Single‐shot Stokes polarimetry of plasmon‐coupled single‐molecule fluorescence

The photophysical properties of single-molecule emitters are altered by nanophotonic structures such as single plasmonic nanoparticles. The intensity and spectral properties of plasmon-coupled emitters have been studied extensively, but little is known about the effect of plasmon coupling on emission polarization. Here, we examine how particle-emitter coupling modifies the polarization of single fluorophores in both experiment and simulation. We quantify degree of linear polarization using Stokes polarimetry with a polarization-sensitive camera and quantify the Stokes parameters with a single-shot acquisition without requiring additional optics in the detection path. We then perform polarization-resolved measurements of plasmon-coupled fluorescence from single-molecule emitters using an approach based on DNA-PAINT. We quantify the effect of the setup and associated noise sources on the measured Stokes parameters. We then quantify the angle of linear polarization (AoLP) and the degree of linear polarization (DoLP) for thousands of single molecules. We compare our results to a numerical model that propagates the plasmon-coupled single-molecule emission through the optical setup to yield the polarized point spread function in the camera plane. Simulations and experiments are in good agreement and shed new light on the polarization of antenna-coupled fluorophores, while it establishes single-shot polarimetry as a promising and straightforward method to quantify polarization properties at the single-molecule level.