Ag-Mediated Charge Transport during Metal-Assisted Chemical Etching of Silicon Nanowires

The charge transport mechanism during metal-assisted chemical etching of Si nanowires with contiguous metal films has been investigated. The experiments give a better insight how the charges and reaction products can penetrate to the etching front. The formation of a layer of porous Si between the metal film and the bulk Si is a prerequisite for the etching process. The electronic holes (positive charges) necessary for the etching of porous Si are generated at the surface of the metal in contact with the oxidative agent. Because of the insulating character of the thin walls of the porous Si, the transport of the electronic holes through this layer is not possible. Instead, it is found that the transport of electronic holes proceeds primarily by means of the Ag/Ag⁺ redox pair circulating in the electrolyte and diffusing through the etched pores in the Si. The charge transport occurs without the ionic contribution at the positions where the metal is in direct contact with the Si. Here, an electropolishing process takes place, leading to an extensive removal of the Si and sinking in of the film into the Si substrate