Enhancement mechanism of red up-conversion emission in single NaYbF4:2%Er3+@NaYbF4 micron core-shell structure

Yan Xue-Wen; Zhang Jing-Lei; Zhang Zheng-Yu; Ding Peng; Han Qing-Yan; Zhang Cheng-Yun; Gao Wei; Dong Jun

doi:10.7498/aps.73.20231663

Abstract

The construction of core-shell structure can effectively reduce the quenching effect on the surface of material and regulate ion-ion interaction, which has become one of the effective ways to enhance and regulate the spectral characteristics of rare-earth upconversion luminescent materials. In this paper, a variety of NaYbF₄: 2%Er³⁺ micron core-shell structures are constructed with the help of epitaxial growth technology, effectively improving the red up-conversion emission of Er³⁺ ions. The prepared microcrystals with core-shell structures are of hexagonal phase microdisks, and their sizes are relatively uniform. In order to better obtain the material spectral data, a confocal microscopic spectroscopy is used to study spectral properties. Under 980 nm near-infrared laser excitation, the red emission intensity of single NaYbF₄:2%Er³⁺@NaYbF₄@NaYF₄ core-shell-shell microdisk is 4.6 times higher than that of NaYbF₄:2%Er³⁺ micron disk, and the red-to-green ratio increases from 6.3 to 8.1. Meanwhile, Ho³⁺ ions are introduced into the NaYbF₄:2%Er³⁺@NaYbF₄: 2%Ho³⁺ @NaYF₄ core-shell-shell microdisk, and the red emission intensity is nearly 6.7 times higher than that of single NaYbF₄: 2%Er³⁺ microdisk, and the red-to-green ratio increases from 6.3 to 9.4 through the interaction between ions. The microcrystal spectral characteristics and luminescence kinetics of different core-shell structures are studied, showing that the red emission enhancement of Er³⁺ ions is mainly derived from the construction of different core-shell structures, which can effectively enhance the cross-relaxation between Er³⁺ ions, the energy back transfer between Yb³⁺ and Er³⁺ ions, and the energy transfer from Ho³⁺ ions to Er³⁺ ions. The micron core-shell structures with efficient red emission in this study has great application prospects in the fields of luminescence, anti-counterfeiting and optoelectronic devices.

Keywords:

Authors and contacts

School of Electronic Engineering, Xi’an University of Posts and Telecommunications, Xi’an 710121, China

Corresponding author: Gao Wei, gaowei@xupt.edu.cn ; Dong Jun, dongjun@xupt.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 12274341, 12004304, 12104366), the Key R & D Plan of Shaanxi Province, China (Grant Nos. 2022SF-333, 2023-YBGY-256), the Natural Science Foundation of Shaanxi Province, China (Grant No. 2022JZ-05), the Youth Program of the Natural Science Foundation of Shaanxi Province, China (Grant No. 2022JQ-041), the Education Department Service Local Special Program of Shaanxi Province, China (Grant No. 22JC057), and the Xi’an University Talents Service Enterprise Project, China (Grant No. 23GXFW0089).

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References

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Cited By

图 1 基于NaYbF₄:2%Er³⁺微米晶体构建的不同核壳结构模型及其相应的能量传递示意图

Figure 1. Schematic diagram of different core-shell structures based on NaYbF₄:2%Er³⁺ micron crystals and their corresponding energy transfer.

DownLoad: Full-Size Img PowerPoint

图 2 NaYbF₄:2%Er³⁺微米晶体及包覆不同核壳结构的XRD图

Figure 2. The XRD patterns of NaYbF₄:2%Er³⁺microcrystals and their coating with different core-shell (CS) structures.

DownLoad: Full-Size Img PowerPoint

图 3 (a)—(f) NaYbF₄:2%Er³⁺微米晶体及其包覆不同壳层核壳结构的SEM图, (a1)—(f1)为其相应的元素映射图

Figure 3. (a)–(f) SEM image of NaYbF₄:2%Er³⁺ microcrystals and coating with different CS structures. (a1)–(f1) The corresponding element maps

DownLoad: Full-Size Img PowerPoint

图 4 在980 nm激发下, 单个NaYbF₄:2%Er³⁺微米盘及其包覆不同壳层微米盘的 (a)上转换发射光谱(插图为对应发光图案), (b) 红绿比及(c) 红光发射强度的增强倍数

Figure 4. (a) The UC emission spectra (the insert is corresponding optical micrographs), (b) R/G ratio and (c) enhancement factor of the red emission of the NaYbF₄:2%Er³⁺ microcrystals and coating with different CS structures under the excitation of a 980 nm NIR laser.

