Metal-assisted etching of silicon in HF/H2O2/H2O solutions with Ag nanoparticles as catalyst agents was investigated. SEM observations and etch rate measurements were carried out as a function of the etching solution composition. Depending on the relative amount of HF and H2O2, different regimes of dissolution take place and a strong similarity with the etching in HF-HNO3 solution is evidenced, for the first time. Formation of meso- and macroporous Si, etched craters and polished Si are observed as the HF/H2O2 ratio decreases. The dissolution mechanisms are discussed on the basis of a localized hole injection from the Ag nanoparticles into Si and in terms of the well known chemistry of Si dissolution in HF-based chemical and electrochemical systems. At high HF/H2O2 ratio, there is no formation of oxide at the surface. Hole injection and Si dissolution occur at the level of the Ag nanoparticle only, resulting in the formation of meso and macropores depending on the Ag nanoparticle size. At low HF/H2O2 ratio, the Si surface is oxidized, the injected holes are homogeneously distributed and thus polishing occurs. There is an intermediate range of composition in which injected holes diffuse away from the Ag nanoparticles and cone-shaped macropores, several tens of mm in diameter are formed. (C) 2008 Elsevier Ltd. All rights reserved.