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Lead-free rare-earth double perovskite Cs2AgIn1−γ−xBixLaγCl6 nanocrystals with highly efficient warm-white emission

具有高效暖白光的非铅稀土双钙钛矿Cs2AgIn1−γ−xBixLaγCl6纳米晶

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Abstract

Lead-free double perovskite nanocrystals (NCs), such as Cs2AgInCl6, have attracted considerable attention as stable and non-toxic alternatives to lead-based perovskites. However, the low photoluminescence (PL) intensity of pristine Cs2AgInCl6 limits its practical applications. In this study, a series of Cs2AgIn1−γ−xBixLaγCl6 NCs were synthesized to break the parity-forbidden transition and modify the associated optical functionalities. A broadband bright warm-white emission in the visible region was achieved, with an excellent PL quantum yield of 60%. The dynamic mechanism, involving ultrafast transient absorption, suggests that high-efficiency PL is induced by triplet self-trapping exciton emission. The incorporation of La3+-Bi3+ facilitated the singlet-triplet transition by increasing the lifetime and quickening the intersystem crossing process. This finding provides a reliable method for optimizing the optical properties of emerging lead-free halide perovskite NCs.

摘要

非铅双钙钛矿纳米晶(NCs), 例如Cs2AgInCl6, 作为稳定、 无毒的铅基钙钛矿替代物, 已经引起了人们的广泛关注. 但其较弱的荧光限制了其在实际中的应用. 在这项工作中, 为了打破禁阻跃迁, 同时优化光学特性, 我们合成了一系列Cs2AgIn1−γ−xBixLaγCl6 NCs. 该材料在可见光区内实现了明亮的宽频带暖白色发光, 量子效率最高达到了60%. 我们利用超快瞬态吸收光谱等先进表征手段研究了其发光动力学机理, 认为高效的白光发射源于三重态自陷激子. La3+和Bi3+的引入延长了荧光衰减寿命并加快了系间窜越进程, 从而促进了单重态–三重态的转换. 这一发现为新型非铅钙钛矿纳米晶材料的光学性能优化提供了可靠的方法.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2017YFA0204800), the National Natural Science Foundation of China (21833009, 21533010, and 21525315), the Scientific Instrument Developing Project of the Chinese Academy of Sciences (YJKYYQ20190003), Liaoning Revitalization Talents Program (XLYC1802126), and Dalian City Foundation for Science and Technology Innovation (2019J12GX031).

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Authors and Affiliations

  1. Institute of Molecular Sciences and Engineering, Shandong University, Qingdao, 266237, China

    Hang Yin  (尹航), Qingkun Kong  (孔庆坤), Ruiling Zhang  (张瑞玲), Daoyuan Zheng  (郑道元) & Keli Han  (韩克利)

  2. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Hang Yin  (尹航), Bin Yang  (杨斌) & Keli Han  (韩克利)

Authors
  1. Hang Yin  (尹航)
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  2. Qingkun Kong  (孔庆坤)
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  3. Ruiling Zhang  (张瑞玲)
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  4. Daoyuan Zheng  (郑道元)
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  5. Bin Yang  (杨斌)
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  6. Keli Han  (韩克利)
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Contributions

Author contributions Yin H and Han K conceived the initial idea. Yin H, Kong Q, Zhang R, Zheng D, and Yang B performed the material characterization and analysis. Han K directed the project. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Keli Han  (韩克利).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Hang Yin received his Master’s degree in physical chemistry from Yanbian University in 2017. He studies at the Institute of Molecular Science and Engineering of Shandong University, instructed by Professor Keli Han from Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences (CAS). He is currently jointly trained in Group 1101 of the Key Laboratory of Molecular Dynamics of DICP. He is interested in the research of new energy materials.

Keli Han received his PhD degree in 1990 from the State Key Laboratory of Molecular Reaction Dynamics at DICP and subsequently became an Assistant Professor. He conducted postdoctoral research at the University of California at Davis and Emory University in 1993–1995. In 1995, he became a Full Professor of chemical physics at DICP. His current research interests involve experimental and theoretical chemical dynamics.

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Yin, H., Kong, Q., Zhang, R. et al. Lead-free rare-earth double perovskite Cs2AgIn1−γ−xBixLaγCl6 nanocrystals with highly efficient warm-white emission. Sci. China Mater. 64, 2667–2674 (2021). https://doi.org/10.1007/s40843-021-1681-7

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