Generation of molecular hot electroluminescence by resonant nanocavity plasmons

Abstract

Control of the radiative properties of functional molecules near metals is a key issue in nano-optics, and is particularly important in the fields of energy transfer and light manipulation at the nanoscale1,2 and the development of plasmonic devices3,4,5. Despite the various vibronic transitions (S1(v′) → S0(v)) available for frequency tuning of fluorescence, the molecular emissions near metals reported to date have been subject to Kasha's rule, with radiative decay from the lowest excited state (S1(0)) (refs 6–10). Here, we show resonant hot electroluminescence arising directly from higher vibronic levels of the singlet excited state (S1(v′ > 0)) for porphyrin molecules confined inside a nanocavity in a scanning tunnelling microscope, by spectrally tuning the frequency of plasmons. We also demonstrate the generation of unexpected upconversion electroluminescence. These observations suggest that the local nanocavity plasmons behave like a strong coherent optical source with tunable energy, and can be used to actively control the radiative channels of molecular emitters by means of intense resonance enhancement of both excitation and emission. Nanocavity plasmons are exploited as a coherent optical source with tunable energy and to actively control the radiative channels of molecules. Intense resonance enhancement of both excitation and emission, in an effect called resonant hot-electroluminescence, is demonstrated for porphyrin molecules confined inside a nanocavity.