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 μm 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 μm 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.