We present a novel approach to create spinodal-like structures appropriately modulating the instability of the solid state dewetting: many materials, indeed, featuring anomalous suppression of density fluctuations over large length scales are emerging systems known as disordered hyperuniform. The underlying hidden order renders them appealing for several applications, as light management and topologically protected electronic states. These applications require scalable fabrication, which is hard to achieve with available top-down approaches. These spinodal materials are used by a hybrid top-down/bottom-up approach based on sol-gel dip-coating and nano-imprint lithography for the faithful reproduction of the disordered metasurfaces in metal oxides (SiO2 and TiO2).
In this work, mechanically, chemically, and thermally resistant broadband and broad-angle antireflection coatings were prepared on 10 cm diameter glass substrates combining sol−gel deposition with nanoimprint lithography. The coatings are composed of water-repellent methylated silica (Si4O7Me2) and exhibit a transverse refractive index gradient created by tapered, nipple-dimple, subwavelength nanostructures, featuring a record vertical aspect ratio of ∼1.7. The structure is composed of hexagonal arrays of nanopillars (∼200 nm height, ∼120 nm width) and holes (∼50 nm depth, ∼100 nm width) with a 270 nm pitch. The corresponding effective refractive index is between 1.2 and 1.26, depending on the fabrication conditions. Total transmission for double-face nanoimprint wafers reaches 96−97% in the visible range; it is limited by specular reflection and mostly by the intrinsic diffusion of the glass substrate. The antireflective effect is effective up to an ∼60° incidence angle. We address the robustness of the inorganic-based coating in various realistic and extreme conditions, comparing them to the organic perfluoropolyether (PFPE) counterpart (master reference). The sol−gel system is extremely stable at high temperature (up to 600 °C, against 200 °C for the polymer reference). Both systems showed excellent chemical stability, except in strong alkaline conditions. The inorganic nanostructure showed an abrasion resistance of more than 2 orders of magnitude superior to the polymer one with less than 20% loss of antireflective performance after 2000 rubbing cycles under an ∼2 N cm−2 pressure. This difference springs from the large elastic modulus of the sol−gel material combined with an excellent adhesion to the substrate and to the specific nipple-dimple conformation. The presence of holes allows maintaining a refractive index gradient profile even after tearing out part of the nanopillar population. Our results are relevant to applications where transparent windows with broadband and broad-angle transmission are needed, such as protective glasses on photovoltaic cells or C-MOS cameras.
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