Phonon Modulation of Strongly Coupled Gold Tetrahedral Plasmonic Nanoparticles and a Carbocyanine J-Aggregate

Abstract

Coupling exciton and plasmon excitations to form polaritons are of high interest for manipulating energy transfer at the nanoscale via the formation of hybrid light-matter states. In this study, we successfully couple gold tetrahedral nanoparticles with the J-aggregate forming dye 5,5′,6,6′-tetrachloro-1,1′-diethyl-3,3′-di(4–sulfobutyl) -benzimidazolocarbocyanine (TDBC) to form a strongly coupled colloidal polariton system with Rabi splitting energy of ~206 meV. These gold tetrahedra exhibit coherent phonon modes upon photoexcitation, which produce transient oscillations of the LSPR energy for isolated tetrahedra. Transient absorption measurements of the polariton system were performed and show how these coherent phonon modes influence the polariton states’ extinction. We find that the oscillation period increases by 0.5 ± 0.14 ps upon surface deposition of TDBC dye, demonstrating LSPR sensitivity to the refractive index environment. Shifts in the plasmon resonance due to the coherent phonon modes transiently alters LSPR alignment with the J-aggregate exciton peak, resulting in shifts of the hybrid polariton states’ oscillator strength.