Plasmon–Exciton Interaction at the Nanoscale: Silver Is More “Precious” than Gold!

Abstract

Predictive understanding of factors affecting plasmon−exciton coupling is crucial for the successful realization of the exciting potentials of plexcitonic nanostructures. Here, we systematically investigate the role of plasmonic metals in controlling the plasmon− exciton coupling strength. We use gold and silver nanoprisms, having identical LSPR maxima, as the plasmonic components and form two plexciton hybrids with the J-aggregates of a cyanine dye. Single-particle spectroscopy is employed to study and compare the abilities of gold and silver in influencing plasmon−exciton interaction at the nanoscale. Despite much faster plasmon dephasing than its gold counterpart, the silver nanoprism exhibits greater Rabi splitting. We reveal that the smaller plasmon mode-volume despite having larger physical volume, superior local electric-field enhancement, and smaller Ohmic losses compared to gold, enables the silver nanoprism to defy the pronounced plasmon decoherence effects and to show stronger plasmon−exciton coupling. These findings suggest that silver nanostructures should be the unequivocal choice over gold when "strong coupling" is desired for any application.