Intrinsic molecular fluorescence from porphyrin molecules on Au(100) has been realized by using a nanoscale multimonolayer decoupling approach with nanoprobe excitation in the tunneling regime. The molecular origin of luminescence is established by the observed well-defined vibrationally resolved fluorescence spectra. The molecules fluoresce at low “turn-on” voltages for both bias polarities, suggesting an excitation mechanism via hot electron injection from either tip or substrate. The excited molecules decay radiatively through Franck-Condon [Formula presented] transitions.
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