Intervalence charge transfer of Cr3+-Cr3+ aggregation for NIR-II luminescence

Abstract

Abstract The increasing demand for high-contrast biological imaging, non-destructive testing, and infrared night vision can be addressed by the development of high-performance NIR light-emitting materials. Unlike lanthanide (Ln3+) with sharp-line multiplets and isolated Cr3+ with NIR-I emission, this study reports the first-ever NIR-II broadband luminescence based on the intervalence charge transfer (IVCT) of Cr3+-Cr3+ aggregation in gallate magentoplumbite. In particular, LaMgGa11O19:0.7Cr3+ exhibits dual-emission (NIR-I, 890 nm and NIR-II, 1200 nm) with a full width at half maximum (FWHM) of 626 nm under 450 nm blue LED excitation. Moreover, this dual-emission exhibits anti-thermal quenching behavior (432% @ 290 K), attributed to the energy transfer among multiple Cr3+ centers. Cryogen absorption spectra, lifetimes decay (2.3 ms), and electron paramagnetic experiments reveal the NIR-II luminescence of the Cr3+-Cr3+ → Cr2+-Cr4+ IVCT transition. The application of LaMgGa11O19:0.7Cr3+ in NIR-II biological imaging as an optical contrast agent, non-destructive testing, and night vision is demonstrated. This work provides new insights into broadband NIR-II luminescence under UV-NIR excitation based on the IVCT of Cr3+-Cr3+ aggregation.