Spin-Triplet-Mediated Up-Conversion and Crossover Behavior in Single-Molecule Electroluminescence

Scanning-tunneling-microscope-induced light emission serves as a powerful approach in revealing and manipulating the optical properties of molecular species, intermolecular energy transfer, and plasmon-molecule coupling. Earlier studies have established the existence of molecular up-conversion electroluminescence in diverse situations, but the underlying microscopic mechanisms are still under active debate, dominated by intermolecular triplet-triplet annihilation and plasmonic pumping. Here we report on the experimental realization of up-conversion electroluminescence from a prototypical single phthalocyanine molecule, allowing us to unambiguously rule out mechanisms based on intermolecular coupling and also offering unprecedented opportunities to elucidate much richer characteristics unforeseen in previous studies. In particular, the bias-dependent emission intensity displays three distinct regions with different nonlinear current dependences, which can be attributed to crossover behavior caused by the interplay between inelastic electron scattering and carrier-injection processes. We also develop a microscopic description to capture the essential physics involved in up-conversion electroluminescence mediated by a proper intermediate spin-triplet state.