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贾恒; 冯晓锐; 李大光; 秦伟平; 杨龙; 何伟艳; 马惠言; 滕英跃

doi:10.37188/CO.2022-0134

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doi: 10.37188/CO.2022-0134

贾恒 ^{1, 2,},
冯晓锐 ¹,
李大光 ²,
秦伟平 ^2,

,,
杨龙 ¹,
何伟艳 ¹,
马惠言 ¹,
滕英跃 ^1,

,

1.
内蒙古工业大学化工学院，内蒙古呼和浩特 010051
2.
吉林大学电子科学与工程学院集成光电子学国家重点联合实验室，吉林长春 130012

基金项目:国家自然科学基金项目（No. 12174150，No. 11774132，No. 21766023）；内蒙古科技计划项目（No. 2019GG268）；内蒙古自治区高等学校科学研究项目（No. NJZZ23073）；内蒙古工业大学科学研究项目（No. ZZ202108）；内蒙古工业大学科研启动金项目(No. DC2200000916)

详细信息

作者简介:
贾　恒（1990—），男，山西阳高人，博士，内蒙古工业大学教师，硕士生导师，2021年于吉林大学获得博士学位，主要从事稀土光电功能材料、上转换发光调控及应用等方面的研究。E-mail：[email protected]

秦伟平（1961—），男，江苏南通人，吉林大学电子科学与工程学院、集成光电子国家重点联合实验室教授，博士生导师，1984年于清华大学工程物理系获得学士学位，1999年于中国科学院长春物理研究所获得博士学位，主要从事先进光子学材料与器件、固体发光学、稀土纳米发光材料、光频上转换发光、红外光光催化、多离子合作量子跃迁、科学创新理论与创新学等方面的研究，2010年荣获吉林省科学技术进步一等奖，2011年荣获国家自然科学奖二等奖，2016年荣获吉林省自然科学奖一等奖，主持并完成各类科研项目30余项，发表SCI论文300余篇，获专利授权40余件，H因子61，2014~2021年连续8年进入Elsevier发布的中国高被引学者榜单。E-mail：[email protected]

滕英跃（1976—），男，山东掖县人，博士，内蒙古工业大学教授，硕士生导师，1998年于内蒙古工业大学化工学院硅酸盐专业任教，2014年至今任化工学院无机非金属材料工程系主任，长期从事非金属材料、褐煤应用等方面的研究，主持国家及自治区科研项目3项，企业横向合作项目1项，校级优秀教学团队负责人，荣获内蒙古工业大学教学成果一等奖、三等奖各1次，发表文章10余篇，授权发明专利2项。E-mail：[email protected]

中图分类号:O433; O614.33
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- 收稿日期: 2022-06-16
- 录用日期: 2022-08-03
- 修回日期: 2022-07-07
- 网络出版日期: 2022-08-03

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JIA Heng ^{1, 2
,},
FENG Xiao-rui ¹,
LI Da-guang ²,
QIN Wei-ping ^{2
,,},
YANG Long ¹,
HE Wei-yan ¹,
MA Hui-yan ¹,
TENG Ying-yue ^{1
,,}

1.
College of Chemical Engineering, Inner Mongolia University of Technology, Huhhot 010051, China
2.
State Key Laboratory on Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun 130012, China

Funds:Supported by National Natural Science Foundation of China (No. 12174150, No. 11774132, No.21766023); Plan of Scientific and Technology of Inner Mongolia (No. 2019GG268); Scientific Research Project of Colleges and Universities in Inner Mongolia Autonomous Region (No. NJZZ23073); Research Project of Inner Mongolia University of Technology (No. ZZ202108); Scientific Research Startup Fund of Inner Mongolia University of Technology (No. DC2200000916)

More Information

Corresponding author: [email protected]; [email protected]

