Control of the polarization distribution of light allows tailoring the electromagnetic response of plasmonic particles. By rigorously extending the generalized multiparticle Mie theory, we show that focused cylindrical vector beams (CVB) can be used to efficiently excite dark plasmon modes in nanoparticle clusters. In addition to the small radiative damping and large field enhancement associated to dark modes, excitation with CVB can give place to unusual phenomenology like the formation of electromagnetic cold spots and the generation of Fano resonances in highly symmetric clusters. Overall, the results show the potential of CVB to tailor the plasmonic response of nanoparticle clusters in a unique way.

The width of the surface plasmon resonance of metallic particles increases as the particle size reduces due to confinement effects that modify the metal dielectric function. In the limit of very low particle concentration, particle size can be directly related to the plasmon width. However, as concentration increases, the interaction among particles induces additional broadening. Numerical computation of the effective dielectric function of systems consisting of monodisperse and randomly distributed particles embedded in a dielectric matrix enable us to quantify the influence of both size and interaction effects. It is shown that for noble metals the contribution of interparticle interaction to plasmon resonance width cannot be neglected even at volume concentrations of a few per cent. The results presented here can be useful in extending nanoparticle sizing from optical extinction spectroscopy beyond the dilute limit required by classical Mie theory.

The potential of random metal-dielectric nanocomposites as constituent elements of metamaterial structures is explored. Classical effective medium theories indicate that these composites can provide a tunable negative dielectric function with small absorption losses. However, the tuning potential of real random composites is significantly lower than the one predicted by classical theories, due to the underestimation of the spectral range where topological resonances take place. This result suggests that a random mixture consisting of a metal matrix with embedded isolated dielectric inclusions is a promising design guideline for the fabrication of tunable composites for metamaterial purposes.

Efficient excitation of Fano resonances in plasmonic systems usually requires complex nano-structure geometries and some degree of symmetry breaking. However, a single-layered concentric core–shell particle presents inherent Fano profiles in the scattering spectra when sphere and cavity modes spectrally overlap. Weak hybridization and suitable choice of core and shell materials gives rise to strong electric dipolar Fano resonances in these systems and retardation effects can result in resonances of higher multipolar order or of magnetic type. Furthermore, suitable tailoring of illumination conditions leads to an enhancement of the Fano resonance by quenching of unwanted electromagnetic modes. Overall, it is shown that single layered core–shell particles can act as robust Fano resonators.

Alternative materials that can potentially replace Au and Ag in plasmonics and broaden its application potential have been actively investigated over the last decade. Cu and Al have been usually overlooked as plasmonic material candidates because they are prone to oxidisation. In this work the plasmonic performance of Cu and Al is investigated using numerical simulations of different nanostructures (spheres, cubes, rods and particle dimers) and taking into account the presence of oxidisation. It is shown that geometry can play a dominant role over material properties and the performance of Cu and Al becomes comparable to that of Ag and Au for systems of non-spherical particles and strong electromagnetic coupling among particles. This observation is experimentally confirmed by the fabrication and characterisation of Cu and Al metal island films. Optical characterisation of the samples reveals a comparable performance of these metals to that obtained for Ag and Au and suggests that Cu and Al metal island films can offer an efficient low-cost platform for solar energy harvesting, as shown in water vapour generation proof of concept experiments.