The large-area fabrication of aligned nano patterns with sub-5 nm feature size is crucial for developing nanodevices. Highly ordered nanostructures fabricated through molecular self-assembly exhibit substantial potential for sub-5 nm patterning techniques. Previously, we had reported the fabrication of silica nanogrooves with sub-5 nm periodicity on a Si substrate by using the outermost surfaces of cylindrical surfactant micelles as a template. However, uniaxial alignment of nanogrooves on the entire substrate surface has not yet been achieved. In this study, uniaxially aligned silica nanogrooves were prepared on the entire surface of a Si substrate (2 cm x 2 cm) by utilizing a poly(dimethylsiloxane) (PDMS) stamp with a striped pattern. The PDMS stamp was placed on the surface of a surfactant thin film precoated on the substrate, although the stamp was not in direct contact with the substrate as in the case of the soft nanoimprint technique. The substrate was then exposed to water vapor, during which cylindrical micelles were aligned in the direction of the guide. Subsequently, by exposing the substrate to an NH3-water vapor mixture, the outermost surfaces of the aligned micelles facing the substrate were replicated with soluble silicate species. The formation of uniaxially aligned nanogrooves on the entire surface of the centimeter-scale substrate was verified by scanning electron microscopy observations and grazing-incidence small-angle X-ray scattering analysis. Thus, herein we provide a simple large-area fabrication method for uniaxially aligned nanopatterns with ultrafine pitch.

The flexible control of nanopatterns by a bottom-up process at the nanometer scale is essential for nanofabrication with a finer pitch. We have previously reported that for the fabrication of linear nanopatterns with sub-5 nm periodicity on Si substrates the outermost surfaces of assembled micelles facing the substrates can be replicated with soluble silicate species generated from the Si substrates under basic conditions. In this study, concentrically arranged nanogrooves with a sub-5 nm periodicity were prepared on Si substrates by replicating the outermost surfaces of bent micelles guided by silica particles. The Si substrates, where silica particles and surfactants films were deposited, were exposed to an NH3-water vapor mixture. During the vapor treatment, cylindrical micelles became arranged in concentric patterns centered on the silica particles, and their outermost surfaces facing the substrates were replicated by soluble silicate species on the Si substrates. The thinness of the surfactant film on the substrate is crucial for the formation of concentric silica nanogrooves because the out-of-plane orientations of the micelles are suppressed at the interface. Surprisingly, the domains of the concentric silica nanogrooves spread to much larger areas than the maximum cross-sectional areas of the particles, and the size of the domains increased linearly with the radii of the particles. The extension of concentric nanogrooves is discussed on the basis of the orientational elastic energies of the micelles around one silica particle. This study of the formation of bent nanogrooves guided by the outlines of readily deposited nanoscale objects provides a new nanostructure-guiding process.