Light Emission from Single Oxygen Vacancies in Cu₂O Films Probed with Scanning Tunneling Microscopy

Abstract

Global photoluminescence (PL) and spatially resolved scanning tunneling microscopy (STM) luminescence are compared for thick Cu 2 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 2 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 2 O films are therefore assigned to excitation channels mediated by single or few O vacancies in the oxide matrix.

Investigating the role of oxygen vacancies in metal oxide for enhanced electrochemical reduction of NO3− to NH3: mechanistic insights

“…However, there are alternative methods to indirectly characterize OVs by examining the changes they bring in the structure or electronic state, as the production of OVs can alter the electronic configuration and coordination of the surrounding metals, which can serve as a unique identifier for the OVs in metal oxides. 77,87 For instance, the STM (scanning tunneling microscope) can be used to visualize the OV caves, 88,89 while PAS (positron annihilation spectroscopy) can be used to monitor them. 90,91 Moreover, the XRD, ND (neutron diffraction), and XAS (X-ray absorption spectroscopy) techniques can detect changes in the crystalline structure caused by OVs.…”