Optoplasmonic Effects in Highly Curved Surfaces for Catalysis, Photothermal Heating, and SERS

Surface curvature can be used to focus light and alter optical processes. Here, we show that curved surfaces (spheres, cylinders, and cones) with a radius of around 5 microm lead to maximal optoplasmonic properties including surface-enhanced Raman scattering (SERS), photocatalysis, and photothermal processes. Glass microspheres, microfibers, pulled fibers, and control flat substrates were functionalized with well-dispersed and dense arrays of 45 nm Au NP using polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP) and chemically modified with 4-mercaptobenzoic acid (4-MBA, SERS reporter), 4-nitrobenzenethiol (4-NBT, reactive to plasmonic catalysis), or 4-fluorophenyl isocyanide (FPIC, photothermal reporter). The various curved substrates enhanced the plasmonic properties by focusing the light in a photonic nanojet and providing a directional antenna to increase the collection efficacy of SERS photons. The optoplasmonic effects led to an increase of up to 1 order of magnitude of the SERS response, up to 5 times the photocatalytic conversion of 4-NBT to 4,4'-dimercaptoazobenzene when the diameter of the curved surfaces was about 5 microm and a small increase in photothermal effects. Taken together, the results provide evidence that curvature enhances plasmonic properties and that its effect is maximal for spherical objects around a few micrometers in diameter, in agreement with a theoretical framework based on geometrical optics. These enhanced plasmonic effects and the stationary-phase-like plasmonic substrates pave the way to the next generation of sensors, plasmonic photocatalysts, and photothermal devices.