N-type porous silicon (PS) layers and thermally oxidized PS layers have been characterized by various measuring techniques such as photoluminescence (PL), Raman spectroscopy, IR, HRSEM and transmittance measurements. The top surface of PS layer shows a stronger photoluminescence peak than its bottom part, and this is ascribed to the difference in number of fine silicon particles of 2~3 nm in diameter. Observed characteristics of PL spectra are explained in terms of microstructures in the n-type PS layers. Common features for both p-type and n-type PS layers are as follows: the parts which can emit visible photoluminescence are not amorphous, but crystalline, and such parts are composed of nanocrystallites of several nm’s whose orientations are slightly different from Si substrate, and such fine silicon particles absorb much hydrogen atoms near the surfaces. Light emission is strongly dependent on such fine silicon particles. Photoluminescence is due to charge carrier confinement in such three dimensional structure (sponge-like structure). Characteristics of visible light emission from ntype PS can be explained in terms of modification of band structure accompanied by bandgap widening and localized levels in bandstructure. It is also shown that hydrogen and oxygen atoms existing on residual silicon parts play an important role on emission stability.