Vibrationally Assisted Polariton-Relaxation Processes in Strongly Coupled Organic-Semiconductor Microcavities

If a semiconductor with an electronic transition that approximates a two‐level system is placed within an optical cavity, strong coupling can occur between the confined photons and the semiconductor excitons. This coupling can result in the formation of cavity polariton states that are a coherent superposition of light and matter. If the material in the cavity is an organic semiconductor, it has been predicted that interactions between Frenkel excitons, polaritons, and molecular vibrational modes will have a profound role in defining the overall relaxation dynamics of the system. Here, using temperature‐dependent spectroscopy on a microcavity containing a J‐ aggregated cyanine dye, it is shown that a spectrum of localized vibrational modes (identified by Raman scattering) enhances the population of certain polaritonic modes by acting as an energy‐loss channel to the excitons as they undergo scattering. Our work demonstrates that simultaneous control of the optical properties of a cavity and the vibrational structure of a molecular dye could promote the efficient population of k = 0 polariton states, from which lasing and other cooperative phenomena may occur. A fast relaxation path for populating lower‐branch polariton states arises from the interactions between excitons and the molecular vibrations of the organic material in a strongly coupled microcavity containing an organic semiconductor. This process, followed by angle‐ and temperature‐ dependent spectroscopy, may allow efficient population of polariton states in the momentum trap from which nonlinear phenomena occur.