Organic Cation Modulation in Manganese Halides to Optimize Crystallization Process and X‐Ray Response Toward Large‐Area Scintillator Screen

Manganese halides are one of the most potential candidates for large-area flat-panel detection owing to their biological safety and all-solution preparation. However, reducing photon scattering and enhancing the efficient luminescence of scintillator screens remains a challenge due to their uncontrollable crystallization and serious nonradiative recombination. Herein, an organic cation modulation is reported to control the crystallization process and enhance the luminescence properties of manganese halides. Given the industrial requirements of the X-ray flat-panel detector, the large-area A₂MnBr₄ screen (900 cm²) with excellent uniformity is blade-coated at 60 °C. Theoretical calculations and in situ measurements reveal that organic cations with larger steric hindrance can slow down the crystallization of the screen, thus neatening the crystal arrangement and reducing the photon scattering. Moreover, larger steric hindrance can also endow the material with higher exciton binding energy, which is beneficial for restraining nonradiative recombination. Therefore, the BPP₂MnBr₄ (BPP = C₂₅H₂₂P⁺) screen with larger steric hindrance exhibits a superior spatial resolution (>20 lp mm^-1) and ultra-low detection limit (< 250 nGy_air s^-1). This is the first time steric hindrance modulation is used in blade-coated scintillator screens, and it believes this study will provide some guidance for the development of high-performance manganese halide scintillators.