摘要

摘要:
稀土掺杂的上转换发光纳米材料在信息安全、生物医学、光纤通信、显示和能源等众多领域有着巨大的应用潜力，受到了相关各领域研究人员的广泛关注。特别是近年来发展起来的具有正交激发发射特性的上转换发光纳米颗粒，其可在不同的激发条件下产生动态变化的光色输出，因而具备一系列新的特性与功能，大大地扩展了应用范围。本文综述稀土离子正交上转换发光的发展历程，系统论述了基于核壳结构的正交激发发射体系的设计原理和构建方法，介绍了其在信息存储、安全防伪、显示、传感、生物成像及治疗等领域的最新研究进展，并探讨了未来相关研究中可能面临的机遇和挑战。
- 稀土 /
- 纳米材料 /
- 正交上转换发光 /
- 核壳结构 /
- 正交激发发射体系
Abstract:
Rare earth-doped upconversion luminescence nanomaterials have received considerable attention from researchers due to their great potential for applications in many fields such as information security, biomedicine, optical fiber communication, digital displays, and energy. The recently-developed upconversion luminescence nanoparticles with orthogonal excitation-emission properties have attracted especially strong research interest because their distinct luminescence outputs can be dynamically modulated by switching the excitation conditions. The orthogonal luminescence properties further endow such nanocrystals with a set of new features and functionalities, which largely expands their potential applications. This review summarizes the progress in the development of orthogonal upconversion luminescence of rare earth ions, and provides a systematic discussion on design principles and construction strategies of orthogonal excitation-emission systems based on core-shell structures, as well as introduces their recent advances in various fields of applications including data storage, security anti-counterfeiting, digital displays, sensing, bioimaging and therapy. Furthermore, the prospective opportunities and challenges in the future research of orthogonal luminescence systems are also provided.
- rare earth /
- nanomaterials /
- orthogonal upconversion luminescence /
- core-shell structure /
- orthogonal excitation-emission systems

HTML全文

图 1 二元正交激发发射体系的结构设计示意图

Figure 1. Schematic diagram of structure design for binary orthogonal excitation-emission systems

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图 2 基于正交双色上转换发光的二元正交激发发射体系。(a)具有蓝-绿双色正交发光的四层核壳纳米结构NaGdF₄:Yb/Tm@NaGdF₄@NaYbF₄:Nd@Na(Yb,Gd)F₄:Ho@NaGdF₄示意图和在980/808 nm二元激发下的发射光谱及对应的发光照片^{[
41
]}；(b) 蓝-绿双色正交发光的NaYF₄: Nd/Yb/Tm@NaYF₄:Nd@NaYF₄@NaYF₄:Yb /Er三层核壳结构示意图和在980/808 nm二元激发下的发射光谱及对应的发光照片^{[
33
]}；(c)具有不依赖于激发功率密度的高色纯度蓝-绿双色正交发射的NaGdF₄:Yb,Er@NaYF₄:Yb@NaGdF₄:Yb,Nd@NaYF₄@NaGdF₄: Yb,Tm@NaYF₄五层核壳结构示意图和在980/796 nm二元激发下的发射光谱及对应的发光照片^{[
42
]}；(d)具有不同中间NaYF₄纳米壳层厚度的NaGdF₄:Yb,Er@NaYF₄@NaYF₄:Yb,Tm@NaYbF₄:Nd@NaYF₄四层核壳结构在808/980 nm二元激发下的发射光谱^{[
43
]}。(a)转载自文献[ 41 ]，版权所有（2013）威立出版集团; (b)转载自文献[ 33 ]，版权所有（2014）威立出版集团; (c)转载自文献[ 42 ]，版权所有（2016）威立出版集团; (d)转载自文献[ 43 ]，版权所有（2017）美国化学学会

