NaYF4:Yb3+/Er3+单颗粒微米棒偏振上转换发光及其取向示踪※

doi:10.6023/A21120618

化学学报 ›› 2022, Vol. 80 ›› Issue (3): 244-248.DOI: 10.6023/A21120618 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究通讯

NaYF₄:Yb³⁺/Er³⁺单颗粒微米棒偏振上转换发光及其取向示踪^※

胡晓柯^a^,^b, 商晓颖^b, 黄萍^a^,^b^,^*(), 郑伟^a^,^b, 陈学元^a^,^b^,^*()

a 福建师范大学化学与材料学院福州 350007
b 中国科学院福建物质结构研究所中国科学院功能纳米结构设计与组装重点实验室福建省纳米材料重点实验室结构化学国家重点实验室福州 350002

投稿日期:2021-12-31 发布日期:2022-02-17
通讯作者: 黄萍, 陈学元
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
中国科学院青年创新促进会专项(2020305); 国家自然科学基金(12174391); 国家自然科学基金(U1805252); 国家自然科学基金(21875250); 国家自然科学基金(12074379); 国家自然科学基金(12104456); 福建省自然科学基金对外合作项目(2020I0037)

Polarized Upconversion Luminescence from a Single NaYF₄:Yb³⁺/Er³⁺ Microrod for Orientation Tracking^※

Xiaoke Hu^a^,^b, Xiaoying Shang^b, Ping Huang^a^,^b(), Wei Zheng^a^,^b, Xueyuan Chen^a^,^b()

a College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007
b State Key Laboratory of Structural Chemistry, Fujian Key Laboratory of Nanomaterials, CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences, Fuzhou 350002

Received:2021-12-31 Published:2022-02-17
Contact: Ping Huang, Xueyuan Chen
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
Youth Innovation Promotion Association of the Chinese Academy of Sciences(2020305); National Natural Science Foundation of China(12174391); National Natural Science Foundation of China(U1805252); National Natural Science Foundation of China(21875250); National Natural Science Foundation of China(12074379); National Natural Science Foundation of China(12104456); Natural Science Foundation of Fujian Province(2020I0037)

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1. Supporting Information-A21120618.pdf(1929KB)

摘要/Abstract

稀土掺杂微/纳材料的偏振上转换发光在单颗粒示踪和生物医学等领域具有广泛的应用前景. 稀土离子的偏振上转换发光主要取决于其局域态的电子结构和激发态动力学. 利用单颗粒偏振上转换光学测试平台对β-NaYF₄:Yb³⁺/ Er³⁺微米棒的偏振上转换发光进行了系统研究. 随发射偏振角的变化, 单个微米棒的上转换发光强度发生周期性改变, 且来自Er³⁺同一光谱支项的不同晶体场子能级跃迁的偏振方向不同. 与光谱支项整体的上转换发光相比, 其晶体场子能级上转换发光表现出更大的发射偏振度. 利用Er³⁺高度偏振的晶体场跃迁谱线, 实现了对单个微米棒空间取向的动态分析, 揭示了NaYF₄:Yb³⁺/Er³⁺微米棒作为偏振各向异性的上转换荧光探针在单颗粒取向示踪方面的潜在应用.

关键词: 稀土, 上转换发光, 偏振各向异性, 单颗粒, 晶体场跃迁

Polarized upconversion luminescence (UCL) of lanthanide (Ln³⁺)-doped micro/nano-crystals has shown great promise in areas such as single-particle tracking and biomedicine. The polarized UCL of Ln³⁺ ions is governed by their localized electronic structures and excited-state dynamics. In this work, β-NaYF₄:Yb³⁺/Er³⁺ microrods with controllable morphologies and sizes were synthesized through a solvothermal method. Based on the customized confocal laser microscopic system, the polarized UCL of a single β-NaYF₄:Yb³⁺/Er³⁺ microrod was systematically investigated. The emission polarization was probed by placing a half-wave plate coupled with a polarizer in front of the detector. As such, the polarized UCL spectra of a single NaYF₄:Yb³⁺/Er³⁺ microrod can be recorded by rotating the half-wave plate under 980-nm excitation. It was observed that the UCL intensity of the microrod exhibited a periodic variation with the emission polarization angle tuning from 0° to 360°, indicating polarization anisotropy of the microrod. Specifically, different crystal-field (CF) transition lines originating from two identical multiplets of Er³⁺ displayed drastically distinct polarization dependence. This results in a higher degree of polarization (DOP) of the UCL intensity for a certain CF transition of Er³⁺ in comparison with that of the integrated UCL intensity of the multiplet. Polar plots of the UCL intensities for the CF transitions of Er³⁺ as a function of polarization angle could provide a qualitative vision of the DOP, with a narrower “neck” indicative of a larger DOP. Moreover, the polar plots of a certain CF transition of Er³⁺ showed a consistent orientation with the corresponding NaYF₄:Yb³⁺/ Er³⁺ microrod and rotated with the rotating of the single microrod. Therefore, by utilizing the polar plots of the highly-polarized CF transition lines of Er³⁺, the spatial orientations of the microrod could be monitored, thus revealing the great potential of NaYF₄:Yb³⁺/Er³⁺ microrods as sensitive anisotropic UCL probes for single-particle tracking.

