Spontaneous fluorescence rates of single-molecule emitters are typically on the order of nanoseconds. However, coupling them with plasmonic nanostructures can substantially increase their fluorescence yields. The confinement between a tip and sample in a scanning tunneling microscope creates a tunable nanocavity, an ideal platform for exploring the yields and excitation decay rates of single-molecule emitters, depending on their coupling strength to the nanocavity. With such a setup, we determine the excitation lifetimes from the direct time-resolved measurements of phthalocyanine fluorescence decays, decoupled from the metal substrates by ultrathin NaCl layers. We find that when the tip is approached to single molecules, their lifetimes are reduced to the picosecond range due to the effect of coupling with the tip-sample nanocavity. On the other hand, ensembles of the adsorbed molecules measured without the nanocavity manifest nanosecond-range lifetimes. This approach overcomes the drawbacks associated with the estimation of lifetimes for single molecules from their respective emission line widths.

• Keywords
• STM, TCSPC, TEPL, nanocavity, photoluminescence, phthalocyanine,
• Publication type
• Journal Article MeSH

Charged optical excitations (trions) generated by charge carrier injection are crucial for emerging optoelectronic technologies as they can be produced and manipulated by electric fields. Trions and neutral excitons can be efficiently induced in single molecules by means of tip-enhanced spectromicroscopic techniques. However, little is known of the exciton-trion dynamics at single molecule level as this requires methods permitting simultaneous subnanometer and subnanosecond characterization. Here, we investigate exciton-trion dynamics by phase fluorometry, combining radio frequency modulated scanning tunnelling luminescence with time-resolved single photon detection. We generate excitons and trions in single Zinc Phthalocyanine (ZnPc) molecules on NaCl/Ag(111), and trace the evolution of the system in the picosecond range. We explore the dependence of effective lifetimes on bias voltage and describe the conversion mechanism from neutral excitons to trions, via charge capture, as the primary pathway to trion formation. We corroborate the dynamics of the system by a causally deterministic four-state model.

• Keywords
• STML, exciton, lifetime, phase fluorometry, photon map, trion, zinc phthalocyanine,
• Publication type
• Journal Article MeSH