Figure 2. Binary orthogonal excitation-emission systems for orthogonal dual-color upconversion luminescence. (a) Schematic illustration of core/quadruple-shell NaGdF₄:Yb/Tm@NaGdF₄@NaYbF₄:Nd@Na(Yb,Gd)F₄:Ho@NaGdF₄ with blue-green dual-color orthogonal luminescence and its corresponding emission spectra and photographs under 980/808 nm binary excitations^{[
41
]}; (b) schematic illustration of core/triple-shell NaYF₄:Nd/Yb/Tm@NaYF₄:Nd@NaYF₄@NaYF₄:Yb/Er with blue-green dual-color orthogonal luminescence and its corresponding emission spectra and photographs under 980/808 nm binary excitations^{[
33
]}; (c) schematic illustration of core/quintuple-shell NaGdF₄:Yb,Er@NaYF₄:Yb@NaGdF₄:Yb,Nd@NaYF₄@NaGdF₄:Yb,Tm@NaYF₄ with excitation power density-independent blue-green high-pure dual-color orthogonal luminescence and its corresponding emission spectra and photographs under 980/796 nm binary excitations^{[
42
]}; (d) emission spectra of core/quadruple-shell NaGdF₄:Yb,Er@NaYF₄@NaYF₄:Yb, Tm@NaYbF₄:Nd@NaYF₄ with varied thickness of an NaYF₄ interlayer under 808/980 nm binary excitations^{[
43
]}. (a) Reproduced with permission ref. [ 41 ]. Copyright 2013, Wiley-VCH; (b) reproduced with permission ref. [ 33 ]. copyright 2014, Wiley-VCH; (c) reproduced with permission ref. [ 42 ]. copyright 2016, Wiley-VCH; (d) reproduced with permission ref. [ 43 ]. copyright 2017, American Chemical Society.

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图 3 正交双色发射的二元正交激发发射体系。(a)基于敏化剂Er³⁺的绿-蓝双色正交发射NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm@NaYF₄三层核壳纳米结构示意图和在1532/980 nm二元激发下的发射光谱及对应的发光照片^{[
44
]}；(b)基于NaErF₄:Tm红光发射核的多层核壳纳米结构示意图和在1550 nm和980/808 nm二元激发下的发光照片^{[
20
]}；(c) 基于Er³⁺自敏化的蓝-绿双色正交发射NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm双层核壳纳米结构示意图和在808/940 nm二元激发下的发射光谱^{[
45
]}；(d) 基于NaErF₄红光发射核的红-蓝双色正交发射NaErF₄@NaYF₄@NaYbF₄:Tm@NaYF₄三层核壳纳米结构示意图和在800/980 nm二元激发下的发射光谱及对应的发光照片^{[

46
]}；(e)基于单发光层的红-绿双色正交发射NaErF₄:Yb/Tm@NaYF₄:Yb@NaNdF₄:Yb双层核壳纳米结构示意图和在980/808 nm二元激发下的发射光谱及对应的发光照片^{[
47
]}；(f) 基于单发光层的二元正交激发发射体系(NaYF₄:Yb/Er/Mn@NaYF₄:Yb@NaNdF₄:Yb)示意图和在980/808 nm二元激发下的发射光谱及对应的发光照片^{[
49
]}。(a)转载自文献[ 44 ]，版权所有（2018）威立出版集团; (b)转载自文献[ 20 ]，版权所有（2019）威立出版集团; (c)转载自文献[ 45 ]，版权所有（2018）皇家化学学会; (d)转载自文献[ 46 ]，版权所有（2018）美国化学学会; (e)转载自文献[ 47 ]，版权所有（2019）自然出版集团; (f)转载自文献[ 49 ]，版权所有（2020）威立出版集团

