Single-Molecule Phosphorescence and Intersystem Crossing in a Coupled Exciton Plasmon System.

Grewal, Abhishek; Imada, Hiroshi; Miwa, Kuniyuki; Imai-Imada, Miyabi; Kimura, Kensuke; Jaculbia, Rafael; Kuhnke, Klaus; Kern, Klaus et al. · ACS Nano · 2025

basic_science · Level V

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Abstract

Scanning the sharp metal tip of a scanning tunneling microscope (STM) over a molecule allows for tuning the coupling between the tip plasmon and a molecular fluorescence emitter. This allows access to local variations in fluorescence field enhancement and wavelength shifts, which are central parameters for characterizing the plasmon-exciton coupling. Performing the same for phosphorescence with molecular-scale resolution remains a significant challenge. In this study, we present the investigation of phosphorescence from isolated Pt-Phthalocyanine molecules by analyzing tip-enhanced emission spectra in both current-induced and laser-induced phosphorescence. The latter directly monitors singlet-to-triplet state intersystem crossing of a molecule below the tip. The study contributes to a detailed understanding of triplet excitation pathways and their potential control at submolecular length scales. Additionally, the coupling of organic phosphors to plasmonic structures is a promising route for improving light-emitting diodes.