Plasmonic coupling with most of the transition metals: a new family of broad band and near infrared nanoantennas

In this article, we show for the first time, both theoretically and empirically, that plasmonic coupling can be used to generate Localized Surface Plasmon Resonances (LSPRs) in transition metal dimeric nanoantennas (NAs) over a broad spectral range (from the visible to the near infrared) and that the spectral position of the resonance can be controlled through morphological variation of the NAs (size, shape, interparticle distance). First, accurate calculations using the generalized Mie theory on spherical dimers demonstrate that we can take advantage of the plasmonic coupling to enhance LSPRs over a broad spectral range for many transition metals (Pt, Pd, Cr, Ni etc.). The LSPR remains broad for low interparticle distances and masks the various hybridized modes within the overall resonance. However, an analysis of the charge distribution on the surface of the nanoparticles reveals these modes and their respective contributions to the observed LSPR. In the case of spherical dimers, the transfer of the oscillator strengths from the "dipolar" mode to higher orders involves a maximum extinction cross-section for intermediate interparticle distances of a few nanometers. The emergence of the LSPR has been then experimentally illustrated with parallelepipedal NAs (monomers and dimers) made of various transition metals (Pt, Pd and Cr) and elaborated by nanolithography. Absolute extinction cross-sections have been measured with the spatial modulation spectroscopy technique over a broad spectral range (300-900 nm) for individual NAs, the morphology of which has been independently characterized by electron microscopy imaging. A clear enhancement of the LSPR has been revealed for a longitudinal excitation and plasmonic coupling has been clearly evidenced in dimers by an induced redshift and broadening of the LSPR compared to monomers. Furthermore, the LSPR has been shown to be highly sensitive to slight modifications of the interparticle distance. All the experimental results are well in agreement with finite element method (FEM) calculations in which the main geometrical parameters characterizing the NAs have been derived from electron microscopy imaging analysis. The main advantage of dimers as compared to monomers lies in the generation of a well-defined and highly enhanced electromagnetic field (the so-called "hot spots") within the interparticle gap that can be exploited in photo-catalysis, magneto-plasmonics or nanosensing.