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

J Phys Chem Lett. 2022 Mar 10;13(9):2150-2157. doi: 10.1021/acs.jpclett.1c03853. Epub 2022 Feb 28.

Abstract

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.