Zhang Siwei, Ma Fulong, Jiang Jinhui, Wang Zaiyu, Kwok Ryan T K, Qiu Zijie, Zhao Zheng, Lam Jacky W Y, Tang Ben Zhong
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, Division of Life Science and State Key Laboratory of Molecular Neuroscience, The Hong Kong University of Science and Technology, Kowloon, 999077, Hong Kong, P. R. China.
School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen (CUHK-Shenzhen), Guangdong, 518172, P. R. China.
Angew Chem Int Ed Engl. 2024 Aug 26;63(35):e202408586. doi: 10.1002/anie.202408586. Epub 2024 Jul 17.
Understanding the properties of the precursor can provide deeper insight into the crystallization and nucleation mechanisms of perovskites, which is vital for the solution-process device performance. Herein, we conducted a detailed investigation into the photophysics properties of CsPbBr precursors in a broad concentration and various solvents. The precursor transformed from the solution state into the colloidal state and exhibited aggregation-induced emission character as the concentration increased. The aggregative luminescence from the precursors originates from the polybromide plumbous that is formed through the coordination of solvent molecules to the lead metal center. Two adducts with monodentate (PbBr ⋅ solvent) and bidentate (PbBr ⋅ 2solvent) ligands can be obtained, accompanied by emission with photoluminescence at 610 and 565 nm, respectively. Furthermore, the aggregative luminescence intensity and color could be regulated by changing the solvent and precursor ratio. Besides, we discussed the difference between the molecular aggregate in the organic system and the ionic aggregate in the inorganic system: the ionic aggregate is composed of solvated ions rather than individual molecules as in organic systems, which could possess properties that ions do not have. The fluorescence that is sensitive to Pb coordination reported here could be applied to screen perovskite additives and judge the precursor aging.
了解前驱体的性质可以更深入地洞察钙钛矿的结晶和成核机制,这对于溶液法制备的器件性能至关重要。在此,我们对CsPbBr前驱体在广泛浓度范围和各种溶剂中的光物理性质进行了详细研究。随着浓度增加,前驱体从溶液状态转变为胶体状态,并表现出聚集诱导发光特性。前驱体的聚集发光源于通过溶剂分子与铅金属中心配位形成的多溴化铅。可以得到具有单齿(PbBr·溶剂)和双齿(PbBr·2溶剂)配体的两种加合物,分别伴随着610和565 nm的光致发光发射。此外,聚集发光强度和颜色可以通过改变溶剂和前驱体比例来调节。此外,我们还讨论了有机体系中的分子聚集体与无机体系中的离子聚集体之间的差异:离子聚集体由溶剂化离子组成,而不是像有机体系中那样由单个分子组成,其可能具有离子所没有的性质。此处报道的对铅配位敏感的荧光可用于筛选钙钛矿添加剂并判断前驱体老化情况。