Qiu Qiangwen, Zhang Guozhen, Chen Jingru, Di Yiming, Wu Liang, Chen Hongming, Chen Shan-Ci, Lin Mei-Jin
College of Chemistry, Fuzhou University, Fuzhou, 350116, P. R. China.
College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350116, P. R. China.
Small. 2024 Dec 4:e2407346. doi: 10.1002/smll.202407346.
X-ray imaging utilizing organic-inorganic hybrid metal halide (OIHMH) glassy scintillators has garnered significant attention. But their inferior radioluminescence makes achieving rapid image acquisition difficult, posing a persistent challenge for dynamic imaging. Herein, organic phosphonium halide side-chain engineering is proposed, introducing bulky aromatic rings at the alkyl chain ends, to improve the radioluminescence of OIHMHs. For Mn(II)-based OIHMHs, the (BUP)MnCl (BUP = butyltriphenylphosphonium) powder has a low relative light yield (5400 photons MeV). After introducing a benzyl group, this value of (BnO-MTP)MnCl (BnO-MTP = (benzyloxy)methyl) triphenylphonium) powder boosts to 60 000 photons MeV. The introduction of benzyl group can restrict molecular non-radiative vibrations, increase exciton binding energy, enhance electron-phonon coupling, and reduce self-absorption, thus significantly improving exciton utilization and scintillation performance of (BnO-MTP)MnCl. Besides, the transparent (BnO-MTP)MnCl glass has a low melting point (167 °C) and high relative light yield (26 000 photons MeV). When applied to X-ray imaging, it can achieve static imaging with a spatial-resolution of up to 24.6 lp mm and clear dynamic imaging under X-ray irradiation. Furthermore, this strategy also applies to Sb(III)-based OIHMHs with self-trapped exciton emissions, where (BnO-MTP)SbCl exhibits superior scintillation performance compared to (BUP)SbCl, demonstrating its broad applicability in constructing high-performance OIHMH glassy scintillators.
利用有机-无机杂化金属卤化物(OIHMH)玻璃闪烁体的X射线成像已引起广泛关注。但其较差的辐射发光性能使得快速图像采集变得困难,这对动态成像构成了持续挑战。在此,提出了有机卤化鏻侧链工程,即在烷基链末端引入庞大的芳香环,以提高OIHMH的辐射发光性能。对于基于Mn(II)的OIHMH,(BUP)MnCl(BUP = 丁基三苯基鏻)粉末的相对光产额较低(5400光子/兆电子伏)。引入苄基后,(BnO-MTP)MnCl(BnO-MTP = (苄氧基)甲基三苯基鏻)粉末的这一数值提高到60000光子/兆电子伏。苄基的引入可以限制分子的非辐射振动,增加激子结合能,增强电子-声子耦合,并减少自吸收,从而显著提高(BnO-MTP)MnCl的激子利用率和闪烁性能。此外,透明的(BnO-MTP)MnCl玻璃熔点低(167℃)且相对光产额高(26000光子/兆电子伏)。当应用于X射线成像时,它可以实现高达24.6线对/毫米空间分辨率的静态成像以及在X射线照射下清晰的动态成像。此外,该策略也适用于具有自陷激子发射的基于Sb(III)的OIHMH,其中(BnO-MTP)SbCl与(BUP)SbCl相比表现出优异的闪烁性能,证明了其在构建高性能OIHMH玻璃闪烁体方面的广泛适用性。