Figure 3. Binary orthogonal excitation-emission systems with orthogonal dual-color emissions. (a) Schematic illustration of Er³⁺ sensitizer-based core/triple-shell NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm@NaYF₄ with green-blue dual-color orthogonal emissions and its corresponding emission spectra and photographs under 1532/980 nm binary excitations^{[
44
]}; (b) schematic illustration of red-emitting NaErF₄:Tm core-based multilayer core-shell nanostructures and their corresponding photographs under 1550 nm and 980/808 nm binary excitations^{[
20
]}; (c) schematic illustration of self-sensitization of Er³⁺-based core/double-shell NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm with blue-green dual-color orthogonal emissions and its corresponding emission spectra under 808/940 nm binary excitations^{[
45
]}; (d) schematic illustration of red-emitting NaErF₄ core-based core/triple-shell NaErF₄@NaYF₄@NaYbF₄:Tm@NaYF₄ with red-blue dual-color orthogonal emissions and its corresponding emission spectra and photographs under 808/980 nm binary excitations^{[
46
]}; (e) schematic illustration of a single-emissive layer-based core/double-shell NaErF₄:Yb/Tm@NaYF₄:Yb@NaNdF₄:Yb with red-green dual-color orthogonal emissions and its corresponding emission spectra and photographs under 980/808 nm binary excitations^{[
47
]}; (f) schematic illustration of a single-emissive layer-based binary orthogonal excitation-emission systems (NaYF₄:Yb/Er/Mn@NaYF₄:Yb@NaNdF₄:Yb) and its corresponding emission spectra and photographs under 980/808 nm binary excitations^{[
49
]}. (a) Reproduced with permission ref. [ 44 ]. Copyright 2018, Wiley-VCH; (b) reproduced with permission ref. [ 20 ]. Copyright 2019, Wiley-VCH; (c) reproduced with permission ref. [ 45 ]. Copyright 2018, Royal Society of Chemistry; (d) reproduced with permission ref. [ 46 ]. Copyright 2018, American Chemical Society; (e) reproduced with permission ref. [ 47 ]. Copyright 2019, Nature Publishing Group; (f) reproduced with permission ref. [ 49 ]. Copyright 2020, Wiley-VCH

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图 4 三元正交激发发射体系的结构设计示意图

Figure 4. Schematic diagram of structure design for ternary orthogonal excitation-emission systems

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图 5 基于正交三基色上转换发光的三元正交激发发射体系。(a)具有不依赖于激发功率密度的高色纯度红-绿-蓝三基色正交发光的NaYF₄:Yb/Tm@NaYF₄@NaYF₄:Er/Ho@NaYF₄@NaYF₄:Nd/Yb/Er@NaYF₄:Nd五层核壳纳米结构示意图和在1560/808/980 nm三元激发下的发射光谱及对应的发光照片^{[
52
]}；(b) 具有不依赖于激发功率密度的正交三基色发光的LiYbF₄:Tm@LiGdF₄@LiGdF₄:Yb/Er@LiYF₄:Nd/Yb@LiGdF₄@LiErF₄:Tm@LiGdF₄六层核壳纳米结构示意图和在1532/980/800 nm三元激发下的发射光谱及对应的发光照片^{[
59
]}；(c)具有不依赖于激发功率密度的正交三基色发光的NaErF₄@NaYF₄@NaGdF₄:Yb/Er@NaGdF₄:Yb@NaGdF₄:Nd/Yb@NaYF₄@NaGdF₄:Yb/Tm@NaYF₄七层核壳纳米结构示意图和在1532/808/980 nm三元激发下的发射光谱及对应的发光照片^{[
60
]}。 (a)转载自文献[ 52 ]，版权所有（2021）美国化学学会; (b)转载自文献[ 59 ]，版权所有（2021）美国化学学会; (c)转载自文献[ 60 ]，版权所有（2021）自然出版集团

