Interstitial Oxygen Modulating Reversible Upconversion Luminescence

Abstract Reversible upconversion luminescence (RUCL) through defect engineering holds great promise for various applications, including photoswitches, information recording, and storage devices. However, the reversible photoluminescence in inorganic crystals is rarely reported. Crucially, the underlying mechanism of reversible luminescence remains unclear, which challenges the design of high‐performance reversible luminescence inorganic materials. Herein, an anomalous RUCL in a class of β‐Ba₂ScAlO₅:Yb³⁺/RE³⁺ (RE = Er, Ho, Tm, Tb, Sm, or Eu) phosphors is reported. By alternating annealing environments (air or hydrogen), a robust and repeatable cycle of luminescence and quenching is observed. The first‐principles calculations reveal that porous β‐Ba₂ScAlO₅:Yb³⁺/RE³⁺ can host oxygen interstitials (during annealing in air) with a low formation energy. The interstitial oxygen state, close to the Yb 4f state, leads to luminescence quenching. Removal of oxygen interstitials (during annealing in hydrogen) can restore the luminescence by initiating radiative energy transfer. Experimentally, the existence of interstitial oxygen is confirmed with neutron diffraction technology. It is worth noting that the strong chemical bonds in crystals make adding and removing anion vacancies challenging, unlike the more “free” interstitials. The findings offer new insights into manipulating upconversion luminescence in inorganic crystals by defect engineering and provide motivation for future research in this field.