Fine Structure of the Optical Absorption Resonance in Cs2AgBiBr6 Double Perovskite Thin Films

The lead-free double perovskite Cs2AgBiX6 (X = Br, Cl) has recently demonstrated great potential for applications in solar cells, photodetectors, and X-ray detectors. This material is characterized by a dominant resonant absorption feature in the UV-blue spectral region, which is still under controversial discussion regarding its origin. Here, we uncover an electronic fine structure of this optical feature in Cs2AgBiBr6 thin films. A detailed temperature-resolved study combining photoluminescence (PL), photoluminescence excitation (PLE), and absorption spectroscopy reveals the existence of three optical transitions, situated approximately 100 meV around the resonance at 2.83 eV. PL measurements under pulsed excitation uncover a short-lived blue emission at the absorption resonance energy that persists up to room temperature and indicates the competition of direct emission from the resonant state and fast relaxation into the red emissive ground state. We derive a comprehensive energy scheme and suggest possible mechanisms leading to the observed fine structure splitting.