Polyoxometalates (POMs) have shown prominence in the field of semiconductive materials in recent years. However, electronic applications based on these emerging materials are still in their early stages. Here, a sensitive and water-stable F-PEA-ZnW12 X-ray detector has been designed and constructed for hard X-ray detection and imaging. Supramolecular interactions of H···O bonding, electrostatic, and anion-π interactions not only enable FPEA-ZnW12 excellent water stability but also shorten the distance between [ZnW12O40]6- clusters, which reduces ion migration and dark current simultaneously, resulting in the conductivity of 3.2 × 10-11 S cm-1. Furthermore, the heteropoly blue formed on the surface of the O-FPEA-ZnW12 wafer device promotes the effective separation and extraction of X-ray-induced carriers, enhancing the sensitivity for X-ray detection. The R/O-FEPA-ZnW12 wafer device yields a high sensitivity of 3.1 × 104 μC Gyair-1 cm-2 with the lowest detectable dose rate of 69 nGyair s-1 under 120 kV hard X-ray irradiation. In addition, the O-FPEA-ZnW12 wafer detector exhibits the potential for X-ray detection in water with a sensitivity of 1.0 × 104 μC Gyair-1 cm-2. Moreover, the fabricated POM X-ray detector shows excellent X-ray imaging capability and long-term operational stability without any attenuation of 1 year exposure to air without any encapsulation.
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