Lattice distortion enhanced self-trapped excitons emission in antimony halide crystalline clusters  

晶格畸变增强卤化锑晶体团簇的自陷激子发射

作　　者：Da Liu Jingjing He Yuting Sun Xinyi Liu Yu Peng Qing Li Hua Gui Yang Qiang Niu Shuang Yang Yu Hou 刘达;何敬敬;孙玉婷;刘心翊;彭玉;李庆;杨化桂;牛强;杨双;侯宇(Key Laboratory for Ultrafine Materials of Ministry of Education,Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China;China National Enterprise Technology Center,Inner Mongolia Erdos Electric Power and Metallurgy Group Company Limited,Ordos 016064,China²Equally contributed to this paper.)

机构地区：[1]Key Laboratory for Ultrafine Materials of Ministry of Education,Shanghai Engineering Research Center of Hierarchical Nanomaterials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China [2]China National Enterprise Technology Center,Inner Mongolia Erdos Electric Power and Metallurgy Group Company Limited,Ordos 016064,China

出　　处：《Science China Materials》2025年第1期132-140,共9页中国科学(材料科学)(英文版)

基　　金：financially supported by the National Ten Thousand Talent Program for Young Top-notch Talent;National Natural Science Foundation of China (22379044 and 52203330);Shanghai Pilot Program for Basic Research (22TQ1400100-5);“Dawn”Program of Shanghai Education Commission (22SG28);Shanghai Municipal Natural Science Foundation (22ZR1418000);Shanghai Sailing Program(22YF1410000);Postdoctoral Research Foundation of China(2021M701190);Fundamental Research Funds for the Central Universities (JKD01241607 and JKVD1241041);Major Science and Technology Projects of Inner Mongolia Autonomous Region (2021ZD0042);Shanghai Engineering Research Center of Hierarchical Nanomaterials(18DZ2252400);Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism。

摘　　要：Zero-dimensional perovskite materials,characterized by broadband emission caused by self-trapped excitons,are promising materials for stimuli-responsive and photo-writeable encryption.However,existing research is focused on the effects of structural phase transitions on photophysical properties,and lacks in-depth understanding of the mechanisms of self-trapped excitons emission.Here,we demonstrate that the dehydration reaction in zero-dimensional antimony halide clusters significantly enhances the self-trapped excitons emission without inducing structural phase transition,resulting in a substantial increase in photoluminescence(PL)quantum yield from 3.5%to 91.4%.In-situ X-ray diffraction and PL techniques were employed to shed light on the relationship between the crystal structure and radiative recombination,demonstrating the introduction of rich lattice distortion during the dehydration process.Temperature-dependent PL spectra and transient absorption spectra suggest that the lattice distortion causes the moderate electron-phonon coupling strength and high exciton binding energy,facilitating self-trapped excitons to relax from the non-radiative recombination singlet state to the radiative recombination triplet state,corresponding to the enhanced emission intensity.As a proof of concept,several switchable PL applications have been established in scenarios such as anti-counterfeiting,rewritable luminescent paper,and humidity sensing.This finding elucidates the emission mechanism of self-trapped excitons and provides a novel avenue for designing switchable luminescent materials.零维钙钛矿材料以自陷激子引起的宽带发射为特征,是一种很有前途的刺激响应和光加密材料.然而,现有的研究主要集中在结构相变对光物理性质的影响上,对自陷激子的发射机制缺乏深入了解.本文证明了零维卤化锑单晶中的脱水反应,在不诱导结构相变的基础上显著增强了自陷激子的发射,导致光致发光量子产率从3.5%大幅提高到91.4%.利用原位X射线衍射和光致发光技术揭示了晶体结构和光致发光强度之间的定性关系,证明了在脱水过程中引入了丰富的晶格畸变.温度依赖的荧光光谱和瞬态吸收光谱表明,晶格畸变导致中等的电子-声子耦合强度和更高的激子结合能,加速了自陷激子从非辐射复合单重态弛豫到辐射复合三重态,进而表现出增强的光致发光.作为概念验证,在防伪、可重写发光纸和湿度传感等多重场景中实现了应用.这一发现阐明了自陷激子的发射机制,并为设计可切换发光材料提供了一条新途径.

关 键 词：self-trapped excitons zero-dimensional perovskite antimony halides lattice distortion photoluminescence quantum yield 

分 类 号：O641.4[理学—物理化学]