Key words: rare earth, upconversion luminescence, polarization anisotropy, single particle, crystal-field transition

引用此文

胡晓柯, 商晓颖, 黄萍, 郑伟, 陈学元. NaYF₄:Yb³⁺/Er³⁺单颗粒微米棒偏振上转换发光及其取向示踪^※[J]. 化学学报, 2022, 80(3): 244-248.

Xiaoke Hu, Xiaoying Shang, Ping Huang, Wei Zheng, Xueyuan Chen. Polarized Upconversion Luminescence from a Single NaYF₄:Yb³⁺/Er³⁺ Microrod for Orientation Tracking^※[J]. Acta Chimica Sinica, 2022, 80(3): 244-248.

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图/表 4

图1. NaYF4:Yb3+/Er3+微米棒的(a)透射电镜照片(插图为相应的高分辨透射电镜照片)、(b) X射线粉末衍射谱图、(c)单个微米棒的元素分析面扫和(d) X射线能谱

Figure 1. (a) TEM image (inset shows the high-resolution TEM image), (b) XRD pattern, (c) elemental mappings and (d) EDS of NaYF4:Yb3+/Er3+ microrods

图2. (a)微米棒取向示意图和发射偏振角θ定义、(b) 980-nm线偏振激光(功率为2 W)激发下, NaYF4:Yb3+/Er3+微米棒聚集态的上转换光谱、(c)不同偏振角θ (0°到360°)采集得到的NaYF4:Yb3+/Er3+微米棒聚集态的偏振上转换光谱(插图为微米棒聚集态的上转换发光照片)和(d)微米棒聚集态Er3+晶体场子能级跃迁的上转换发光强度(按最大值归一化)随θ变化的极坐标曲线

Figure 2. (a) Schematic illustration of the microrod orientation and the definition of the emission polarization angle (θ), (b) UCL spectrum of NaYF4:Yb3+/Er3+ microrod aggregates under excitation with a 980-nm linearly polarized laser (at a power of 2 W), (c) polarized UCL spectra of NaYF4:Yb3+/Er3+ microrod aggregates obtained by varying the emission polarization angle (θ) from 0° to 360° (The inset shows the UCL image of the microrod aggregates) and (d) polar plots of the UCL intensities (normalized at their maxima) for the CF transitions of Er3+ as a function of θ

图3. (a) 980-nm线偏振激光(功率为2 W)激发下, 不同偏振角θ (0°到360°)采集得到的NaYF4:Yb3+/Er3+单个微米棒的偏振上转换光谱(插图为单个微米棒的上转换发光照片)、(b)单个NaYF4:Yb3+/Er3+微米棒Er3+晶体场子能级上转换发光强度(按最大值归一化)随θ变化的极坐标曲线、(c) Er3+的4F9/2→4I15/2跃迁的偏振上转换光谱随θ(从0°到90°)的变化和(d) Er3+的4F9/2→4I15/2跃迁的上转换发光积分强度随θ变化的极坐标曲线

Figure 3. (a) Polarized UCL spectra of a single NaYF4:Yb3+/Er3+ microrod obtained by varying the polarization angle (θ) from 0° to 360° upon excitation with a 980-nm linearly polarized laser (power: 2 W) (The inset shows the UCL image of a single microrod), (b) polar plots of the UCL intensities (normalized at their maxima) for the CF transitions of Er3+ of a single NaYF4:Yb3+/Er3+ microrod from the 4F9/2 multiplet to the 4I15/2 ground state as a function of θ, (c) polarized UCL spectra of Er3+ from 4F9/2 to 4I15/2 obtained by varying the emission polarization angle (θ) from 0° to 90° and (d) polar plot of the integrated UCL intensity for the 4F9/2→4I15/2 transition of Er3+ as a function of θ

图4. (a) 980-nm线偏振激光激发下, 不同取向NaYF4:Yb3+/Er3+单个微米棒的偏振上转换光谱(插图为四个不同取向微米棒的上转换发光照片. 白色和红色箭头分别代表偏振片和微米棒c-轴的方向)、(b)四个不同取向微米棒Er3+晶体场能级跃迁位于653.60 nm处的上转换发光强度随偏振角θ变化的极坐标曲线、(c)不同取向微米棒Er3+晶体场能级跃迁位于653.60 nm处的上转换发光强度随θ的变化和(d)四个不同取向的微米棒Er3+晶体场能级跃迁位于653.60和661.40 nm处的上转换发光强度比值随θ变化的极坐标曲线

Figure 4. (a) Polarized UCL spectra for a single NaYF4:Yb3+/Er3+ microrod at different spatial orientations upon excitation with a 980-nm linearly polarized laser (The insets show the corresponding UCL images of the microrod at different orientations. The white and red arrows denote the directions of the polarizer and the microrod c-axis, respectively), (b) polar plots of the UCL intensities of Er3+ at 653.60 nm for the four orientations of the microrod as a function of θ, (c) UCL intensities of Er3+ at 653.60 nm for the four orientations of the microrod as a function of θ and (d) polar plots of the UCL intensity ratio between the CF transitions of Er3+ at 653.60 and 661.40 nm for the four orientations of the microrod as a function of θ

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NaYF₄:Yb³⁺/Er³⁺单颗粒微米棒偏振上转换发光及其取向示踪^※

Polarized Upconversion Luminescence from a Single NaYF₄:Yb³⁺/Er³⁺ Microrod for Orientation Tracking^※

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