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中国物理学会期刊

基于可控合成与原位光谱的CsPbBr3纳米晶激子行为动态演化研究

Dynamic Evolution of Exciton Behavior in CsPbBr3 Nanocrystals via Controlled Synthesis and In Situ Spectroscopy

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  • 铅钙钛矿纳米晶的优异光电性能源于其独特的激子行为,然而传统合成方法反应迅速,难以对纳米晶激子动力学过程进行原位研究。为解决这一挑战,本文开发了一种室温可控合成新策略,通过使用三辛基氧化膦络合铅并与铯前驱体分离,延缓CsPbBr3纳米晶的生长时间至数十分钟,为原位监测其光学性质的动态演化提供了可能。利用搭建的原位光谱测试系统,成功获得了纳米晶生长与熟化过程中吸收及荧光光谱的连续变化数据。光谱分析显示,第一激子吸收峰随生长时间发生红移。进一步通过Elliott模型拟合吸收光谱,观察到在CsPbBr3纳米晶生长阶段,激子结合能与禁带宽度之间呈现出清晰的线性关联。本研究不仅为实现钙钛矿纳米晶形成过程的动态观测提供了新方法,所揭示的激子参数间的内在规律更为理解其光物理机制及实现性能精准调控奠定了重要基础。

    In recent years, lead halide perovskite (LHP) nanocrystals have attracted considerable attention due to their excellent optical properties, including high photoluminescence quantum yield (PLQY), tunable band gap, narrow emission peak, large absorption cross-section, and long exciton coherence time. The excellent optoelectronic properties of LHP nanocrystals stem from their unique exciton behavior. However, conventional synthesis methods involve rapid reactions, making it challenging to conduct in-situ studies on the exciton dynamics of nanocrystals. To address this challenge, this work developed a novel room-temperature synthesis method that separately controls ionized \mathrmCs^+and coordinated \mathrmPb^2+, successfully achieving the slow growth of \mathrmCsPbBr_3 nanocrystals and laying a foundation for the measurement and research of their in-situ spectra. By establishing an in-situ spectroscopic measurement system, the dynamic evolution of absorption and photoluminescence (PL) spectra during the formation of \mathrmCsPbBr_3 nanocrystals was tracked in real time. The spectra were fitted using the Elliott model, and the temporal evolution laws of key physical parameters such as exciton binding energy ( E_b ) and band gap \left(E_\mathrmg\right) were quantitatively obtained. It was found that during the growth stage of \mathrmCsPbBr_3 nanocrystals (after \sim 4 minutes), E_b and E_\mathrmg exhibit a significant linear correlation, which is in excellent agreement with first-principles calculations. This study not only provides a new method for the dynamic observation of the formation process of LHP nanocrystals but also the revealed intrinsic laws between exciton parameters lay a crucial foundation for understanding their photophysical mechanisms and realizing precise performance regulation.

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