Far-field, near-field and photothermal response of plasmonic twinned magnesium nanostructures.

Magnesium nanoparticles offer an alternative plasmonic platform capable of resonances across the ultraviolet, visible and near-infrared. Crystalline magnesium nanoparticles display twinning on the (101̄1), (101̄2), (101̄3), and (112̄1) planes leading to concave folded shapes named tents, chairs, tacos, and kites, respectively. We use the Wulff-based Crystal Creator tool to expand the range of Mg crystal shapes with twinning over the known Mg twin planes, i.e., (101̄x), x = 1, 2, 3 and (112̄y), y = 1, 2, 3, 4, and study the effects of relative facet expression on the resulting shapes. These shapes include both concave and convex structures, some of which have been experimentally observed. The resonant modes, far-field, and near-field optical responses of these unusual plasmonic shapes as well as their photothermal behaviour are reported, revealing the effects of folding angle and in-filling of the concave region. Significant differences exist between shapes, in particular regarding the maximum and average electric field enhancement. A maximum field enhancement (|E|/|E0|) of 184, comparable to that calculated for Au and Ag nanoparticles, was found at the tips of the (112̄4) kite. The presence of a 5 nm MgO shell is found to decrease the near-field enhancement by 67% to 90% depending on the shape, while it can increase the plasmon-induced temperature rise by up to 42%. Tip rounding on the otherwise sharp nanoparticle corners also significantly affects the maximum field enhancement. These results provide guidance for the design of enhancing and photothermal substrates for a variety of plasmonic applications across a wide spectral range.

Bimetallic copper palladium nanorods: plasmonic properties and palladium content effects.

Cu is an inexpensive alternative plasmonic metal with optical behaviour comparable to Au but with much poorer environmental stability. Alloying with a more stable metal can improve stability and add functionality, with potential effects on the plasmonic properties. Here we investigate the plasmonic behaviour of Cu nanorods and Cu-CuPd nanorods containing up to 46 mass percent Pd. Monochromated scanning transmission electron microscopy electron energy-loss spectroscopy first reveals the strong length dependence of multiple plasmonic modes in Cu nanorods, where the plasmon peaks redshift and narrow with increasing length. Next, we observe an increased damping (and increased linewidth) with increasing Pd content, accompanied by minimal frequency shift. These results are corroborated by and expanded upon with numerical simulations using the electron-driven discrete dipole approximation. This study indicates that adding Pd to nanostructures of Cu is a promising method to expand the scope of their plasmonic applications.

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 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.