DownLoad: Full-Size Img PowerPoint

图 5 在近红外光980 nm激光激发下, 单个NaYbF₄:2%Er³⁺微米盘及掺杂2%Ho³⁺离子的不同核壳结构的　(a)上转换发射光谱(插图为对应发光图案), (b)红绿比及(c)红光发射强度的增强倍数

Figure 5. (a) The UC emission spectra (the insert is corresponding optical micrographs), (b) R/G ratio and (c) enhancement factor of the red emission of the NaYbF₄:2%Er³⁺ microcrystals and coating with different CS structures with doping 2%Ho³⁺ ions under the excitation of a 980 nm NIR laser.

DownLoad: Full-Size Img PowerPoint

图 6 在980 nm不同泵浦功率激发下, 单颗粒NaYbF₄:2%Er³⁺, NaYbF₄:2%Er³⁺@NaYbF₄:2%Ho³⁺ 与NaYbF₄:2%Er³⁺@NaYbF₄@NaYF₄核-壳-壳结构微米盘的上转换发射光谱(插图为其对应发光图案)及其红、绿光发射依赖关系

Figure 6. Under different pump power excitation at 980 nm, the upconversion emission spectra of a single particle NaYbF₄:2%Er³⁺, NaYbF₄:2%Er³⁺@NaYbF₄:2%Ho³⁺, and NaYbF₄:2%Er³⁺@NaYbF₄ @ NaYF₄ core-shell-shell micron disks (the corresponding luminescence pattern is inset) and their red and green emission dependencies.

DownLoad: Full-Size Img PowerPoint

图 7 在980 nm激光激发下, 不同结构中Yb³⁺, Er³⁺及Ho³⁺离子间的能量传递及其可能的跃迁机理图

Figure 7. Diagram of energy transfer between Yb³⁺, Er³⁺ and Ho³⁺ ions in different structures and their possible transition mechanisms under 980 nm laser excitation.

DownLoad: Full-Size Img PowerPoint

图 8 在近红外光980 nm脉冲激光激发下, NaYbF₄:2%Er³⁺微米盘及不同核壳结构中Er³⁺离子在⁴F_9/2激发态能级(654 nm)处的发光寿命衰减曲线

Figure 8. Luminescence lifetime attenuation curve of Er³⁺ ions at⁴F_9/2 excited state level (654 nm) in NaYbF₄:2%Er³⁺ microdisks and different core-shell structures under near-infrared 980 nm pulsed laser excitation.

