Nanofabrication of double-gyroid thin films

Nanoporous silica films with the double-gyroid structure offer tremendous technological potential for sensors and separations because of their high surface area and potentially facile transport properties. Further, metals and semiconductors with similar structure open up new opportunities for high-surface-area electrodes, photoelectrochemical devices, photovoltaics, and thermoelectrics. Here, we report a new robust synthesis of highly ordered nanoporous silica films with the double-gyroid structure by evaporation-induced self-assembly (EISA) at room temperature and laboratory humidity using a commercially available EO17-PO12-C-14 surfactant. The continuous nanoporous films are synthesized on conducting electrodes. Electrochemical impedance spectroscopy is then used to quantitatively measure the accessible surface area of the underlying electrode via transport through the pore system. It is found that the double-gyroid-structure silica films expose a much higher fraction of the electrode than other commonly synthesized nanostructures such as 2D centered rectangular or 3D rhombohedral nanostructures. The double-gyroid nanoporous-film-coated electrodes are then used to fabricate inverse double-gyroid platinum nanostructures by electrodeposition, followed by etching to remove the silica. The structure of both the nanoporous silica films and the nanoporous platinum films (after etching) have been elucidated using high-resolution field-emission scanning electron microscopy (FESEM), comparing measured and simulated 2D grazing angle-of-incidence small-angle X-ray scattering (GISAXS) patterns, and comparing observed and simulated transmission electron microscopy (TEM) images. Both films are highly (211) oriented and described by a cubic Ia (3) over bard space group that has undergone uniaxial contraction perpendicular to the substrate. Upon this contraction, Ia (3) over bard symmetry is broken, but the films retain the double-gyroid topology. The nanoporous silica and the platinum nanowires have a characteristic wall or wire thicknesses of approximately 3 nm. This nanofabrication process opens up a facile general route for fabrication of ordered structures on the sub-5 nm length scale.