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Porous silicon (PSi) layer were formed on crystalline silicon (c-Si) substrates by using metal (Ag)-assisted chemical etching in hydrofluoric acid solution. The structure and optical (infrared absorption, photoluminescence, Raman scattering) properties of the formed PSi layers were investigated to reveal dependences on the preparation conditions. The formed PSi layers exhibit efficient band-gap-related photoluminescence (PL) at 1.1 µm of silicon nanowires (SiNWs) with mean diameters of about 50–200 nm . Additionally the PL band at 700 nm, which is re-lated to the radiative recombination of excitons confined in small Si nanocrystals on SiNW surfaces, was de-tected.