Zero‐Dimensional Metal Halides Inorganic Frameworks Modulation for Sensitivity and Stable Direct X‐Ray Detection

Zero‐Dimensional (0D) metal halides (MHs) exhibit unique optoelectronic properties in next‐generation X‐ray imaging technology, stemming from their isolated polyhedral structures. However, the limited understanding of the insulating behaviors of organic cationic spacers, the kinetic mechanisms regulating charge transport within isolated inorganic frameworks, and the synergistic effects between these components have resulted in suboptimal carrier transport and collection efficiencies. Herein, the correlation between the coordination and performance of inorganic frameworks is investigated, and it is concluded that the inorganic framework exhibits unique charge transport characteristics with organic cations. 0D single crystals, namely MPAZE‐ZnBr 4 ·H 2 O (15 × 5 × 3 mm 3 ) and MPAZE‐MnBr 3 (H 2 O) 3 ·Br (15 × 10 × 8 mm 3 ), are successfully synthesized. The inorganic framework significantly governs the steric hindrance within the material and dictates the involvement of organic cations in the conduction process. Density functional theory (DFT) is employed to analyze the coordination geometries of organic cations with inorganic frameworks, as well as the impacts of binding energies and band structure contributions on charge transport dynamics and device performance. The resulting X‐ray detector demonstrates a high sensitivity of 9185 µC Gy air −1 cm −2 and a low detection limit of 0.573 µGy air s −1 , alongside excellent environmental stability.