The Journal of Physical Chemistry Letters · 2023 · 11 citations · 32 references
Global photoluminescence (PL) and spatially resolved scanning tunneling microscopy (STM) luminescence are compared for thick Cu<sub>2</sub>O films grown on Au(111). While the PL data reveal two peaks at 750 and 850 nm, assigned to radiative electron decays via localized gap states induced by O vacancies, a wide-band emission between 700 and 950 nm is observed in STM luminescence. The latter is compatible with cavity plasmons stimulated by inelastic electron tunneling and contains no spectral signature of the Cu<sub>2</sub>O defects. The STM luminescence is nonetheless controlled by O vacancies that provide inelastic excitation channels for the cavity plasmons. In fact, the emission yield sharply peaks at 2.2 V sample bias, when tip electrons are resonantly injected into O defect states and recombine with holes at the valence-band top via plasmon stimulation. The spatially confined emission centers detected in photon maps of the Cu<sub>2</sub>O films are therefore assigned to excitation channels mediated by single or few O vacancies in the oxide matrix.
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