Figure 5. Ternary orthogonal excitation-emission systems for orthogonal three-primary-color upconversion luminescence. (a) Schematic illustration of core/quintuple-shell NaYF₄:Yb/Tm@NaYF₄@NaYF₄:Er/Ho@NaYF₄@NaYF₄:Nd/Yb/Er@NaYF₄:Nd with excitation power density-independent red-green-blue high-pure three-primary-color orthogonal emissions and its corresponding emission spectra and photographs under 1560/808/980 nm ternary excitations^{[
52
]}; (b) schematic illustration of core/sextuple-shell LiYbF₄:Tm@LiGdF₄@LiGdF₄:Yb/Er@LiYF₄:Nd/Yb@LiGdF₄@LiErF₄:Tm@LiGdF₄ with excitation power density-independent orthogonal three-primary-color luminescence and its corresponding emission spectra and photographs under 1532/980/800 nm ternary excitations^{[
59
]}; (c) transmission electron microscopy image and schematic illustration of core/septuple-shell NaErF₄@NaYF₄@NaGdF₄:Yb/Er@NaGdF₄:Yb@NaGdF₄:Nd/Yb@NaYF₄@NaGdF₄:Yb/Tm@NaYF₄ with excitation power density-independent orthogonal three-primary-color luminescence and its corresponding emission spectra and photographs under 1532/808/980 nm ternary excitations^{[

60
]}. (a) Reproduced with permission ref. [ 52 ]. Copyright 2021, American Chemical Society; (b) reproduced with permission ref. [ 59 ]. Copyright 2021, American Chemical Society; (c) reproduced with permission ref. [ 60 ]. Copyright 2021, Nature Publishing Group.

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图 6 正交激发发射体系的应用领域

Figure 6. Applications of orthogonal excitation-emission systems

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图 7 正交激发发射体系在光学存储、安全防伪及显示领域的应用。(a)二元正交激发发射体系用于近红外光驱动下的光学数据存储^{[
44
]}；(b)二元正交激发发射体系用于多级防伪^{[
42
]}；(c)三元正交激发发射体系用于信息的加密与解密^{[
52
]}；(d)三元正交激发发射体系用于高级防伪^{[

58
]}；(e)二元正交激发发射体系用于多维度防伪^{[
43
]}；(f)三元正交激发发射体系用于二维彩色显示^{[
59
]}。(a)转载自文献[ 44 ]，版权所有（2018）威立出版集团; (b)转载自文献[ 42 ]，版权所有（2016）威立出版集团; (c)转载自文献[ 52 ]，版权所有（2021）美国化学学会；(d)转载自文献[ 58 ]，版权所有（2022）美国化学学会；(e)转载自文献[ 43 ]，版权所有（2017）美国化学学会；(f)转载自文献[ 59 ]，版权所有（2021）美国化学学会

Figure 7. Typically applications of orthogonal excitation-emission systems in the fields of optical storage, security anticounterfeiting and displays. (a) Binary orthogonal excitation-emission system for NIR-guided optical data storage^{[
44
]}; (b) binary orthogonal excitation-emission system for multi-level anti-counterfeiting^{[
42
]}; (c) ternary orthogonal excitation-emission system for information encryption and decryption^{[
52
]}; (d) ternary orthogonal excitation-emission system for advanced anti-counterfeiting^{[
58
]}; (e) binary orthogonal excitation-emission system for multi-dimensional anti-counterfeiting^{[
43
]}; (f) ternary orthogonal excitation-emission system for 2D color display^{[
59
]}. (a) Reproduced with permission ref. [ 44 ]. Copyright 2018, Wiley-VCH; (b) reproduced with permission ref. [ 42 ]. Copyright 2016, Wiley-VCH; (c) reproduced with permission ref. [ 52 ]. Copyright 2021, American Chemical Society; (d) reproduced with permission ref. [ 58 ]. Copyright 2022, American Chemical Society; (e) reproduced with permission ref. [ 43 ]. Copyright 2017, American Chemical Society; (f) reproduced with permission ref. [ 59 ]. Copyright 2021, American Chemical Society

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图 8 正交激发发射体系在传感及生物医学领域的应用。(a)二元正交激发发射体系用于对指纹内残留物TNT的检测^{[
49
]}；(b)二元正交激发发射体系用于对黄曲霉毒素B1的检测^{[
48
]}；(c)二元正交激发发射体系用于超分辨成像^{[
45
]}；(d) 二元正交激发发射体系用于成像引导的光动力/化疗联合治疗^{[
42
]}。(a)转载自文献[ 49 ]，版权所有（2020）威立出版集团; (b)转载自文献[ 48 ]，版权所有（2021）美国化学学会; (c)转载自文献[ 45 ]，版权所有（2021）皇家化学学会；(d)转载自文献[ 42 ]，版权所有（2016）威立出版集团

