Atomic-scale sensing of photoexcitation processes in electronically isolated molecules via atomic force microscopy

Atomic-scale insights into light-matter interaction can be obtained using light-assisted scanning probe microscopy techniques. Recently, photoexcited charge carriers have been detected by means of scanning tunnelling microscopy, enabling the study of photo-induced charge transfer with atomic-scale spatial resolution. Here, we propose an approach based on atomic force microscopy (AFM), namely photoexcitation single-charge AFM (PE-AFM), to detect photoexcitation in single molecules adsorbed on non-conductive dielectric films. Synchronizing laser pulses to the oscillation of the tip of an AFM enables the detection of electron tunnelling events that follow photoexcitation. We demonstrate the PE-AFM technique for individual copper phthalocyanine molecules and achieve photoexcitation-driven AFM contrast with {\aa}ngstr\"om spatial resolution. The observed sub-molecular contrast suggests the involvement of a long-lived quadruplet excited state. When combined with the recently developed AFM excited-state spectroscopy including lifetime measurements, PE-AFM enables comprehensive characterization of electronic states involved in photoexcitation and subsequent intersystem crossing, establishing a powerful platform for investigating photophysical processes at the single-molecule level.