Metal-free perovskites (MFPs) possess excellent photophysical properties of perovskites while avoiding the introduction of toxic metal ions and organic solvents, and have been expanded to X-ray detection. However, iodine-based high-performance MFPs are tended to oxidation, corrosion, and uncontrolled ion migration, resulting in poor material stability and device performance. Herein, the strongly electronegative PF6 - pseudohalide is used to fabricate the large-size MDABCO-NH4 (PF6 )3 (MDBACO = methyl-N'-diazabicyclo[2.2.2]octonium) single crystals (SCs) for solving the problems of iodine ions. After the introduction of PF6 - pseudohalides, the Coulomb interaction and hydrogen bonding strength are enhanced to alleviate the ion-migration and stability problems. Moreover, combined with theoretical calculations, PF6 - pseudohalides increase the ion-migration barrier, and affect the contribution of its components to the energy band for a broadening bandgap. Meanwhile, the improved physical properties, such as large activation energy of ionic migration, high resistivity, and low current drift, further expand its application in low-dose and sensitive X-ray detection. Finally, the X-ray detector based on MDABCO-NH4 (PF6 )3 SCs achieves a sensitivity of 2078 µC Gyair -1 cm-2 (highest among metal-free SCs-based detectors) and the lowest detectable dose rate (16.3 nGyair s-1 ). This work has expanded the selection of MFPs for X-ray detectors and somewhat advanced the development of high-performance devices.
Keywords: PF6− pseudohalides; coulomb interaction; hydrogen bond; metal-free perovskite; x-ray detection.
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