Figure 8. Typically applications of orthogonal excitation-emission systems in the fields of sensing and biomedicine. (a) Binary orthogonal excitation-emission system for the detection of TNT residues in the fingerprint^{[
49
]}; (b) binary orthogonal excitation-emission system for the detection of aflatoxin B1^{[
48
]}; (c) binary orthogonal excitation-emission system for super-resolution image^{[
45
]}; (d) binary orthogonal excitation-emission system for imaging-guided combined photodynamic therapy/ chemotherapy^{[
42
]}. (a) Reproduced with permission ref. [ 49 ]. Copyright 2020, Wiley-VCH; (b) reproduced with permission ref. [ 48 ]. Copyright 2021, American Chemical Society; (c) reproduced with permission ref. [ 45 ]. Copyright 2021, Royal Society of Chemistry; (d) reproduced with permission ref. [ 42 ]. Copyright 2016, Wiley-VCH.

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表 1 正交激发发射体系类型及研究进展与应用前景汇总

Table 1. Summary of system types, research progress and application prospects for orthogonal excitation-emission

Core-shell nanomaterials with orthogonal excitations-emissions	Orthogonal excitation type	Sensitizer-Activator	Luminescence color@ Excitation wavelength	Application fields	Reference/ PublicationYear
NaErF₄:Tm@NaYF₄@ NaYF₄:Yb/Ho@NaYF₄	Binary	Er³⁺-Tm³⁺/ Yb³⁺-Ho³⁺	Red@808/1550 nm Green@980 nm	—	[ 20 ] 2019
NaErF₄:Tm@NaYF₄@ NaYF₄:Yb/Tm@NaYF₄	Binary	Er³⁺-Tm³⁺/ Yb³⁺-Tm³⁺	Red@808/1550 nm Blue@980 nm	—	[ 20 ] 2019
NaYF₄:Nd/Yb/Tm@NaYF₄:Nd@ NaYF₄@NaYF₄:Yb/Er	Binary	Nd³⁺-Yb³⁺-Tm³⁺/ Yb³⁺-Er³⁺	UV/blue@808 nm Green@980 nm	Photo-switching	[ 33 ] 2014
NaGdF₄:Yb/Tm@NaGdF₄@NaYbF₄:Nd@Na(Yb,Gd)F₄:Ho@NaGdF₄	Binary	Yb³⁺-Tm³⁺/ Nd³⁺-Yb³⁺-Ho³⁺	UV/blue@980 nm Green@808 nm	—	[ 41 ] 2013
NaGdF₄:Yb,Er@NaYF₄:Yb@ NaGdF₄:Yb,Nd@NaYF₄@ NaGdF₄:Yb,Tm@NaYF₄	Binary	Nd³⁺-Yb³⁺-Er³⁺/ Yb³⁺-Tm³⁺	Green@796 nm UV/blue@980 nm	anticounterfeiting/PDT/CT	[ 42 ] 2016
NaGdF₄:Yb,Er@NaYF₄@ NaYF₄:Yb,Tm@NaYbF₄:Nd@NaYF₄	Binary	Yb³⁺-Er³⁺/ Nd³⁺-Yb³⁺-Tm³⁺	Green@980 nm UV/blue@808 nm	Fingerprint imaging	[ 43 ] 2017
NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm@NaYF₄	Binary	Er³⁺/ Yb³⁺-Tm³⁺	Green@1532 nm UV/blue@980 nm	Optical data storage	[ 44 ] 2018
NaYF₄:Er@NaYF₄@NaYF₄:Yb/Tm	Binary	Er³⁺/ Yb³⁺-Tm³⁺	Green@808 nm Blue@980 nm	Super-resolution image	[ 45 ] 2018
NaErF₄@NaYF₄@NaYbF₄:Tm @NaYF₄	Binary	Er³⁺/ Yb³⁺-Tm³⁺	Red@800 nm Blue@980 nm	Imaging-guided PDT	[ 46 ] 2018
NaErF₄:Yb/Tm@NaYF₄:Yb@ NaNdF₄:Yb	Binary	Er³⁺-Tm³⁺/ Nd³⁺-Yb³⁺-Er³⁺	Red@980 nm Green@808 nm	Photoactivation/detection	[ 47 , 48 ] 2019/2021
NaYF₄:Yb/Er/Mn@NaYF₄:Yb@ NaNdF₄:Yb	Binary	Yb³⁺-Er³⁺-Mn²⁺/Nd³⁺-Yb³⁺-Er³⁺	Red@980 nm Green@808 nm	Latent fingerprint sensing	[ 49 ] 2020
NaGdF₄:Yb,Er@NaYF₄@NaYF₄:Yb,Tm@NaYbF₄:Nd@NaYF₄	Binary	Yb³⁺-Er³⁺/ Nd³⁺-Yb³⁺-Tm³⁺	Green@980 nm UV/blue@808 nm	Tumor cell recognition/PDT	[ 50 ] 2020
NaErF₄:Yb/Tm@NaYbF₄	Binary	Er³⁺-Tm³⁺/ Yb³⁺-Er³⁺	Green@808 nm Red@980 nm	Information security	[ 51 ] 2021
NaYF₄:Yb/Tm@NaYF₄@NaYF₄:Er/Ho@NaYF₄@NaYF₄:Nd/Yb/Er@ NaYF₄:Nd	Ternary	Yb³⁺-Tm³⁺/ Er³⁺-Ho³⁺/ Nd³⁺-Yb³⁺-Er³⁺	UV/blue@980 nm Red@1560 nm Green@808 nm	Information Security/ anticounterfeiting	[ 52 - 54 , 55 - 58 ] 2021/2022
LiYbF₄:Tm@LiGdF₄@LiGdF₄:Yb/Er@LiYF₄:Nd/Yb@LiGdF₄@ LiErF₄:Tm@LiGdF₄	Ternary	Yb³⁺-Tm³⁺/ Nd³⁺-Yb³⁺-Er³⁺/ Er³⁺-Tm³⁺	UV/blue@980 nm Green@808 nm Red@1532 nm	2D full-color display	[ 59 ] 2021
NaErF₄@NaYF₄@NaGdF₄:Yb/Er@ NaGdF₄:Yb@NaGdF₄:Nd/Yb@ NaYF₄@ NaGdF₄:Yb/Tm@NaYF₄	Ternary	Er³⁺/ Nd³⁺-Yb³⁺-Er³⁺/ Yb³⁺-Tm³⁺	Red@1532 nm Green@808 nm Blue@980 nm	Neuronal population	[ 60 ] 2021
NaYF₄:Yb/Tm@NaYF₄:Yb/Nd@ NaLuF₄@NaYF₄:Yb/Er@NaLuF₄@ NaErF₄:Tm@NaLuF₄	Ternary	Nd³⁺-Yb³⁺-Tm³⁺/ Yb³⁺-Er³⁺/ Er³⁺-Tm³⁺	Blue@808 nm Green@980 nm Red@1532 nm	Multiplexed detection	[ 61 ] 2022
NaErF₄:Tm@NaYF₄@NaYF₄:Yb/Ho@NaYF₄:Nd/Yb@NaYF₄@ NaYbF₄:Tm@ NaYF₄:Yb	Ternary	Er³⁺-Tm³⁺/ Nd³⁺-Yb³⁺-Ho³⁺/ Yb³⁺-Tm³⁺	Red@1550 nm Green@808 nm UV/blue@980 nm	Flexible display/ anticounterfeiting	[ 62 ] 2022

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