Surface Plasmon Tunability of Core-Shell Au@Mo₆ Nanoparticles by Shell Thickness Modification

Plasmon resonances of noble metal nanoparticles are used to enhance light-matter interactions in the nanoworld. The nanoparticles' optical response depends strongly on the dielectric permittivity of the surrounding medium. We show that the plasmon resonance energy of core-shell Au@Mo₆ nanoparticles can be tuned from 2.4 to 1.6 eV by varying the thickness of their Mo₆ cluster shells between zero and 70 nm, when the core diameter is fixed at 100 nm. We probe their plasmonic response by performing nanometer-resolution plasmon mapping on individual nanoparticles, using electron energy-loss spectroscopy inside a transmission electron microscope. Our experimental results are corroborated by numerical simulations performed using boundary element methods. The simulations predict a similar dependency for the extinction energy, showing that this effect could also be observed by light-optical experiments outside the electron microscope, although limited by the size distribution of the nanoparticles in solution and the substantial scattering effects.