Micro-Raman spectra of porous silicon (PS) samples as-formed, from stain etching process using heavily doped silicon wafers, and after 750 days storage in air were analyzed around Si peak (300-600 cm(-1)) and at photouminescence (PL) range (300-8000 cm(-1) 1). The first-order Raman spectra in the vicinity of Si peak were fitted from phonon confinement model including a term taking into account the amorphous phase. This analysis allowed the determination of the correlation length, which corresponds to the crystallite size, also considering the PS natural oxidation process. The photoluminescence band, generated by Si crystallites located on the outermost part of the PS layer, was also fitted with a Gaussian distribution. In order to investigate the porous silicon nanostructure, the micro-Raman spectra were measured for different sets of porous silicon samples. These spectra showed good reproducibility and the effects of the natural oxidation at different periods. A slight decrease in the crystallite size was observed for all samples sets studied, while the spectral part related to the amorphous phase did not describe significant changes. The central position of PL band, analyzed after the oxidation process, exhibited consistently a shift to higher energies. In addition, top view high resolution scanning electron microscopy (HRSEM) images also confirmed a reasonable reproducibility and homogeneity. The results showed that after storing in air, natural oxidation can modify the Si crystallites size at the surface but not increase the amorphous phase. (c) 2007 Elsevier B.V. All rights reserved.