oxidation of the porous layer, respectively. FT-IR characterisation of the PSLs shows that UV irradiations modify the transformation kinetics replacing instable Si-H-x by Si-O-x or Si-O-H bonds. When fresh PSLs undergo free air oxidation within 7 days, the surface reflectivity decreases from 10 to about 8%, while it drops to about 4% when a 10 min free air UV irradiation is applied. Long periods of free air oxidation do not ensure the reflectivity to be stable, whereas it becomes stable after only 10 min of UV irradiation. This behaviour was explained taking into account the kinetic differences between oxidation with and without UV irradiation. Fresh VE-based PSLs were found to improve efficiently the photovoltaic (PV) characteristics of crystalline silicon solar cells. The passivating action of VE-based PSLs was discussed. An improvement of the PV performances was observed solely for stable oxidized porous silicon (PS) structures obtained from UV irradiations. (C) 2004 Published by Elsevier B.V.