DownLoad: Full-Size Img PowerPoint

[1]	Suo H, Zhu Q, Zhang X, Chen B 2021 Mater. Today Phys. 21 100520 Google Scholar
[2]	Liu S B, Yan L, Li Q Q, Huang J S, Tao L L, Zhou B 2020 Chem. Eng. J. 397 125451 Google Scholar
[3]	Zhang C Y, Ji M, Zhou X L, Mi X H, Chen H, Zhang B B, Fu Z K, Zhang Z L 2023 Adv. Funct. Mater. 33 2208561 Google Scholar
[4]	Zhuang Y X, Chen D R, Chen W J, Zhang W X, Su X, Deng R R, An Z F 2021 Light-Sci. Appl. 10 132 Google Scholar
[5]	Xiang Y, Zheng S S, Yuan S S, Wang J, Wu Y H, Zhu X H 2022 Mikrochim. Acta 189 120 Google Scholar
[6]	Zhang Z J, Han Q Y, Lau J W, Xing B G 2020 ACS Mater. Lett. 2 1516 Google Scholar
[7]	Chihara T, Umezawa M, Miyata K 2019 Sci. Rep. 9 12806 Google Scholar
[8]	Jiang T, Qin W P, Zhou J 2014 J. Alloys Compd. 593 79 Google Scholar
[9]	Venkataramanan Mahalingam, Chanchal Hazra, Rafik Naccache, Fiorenzo Vetroneb 2013 J. Mater. Chem. C 1 6536 Google Scholar
[10]	何恩节, 郑海荣, 高伟, 鹿盈, 李俊娜, 魏映, 王灯, 朱刚强 2013 物理学报 62 237803 Google Scholar He E J, Zheng H R, Gao W, Lu Y, Li J N, Wei Y, Wang D, Zhu G Q 2013 Acta Phys. Sin 62 237803 Google Scholar
[11]	Sheng W, Yan L, Tan Y Y, Zhao Y, Huang H Z, Zhou B 2023 Adv. Photonics Res. 4 2300172 Google Scholar
[12]	Wang Z J, Lin S B, Liu Y J, Hou J, Xu X Y, Zhao X 2022 Nanomaterials 12 3288 Google Scholar
[13]	Gao W, Sun Z Y, Han Q Y, Han S S, Cheng X T, Wang Y K, Yan X W, Dong J 2021 J. Alloys Compd. 857 157578 Google Scholar
[14]	Sun Y Z, Bi H F, Wang T, Li Z X, Song H N, Sun F L, Zhou G J 2020 Mater. Sci. Eng. , C 261 114674 Google Scholar
[15]	Peng Y H, Peng J C, Han J J, Wang T H, Yin Z Y, Qiu J B, Wang Q, Yang Z W 2020 J. Rare Earths 38 577 Google Scholar
[16]	Gao D L, Zhang X Y, Gao W 2013 ACS Appl. Mater. Interfaces 5 9732 Google Scholar
[17]	Gao W, Zhang C X, Han Q Y, Lu Y R, Yan X W, Wang Y K, Yang Y, Liu J H, Dong J 2022 J. Lumin. 241 118501 Google Scholar
[18]	Zhao J Y, Sun Y J, Kong X G, Tian L J, Wang Y, Tu L P, Zhao J L, Zhang H 2008 J. Phys. Chem. B 112 15666 Google Scholar
[19]	Chen Y S, Zhou J P, Jiao Y C, He W, Wang H H, Hao X L, Lu J X, Yang S E 2013 J. Lumin. 134 504 Google Scholar
[20]	Zhou Z Q, Xue J B, Zhang B P, Wang C, Yang X C, Fan W, Ying L Y, Zheng Z W 2021 Appl. Phys. Lett. 118 173301 Google Scholar
[21]	Zhang G, Dong H, Wang D, Sun L D, Yan C H 2017 J. Rare Earths 35 1 Google Scholar
[22]	高伟, 董军, 王瑞博, 王朝晋, 郑海荣 2016 物理学报 65 084205 Google Scholar Gao W, Dong J, Wang R B, Wang Z J, Zheng H R 2016 Acta Phys. Sin. 65 084205 Google Scholar
[23]	Gao D L, Zhang X Y, He E J 2013 J. Alloys Compd. 554 395 Google Scholar
[24]	M Pollnau, D. R. Gamelin, S. R. Lüthi, H. U. Güdel, M. P. Hehlen 2000 Phys. Rev. B 61 3337 Google Scholar
[25]	Xu F, Luo W, Li A H, Sun Z J 2023 J. Lumin. 253 119487 Google Scholar
[26]	Shang Y F, Hao S W, Lv W Q, Chen T, Tian L, Lei Z T, Yang C H 2018 J. Mater. Chem. C 6 3869 Google Scholar
[27]	Lee C, Park H, Kim W 2019 Phys. Chem. Chem. Phys. 21 24026 Google Scholar
[28]	Lin H, Xu D K, Chen Z Y, Li Y J, Xu L Q, Ma Y, Yang S H 2020 Appl. Surf. Sci. 514 146074 Google Scholar
[29]	Gao W, Xing Y, Chen B H, Shao L, Zhang J J, Yan X W, Han Q Y, Zhang C Y, Liu L, Dong J 2023 J. Alloys Compd. 936 168371 Google Scholar
[30]	Gao W, Wang B Y, Han Q Y, Gao L, Wang Z J, Sun Z Y, Zhang B, Dong J 2020 J. Alloys Compd. 818 152934 Google Scholar
[31]	Luwang M N, Ningthoujam R S, Srivastava S K, Vatsa R K 2011 J. Mater. Chem. 21 5326 Google Scholar
[32]	Cheng X W, Ge H, Wei Y, Huang L 2018 ACS Nano 12 10992 Google Scholar

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Enhancement mechanism of red up-conversion emission in single NaYbF₄:2%Er³⁺@NaYbF₄micron core-shell structure