Large-Area Fabrication of Vertical Silicon Nanotube Arrays via Toroidal Micelle Self-Assembly

We present a highly scalable, room-temperature strategy for fabricating vertical silicon nanotube arrays derived from a toroidal micelle pattern via a water vapor-induced block copolymer (BCP) self-assembly mechanism. A polystyrene-b-poly(ethylene oxide) (PS-b-PEO) BCP system can be self-assembled into toroidal micelle structures (diameter: 400-600 nm) on a PS-OH-modified substrate in a facile manner contrasting with other complex processes described in the literature. It was found that a minimum PS-b-PEO thickness of ∼86 nm is required for the toroidal self-assembly. Furthermore, a water vapor annealing treatment at room conditions (∼25 °C, 60 min) is shown to vastly enhance the ordering of micellar structures. A liquid-phase infiltration process was used to generate arrays of iron and nickel oxide nanorings. These oxide structures were used as templates for pattern transfer into the underlying silicon substrate via plasma etching, resulting in large-area 3D silicon nanotube arrays. The overall simplicity of this technique, as well as the wide potential versatility of the resulting metal structures, proves that such room-temperature synthesis routes are a viable pathway for complex nanostructure fabrication, with potential applicability in fields such as optics or catalysis.