The anodic dissolution of p -Si has been investigated by in situ infrared spectroscopy. The combination of potential-difference and electromodulated spectroscopies allows for the acquisition of a rather complete picture of the various regimes of the dissolution. After a review of general principles for studying electrochemical interfaces, a study of the interfacial oxide layer formed in the electropolishing regime is presented. Quantitative analysis shows that the thickness and quality of the oxide (density and defect content) depend upon electrode potential. Free-carrier absorption detected in electromodulated spectra shows that the blocking character of the oxide is correlated with the buildup of a stoichiometric oxide of low defectivity at sufficiently positive potentials. Furthermore, the dynamic response to the modulation reveals that oxides formed at weak positive potentials interact with electrolyte species through electro-induced adsorptions/desorptions on charged SiOH sites. At more positive potentials, charge is transported across the oxide by charged defects which could be associated with tricoordinated, positively charged SiO species. Finally, results obtained during porous silicon formation at weak positive potentials are presented. Potential-difference spectroscopy indicates that the electrode exhibits a very large specific surface area, and that the surface is covered by SiH bonds. Electromodulated infrared spectroscopy reveals that the SiH species are generated upon anodic current flowing and that the breaking of these bonds is the rate-limiting step of the anodic reaction. These unexpected results have given rise to the elaboration of new microscopic models for the direct anodic dissolution of silicon in fluoride electrolytes.
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