Plasmon-enhanced S2 electroluminescence from the high-lying excited state of a single porphyrin molecule

We demonstrate the B-band electroluminescence from the high-lying S-2 excited state of a single zinc porphyrin molecule with the scanning tunneling microscope-induced luminescence technique by using an aluminum tip. The nanocavity plasmon mode is found to be critical for the occurrence of S-2 electroluminescence. When using a silver tip to excite the molecule electronically decoupled from the Ag(100) substrate by an ultrathin sodium chloride spacer, we only observe the Q-band electroluminescence originating from the radiative decay of the S-1 first excited state, without any B-band emission due to the lack of effective plasmonic enhancement for the B-band. However, when the nanocavity plasmon resonance is tuned to a bluer range by using an aluminum tip, the S-2 electroluminescence from a single zinc porphyrin shows up because the nanocavity plasmon mode can now spectrally overlap with the B-band emission to generate efficient plasmonic enhancement for the radiative decay directly from the S-2 state. Interestingly, the excitation mechanisms for these two types of emission are found to be different. While the Q-band emission is attributed mainly to a carrier-injection mechanism, the B-band electroluminescence is found to be excited via an inelastic electron scattering process. Our results open a route to investigate the photophysical property and dynamic behavior of isolated molecules in their excited states. Published under license by AIP Publishing.