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Near-unity broadband luminescent cuprous halide nanoclusters as highly efficient X-ray scintillators

具有高效发光性能的亚铜卤化物纳米团簇应用于X-射线闪烁体

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Abstract

X-ray scintillators as functional energy materials possess the powerful ability to convert high-energy radiation into visible light with wide applications in various nuclear radiation fields. In this regard, three-dimensional (3D) lead perovskite nanocrystal-based X-ray scintillators have attracted extensive attention, but their low light yield and serious toxicity extremely restrict their further applications. To address these issues, a family of 0D hybrid cuprous halides of A2Cu4X6 (A = PTPP, TPA; X = Br, I) based on discrete [Cu4X6]2− nanoclusters were demonstrated as highly desirable lead-free scintillators. Upon excitation of both ultraviolet and blue light, these halide nanoclusters displayed that self-trapped excitons induced broadband light emissions from green to red with near-unity photoluminescent quantum yield (PLQY, 93.1%) andlarge Stokes shifts (>1.3 eV). Significantly, the high PLQY, negligible self-absorption, and strong X-ray attenuation from [Cu4X6]2− nanoclusters endowed them with extraordinary radioluminescence properties. The linear radioluminescence intensity response to a wide range of X-ray dose rates gave an acceptable detection limit of 0.7563 µGyair s−1, which was lower than the required value for regular medical diagnostics (5.5 µGyair s−1). X-ray imaging demonstrated an ultrahigh spatial resolution of 14.83 lp mm−1 and negligible afterglow (1.3 ms), showcasing potential applications in X-ray radiography. Overall, the combined superiorities of nontoxicity, high light yield, excellent stability, and good radiation hardness make cuprous halide nanoclusters excellent scintillators.

摘要

闪烁体可以将高能辐射转化为可见光, 作为一种光电功能材料 已经广泛应用于各种放射探测领域. 虽然三维Pb基钙钛矿纳米晶可以 开发为X射线闪烁体材料, 但是其较低的光产额和铅毒性问题在一定程 度上限制了其应用. 为解决这一问题, 本文重点关注零维金属卤化物发 光材料, 合成了一系列基于孤立[Cu4X6]2−纳米团簇的零维卤化物, 并将 其开发应用为闪烁体发光材料. 在紫外线或蓝光激发下, 该卤化物纳米 团簇均显示出宽带光发射, 发光颜色可覆盖绿色、橙色到红色, 并且具 有近乎100%的光量子产率和较大的Stokes位移(>1.3 eV). 特别突出的 是, 该类卤化物纳米团簇由于较高的发光量子产率、较小的光学自吸 收和较强的X射线衰减效率, 表现出优异的X-射线闪烁发光性能, 光产 额最高可达到24,240 photons MeV−1. 材料的闪烁发光强度与X射线剂 量呈现线性关系, 检测范围较宽, 且检测极限(0.7563 µGyair s−1)远低于 常规医学诊断所要求的计量(5.5 µGyair s−1). X-射线成像结果表明该纳 米团簇余晖衰减时间较短(1.3 ms), 空间分辨率较高(14.83 lp mm−1), 在医学成像等领域具有潜在的应用价值. 该项工作表明, 亚铜卤化物纳 米团簇具有高效、稳定、无毒、发光效率高等优点, 有望成为一种优 异的新型闪烁体发光材料.

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Acknowledgements

This work was supported by the National Nature Science Foundation of China (22171105 and 12004384), Shandong Provincial Natural Science Foundation (ZR2020KB012, ZR2021MB001, and ZR2022YQ14), the Fund of State Key Laboratory of Structural Chemistry (20210015), and the Special Foundation of Taishan Scholar Project.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu, 273155, China

    Dong-Yang Li  (李东阳), Meng-Ping Ren  (任梦萍), Wen-Qi Wang  (王文琦), Bing-Lin Zhang  (张炳林), Zhongliang Gong  (宫仲亮) & Xiao-Wu Lei  (雷晓武)

  2. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165, China

    Dong-Yang Li  (李东阳)

  3. Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, 430074, China

    Qingwen Tan  (谭清文) & Guangda Niu  (牛广达)

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  1. Dong-Yang Li  (李东阳)
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  2. Qingwen Tan  (谭清文)
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Contributions

Author contributions Li DY and Tan Q conceived and designed the experiments. Ren MP and Wang WQ carried out material synthesis. Zhang BL assisted in the measurements and data analysis. Niu G, Gong Z and Lei XW helped with data analysis and revised the manuscript. All authors participated in discussing the data and writing the manuscript.

Corresponding authors

Correspondence to Zhongliang Gong  (宫仲亮) or Xiao-Wu Lei  (雷晓武).

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

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Dong-Yang Li received his Master’s degree (2023) in chemistry from Qufu Normal University. He is currently studying at Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University. His research mainly focuses on the structural design and application development of metal halide luminescent materials.

Zhongliang Gong is currently a lecturer at Jining University. He earned his PhD degree (2019) from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS). His research interest is the controlled synthesis, photophysics and applications of metal halide perovskites.

Xiao-Wu Lei is presently a professor at Jining University. He obtained his PhD degree from Fujian Institute of Research on the Structure of Matter, CAS in 2010. His research area focuses on the structural design of inorganic luminescent materials and their applications in optoelectronic devices.

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Li, DY., Tan, Q., Ren, MP. et al. Near-unity broadband luminescent cuprous halide nanoclusters as highly efficient X-ray scintillators. Sci. China Mater. 66, 4764–4772 (2023). https://doi.org/10.1007/s40843-023-2649-1

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