Spontaneous Symmetry Breaking of Nanoscale Spatiotemporal Pattern as the Origin of Helical Nanopore Etching in Silicon.

Abstract

Nanometric chiral objects such as twisted or helical nanoribbons represent a new class of objects having important potential in a large panel of applications, taking advantage, for example, of electromechanical or optical chirality, local chiral environment for catalysis, and chiral recognition. Supramolecular chemistry has played a central role in the production of such structures through either chiral macromolecules/foldamers or the self-assembly of chiral molecules; the latter can also be used as templates for the sol-gel transcription to silica materials, offering them polymorphisms with further structural stability. Here, we report a totally different and dynamic approach to produce helical mesostructures. This study focuses on helical nanopores that are spontaneously formed in the platinum-assisted chemical etching of silicon by dynamic self-organization under a nonequilibrium state. The symmetry breaking of a helical nanopore formation is achieved by the spatial symmetry breaking of a spatiotemporal pattern at the nanoscale and without incorporation of chiral molecules. Rotational motion of the platinum nanocatalyst, which is regarded as a spatiotemporal pattern at the etching frontier (the platinum/silicon interface), induces precession movement of the nanocatalyst, and movement of the catalyst during etching forms helical nanopores in the silicon. We consider that this study is an important milestone to understand the close relation between spatiotemporal pattern formation and the dynamic emergence of symmetry breaking in chemical reactions.