The mechanism of galvanic/metal-assisted etching of silicon

Metal-assisted etching is initiated by hole injection from an oxidant catalyzed by a metal nanoparticle or film on a Si surface. It is shown that the electronic structure of the metal/Si interface, i.e., band bending, is not conducive to diffusion of the injected hole away from the metal in the case of Ag or away from the metal/Si interface in the cases of Au, Pd, and Pt. Since holes do not diffuse away from the metals, the electric field resulting from charging of the metal after hole injection must instead be the cause of metal-assisted etching.