Enhancement of the Photocurrent of a Single Photosystem I Complex by the Localized Plasmon of a Gold Nanorod.

A combination of conductive atomic force microscopy (AFM) and confocal fluorescence microscopy was used to measure photocurrents passing through single trimeric photosytem I (PSI) complexes located in the vicinity of single gold nanorods (AuNRs). Simultaneous excitation of PSI and of the AuNR longitudinal plasmon mode and detection of photocurrents from individual PSI in relation to the position of single AuNRs enable insight into plasmon-induced phenomena that are otherwise inaccessible in ensemble experiments. We have observed photocurrent enhancement by the localized plasmons by a factor of 2.9 on average, with maximum enhancement values of up to 8. Selective excitation of the longitudinal plasmon modes by the polarization of the excitation laser enables controllable switch-on of the photocurrent enhancement. The dependence of the extent of enhancement on the distance between PSI and AuNRs indicates that, apart from the enhancement of absorption, there is an additional enhancement mechanism affecting directly the electron transport process. The present study provides deeper insight into the molecular mechanisms of plasmon-enhanced photocurrents, not only in PSI but also potentially in other systems as well.