Super‐Resolution Lifetime Imaging of Single Molecules Near Gold Bowtie Nanoparticles

Abstract Interactions between light and matter serve as the basis of many technologies, but the quality of these devices is inherently limited by the optical properties of their constituents. Plasmonic nanoparticles are a highly versatile and tunable platform for the enhancement of such optical properties. However, the near‐field nature of these effects has made thorough study and understanding of these mechanisms difficult. In this work, we introduce a fully confocal technique combining photoswitching super‐resolution microscopy with fluorescence lifetime imaging microscopy to study single‐molecule decay rate enhancement. We demonstrate that the technique combines a spatial resolution better than 20 nm, and a 16 ps temporal resolution. Simultaneously, an autocorrelation measurement is also performed to confirm that the data indeed originates from single molecules. This work provides insight into the various mechanisms of plasmon‐enhanced emission, and allows the study of the correlation between emission intensity and lifetime enhancement. This complicated relationship is shown to be dependent upon the relative influence of various radiative and nonradiative decay pathways. Here, we provide a platform for further study of emission mislocalization, the position‐dependent prominence of different decay pathways, and the direct super‐resolved measurement of the local density of states.