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Polarized upconversion luminescence from a single LiLuF4:Yb3+/Er3+ microcrystal for orientation tracking

LiLuF4:Yb3+/Er3+单颗粒微米晶的偏振上转换发光和 取向示踪应用

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Abstract

Polarized upconversion luminescence (UCL) of lanthanide-doped micro/nano-crystals has shown great promise in single-particle tracking and super-resolution bioimaging. However, because of the spectral line broadening and multiple sites of lanthanide in upconversion particles (UCPs), the crystal-field (CF) polarization components of UCL are usually undistinguishable. Herein, we report the linearly polarized UCL in LiLuF4:Yb3+/Er3+ single microcrystals with resolvable CF transition lines and a polarization degree up to 0.82. The CF levels and CF transition lines of Er3+, as well as their emission polarization anisotropy, are unraveled for the first time through low-temperature and high-resolution photoluminescence (PL) and UCL spectroscopies. By taking advantage of the well-resolved and highly-polarized CF transition lines of Er3+, we demonstrate the application of LiLuF4:Yb3+/Er3+ single microcrystals as anisotropic UCL probes for orientation tracking. These findings provide fundamental insights into the polarization anisotropy of UCL in lanthanide-doped single particles, thus laying a foundation for the future design of anisotropic luminescent probes towards versatile applications.

摘要

稀土掺杂微/纳晶体的偏振上转换发光在单颗粒示踪和高分辨成 像等领域具有广泛的应用前景. 然而, 由于稀土上转换颗粒的多位置发 光和谱线展宽, 其上转换发光的晶体场偏振组分往往难以区分. 本文报 道了LiLuF4:Yb3+/Er3+单颗粒微米晶的线偏振上转换发光, 其晶体场跃 迁谱线容易分辨, 偏振度达到0.82. 通过低温高分辨荧光光谱和上转换 光谱测试, 我们揭示了LiLuF4:Yb3+/Er3+微米晶Er3+的晶体场能级、晶体 场跃迁谱线及其上转换发光的偏振各向异性. 利用Er3+易分辨且高度偏 振的晶体场跃迁谱线, 我们还证明了LiLuF4:Yb3+/Er3+单颗粒微米晶作 为各向异性上转换荧光探针在取向示踪方面的潜在应用. 这些发现为 稀土掺杂单颗粒的上转换偏振各向异性研究提供了理论基础, 也为各 向异性荧光探针的设计和多功能用途的开发提供了新思路.

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Acknowledgements

This work was supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (CAS, XDB20000000), the National Natural Science Foundation of China (U1805252, 21875250, 11774345, 12074379, 21771185, 12074380, and 21975257), the Youth Innovation Promotion Association of the CAS (2020305), and the Natural Science Foundation of Fujian Province (2020I0037).

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Authors and Affiliations

  1. CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Shouquan Wei  (魏寿权), Xiaoying Shang  (商晓颖), Ping Huang  (黄萍), Wei Zheng  (郑伟), Jin Xu  (徐金), Meiran Zhang  (张美然), Datao Tu  (涂大涛) & Xueyuan Chen  (陈学元)

  2. College of Chemistry, Fuzhou University, Fuzhou, 350116, China

    Shouquan Wei  (魏寿权), Wei Zheng  (郑伟), Datao Tu  (涂大涛) & Xueyuan Chen  (陈学元)

  3. Xiamen Institute of Rare-Earth Materials, Haixi Institutes, Chinese Academy of Sciences, Xiamen, 361021, China

    En Ma  (马恩)

  4. Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou, 350108, China

    Ping Huang  (黄萍), Wei Zheng  (郑伟), Jin Xu  (徐金), Datao Tu  (涂大涛) & Xueyuan Chen  (陈学元)

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  1. Shouquan Wei  (魏寿权)
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  2. Xiaoying Shang  (商晓颖)
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Contributions

Wei S, Huang P and Chen X conceived the projects, wrote the paper and were primarily responsible for the experiments. Wei S, Shang X and Huang P carried out the polarized UCL measurements and analyses. Wei S, Huang P and Zheng W carried out the low-temperature PL and UCL measurements. Huang P, Zheng W, Ma E, Tu D and Chen X analyzed the crystal-field levels and polarization directions. Xu J and Zhang M synthesized the microcrystals and measured the room-temperature PL and UCL spectra. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Ping Huang  (黄萍) or Xueyuan Chen  (陈学元).

Additional information

Shouquan Wei earned her BSc from Zhengzhou University (2018). She is currently a master student in materials engineering at Fuzhou University. She joined Prof. Xueyuan Chen’s group at Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS) in September 2018. Her research interest focuses on the controlled synthesis and optical spectroscopy of lanthanide-doped luminescent materials.

Ping Huang was born in Hebei province of China. She earned her BSc from Hebei University (2008) and PhD in materials physics and chemistry from FJIRSM, CAS (2014). She joined Prof. Xueyuan Chen’s group as a research assistant professor in 2014 and was promoted to a research associate professor in 2016. Her research interest focuses on the chemical synthesis, optical properties and bioapplication of lanthanide-doped luminescent nanomaterials.

Xueyuan Chen is Editor-in-Chief of Journal of Luminescence. He earned his BSc from the University of Science and Technology of China (1993) and his PhD degree from FJIRSM, CAS (1998). From 2001 to 2005, he was a postdoctoral research associate at the Chemistry Division of Argonne National Laboratory, U.S. Department of Energy, where he studied the photophysics and photochemistry of heavy elements. In 2005, he joined the faculty at FJIRSM, where he is currently a professor and group leader in materials chemistry and physics. His research focuses on the electronic structures, optical properties and applications of inorganic luminescent materials, such as lanthanide (rare-earth) nano-bioprobes and LED phosphors.

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The authors declare that they have no conflict of interest.

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Wei, S., Shang, X., Huang, P. et al. Polarized upconversion luminescence from a single LiLuF4:Yb3+/Er3+ microcrystal for orientation tracking. Sci. China Mater. 65, 220–228 (2022). https://doi.org/10.1007/s40843-021-1713-x

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