Porous silicon layers (PSL) of nano and micro-structures were prepared by metal-assisted electroless etching of silicon in HF-oxidizing agent aqueous solutions The effect of oxidizing agent and HF content on the characteristics of the formed porous layers was investigated A thin Pt film was electroless deposited on p-Si(1 0 0) prior to immersion in the etching solution The properties and morphology of the PSL formed by this method were investigated by electrochemical impedance spectroscopy (EIS) scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) technique The characteristics of the PSL were found to be affected by the constituents of the etching medium and also the etching time Potassium bromate (KBrO3) potassium iodate (KIO3) and potassium dichromate (K2Cr2O7) have been used as oxidizing agents Pt assisted etching of p Si for 1 h in an etching solution consisting of 22 0 M HF and 005 M of KBrO3 results in the formation of nano- and micro-pores on the Si sui face The use of 005 M KIO3 or K2Cr2O7 as oxidizing agent has led to the formation of a deposit on the silicon surface At relatively higher concentration [>0 05 M] of K2Cr2O7 the surface deposit becomes clear and was found to consist of an insoluble passive solid-phase of K2SiF6 which increases the film impedance and blocks the porous structure formation The use of higher concentration [>22 M] of HF in the etching electrolyte is accompanied by an increase in the dissolution rate of the insoluble K2SiF6 layer and a decrease in the PSL passivity The experimental impedance data were fitted to theoretical data according to a proposed equivalent circuit model which accounts for the mechanism of the porous film formation at the Si/electrolyte interface (C) 2010 Elsevier Ltd All tights reserved