Wang Chang-Feng, Yang Ye, Hu Yu, Ma Chuang, Ni Hao-Fei, Liu Pei-Guo, Lu Hai-Feng, Zhang Zhi-Xu, Wang Jianguo, Zhang Yujian, Fu Da-Wei, Zhao Kui, Zhang Yi
Institute for Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, 321004, Jinhua, People's Republic of China.
Key Laboratory of Applied Surface and Colloid Chemistry National Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, Institute for Advanced Energy Materials School of Materials Science and Engineering., Shaanxi Normal University, 710119, Xi'an, People's Republic of China.
Angew Chem Int Ed Engl. 2024 Dec 2;63(49):e202413726. doi: 10.1002/anie.202413726. Epub 2024 Oct 24.
Three-dimensional (3D) pseudohalide rare-earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X-ray detection remains unexplored, and the low Curie temperature (T) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)-M3HQ]RbEu(NO) [(R)-M3HQ=(R)-N-methyl-3-hydroxylquinuclidinium] with a low T of 285 K, a novel 3D PREDP ferroelectric [(R)-CM3HQ]CsEu(NO) [(R)-CM3HQ=(R)-N-chloromethyl-3-hydroxylquinuclidinium] are successfully synthesized, for which the T reaches 344 K. More importantly, such a strategy endowed [(R)-CM3HQ]CsEu(NO) with notable X-ray detection capabilities. Centimeter-sized [(R)-CM3HQ]CsEu(NO) single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 μC Gy cm and a low detectable dose rate of 152 nGy s, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco-friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.
三维（3D）伪卤化物稀土双钙钛矿（PREDPs）因其多样的物理性质而备受关注，这些性质包括铁电性、铁弹性、大压电响应和圆偏振发光。然而，它们在X射线检测方面的潜力尚未得到探索，并且低居里温度（T）限制了PREDP铁电体的性能窗口。在此，通过将涉及有机阳离子上卤素取代和Rb/Cs取代的化学调控策略应用于居里温度低至285 K的PREDP [(R)-M3HQ]RbEu(NO) [(R)-M3HQ=(R)-N-甲基-3-羟基奎宁环鎓]，成功合成了一种新型的3D PREDP铁电体[(R)-CM3HQ]CsEu(NO) [(R)-CM3HQ=(R)-N-氯甲基-3-羟基奎宁环鎓]，其居里温度达到344 K。更重要的是，这种策略赋予[(R)-CM3HQ]CsEu(NO)显著的X射线检测能力。由水溶液制备的厘米级[(R)-CM3HQ]CsEu(NO)单晶表现出1307 μC Gy cm的灵敏度和152 nGy s的低可检测剂量率，这是混合双钙钛矿铁电探测器报道的最高灵敏度。这项工作将PREDPs定位为下一代环保型光电子材料的有前途的候选者，也为铁电材料中结构、组成和功能之间的相互作用提供了重要见解。
