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. The etching rate increased with increasing concentration of oxidizing (HO) 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.