Nanostructuring of Si substrates by a metal-assisted chemical etching and dewetting process

In this work, we reported on the development of lithography-free technology for the fabrication of nanopatterned Si substrates. The combination of two phenomena, the solid-state dewetting process and metal-assisted wet chemical etching, allowed for fabrication of Si nanocolumns on large areas in a relatively simple way. The process of dewetting the thin metal layer enabled formation of nickel nanoislands, which were used as a shadow mask in the deposition of a catalytic metal pattern. Application of the two-stage dewetting process with the repetition of the metal deposition and annealing step enabled us to obtain a significant increase in the surface coverage ratio and the surface density of the nanoislands. As a catalytic metal, a gold layer was applied in the metal-assisted wet chemical etching process. The obtained columnar nanostructures showed a great verticality and had a high aspect ratio. In the conducted studies, the maximum etching rate (at RT) was higher than 1.2 μm min^-1. The etching rate increased with increasing concentration of oxidizing (H₂O₂) and etching (HF) agent, with a tendency to saturate for more concentrated solutions. The etching rate was significantly higher for Si substrates with a crystallographic orientation (115) than for (111), but there was no privileged direction of etching except for the direction vertical to the substrate. With increasing layer thickness of the catalytic metal a decrease in the metal-assisted wet chemical etching process efficiency was observed. The developed technology allows for fabrication of patterned substrates with a wide range of lateral dimension of nanocolumns and their density.