Peng Chengdong, Zhuang Zewen, Yang Huimin, Zhang Guiyang, Fei Honghan
Shanghai Key Laboratory of Chemical Assessment and Sustainability , School of Chemical Science and Engineering , Tongji University , 1239 Siping Rd. , Shanghai 200092 , P. R. China . Email:
Chem Sci. 2017 Dec 19;9(6):1627-1633. doi: 10.1039/c7sc04118g. eCollection 2018 Feb 14.
Herein, we report the unusual broadband white-light emission as an intrinsic property from two cationic lead bromide frameworks. This is the first time that the metal halide materials adopting a purely inorganic positively-charged three-dimensional (3D) topology have been synthesized, thus affording highly distorted Pb centers. The single-component white-light emitters achieve an external quantum efficiency of up to 5.6% and a correlated color temperature of 5727 K, producing typical white-light close to that of fluorescent light sources. Unlike the air/moisture-sensitive 3D organolead halide perovskites, our cationic materials are chemically "inert" over a wide range of pH as well as aqueous boiling condition. Importantly, these long-sought ultrastable lead halide materials exhibit undiminished photoluminescence upon continuous UV-irradiation for 30 days under atmospheric condition (∼60% relative humidity, 1 bar). Our mechanistic studies indicate the broadband emission have contributions from the self-trapped excited states through electron-vibrational coupling in the highly deformable and anharmonic lattice, as demonstrated by variable-temperature photoluminescence/absorption spectra as well as X-ray crystallography studies. The chemical robustness and structural tunability of the 3D cationic bromoplumbates open new paths for the rational design of hybrid bulk emitters with high photostability.
在此,我们报道了两种阳离子溴化铅骨架材料具有不寻常的宽带白光发射这一固有特性。这是首次合成采用纯无机带正电荷三维(3D)拓扑结构的金属卤化物材料,从而产生高度扭曲的铅中心。单组分白光发射体的外量子效率高达5.6%,相关色温为5727 K,产生接近荧光光源的典型白光。与对空气/湿气敏感的3D有机铅卤化物钙钛矿不同,我们的阳离子材料在很宽的pH范围以及水沸腾条件下化学性质“惰性”。重要的是,这些长期以来寻求的超稳定铅卤化物材料在大气条件下(相对湿度约60%,1巴)连续紫外照射30天时光致发光不减弱。我们的机理研究表明,宽带发射来自高度可变形和非谐晶格中通过电子 - 振动耦合产生的自陷激发态,变温光致发光/吸收光谱以及X射线晶体学研究证明了这一点。3D阳离子溴化铅酸盐的化学稳定性和结构可调性为合理设计具有高光稳定性的混合体发射体开辟了新途径。