Volume 16 Issue 1
Jan.  2023
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JIA Heng, FENG Xiao-rui, LI Da-guang, QIN Wei-ping, YANG Long, HE Wei-yan, MA Hui-yan, TENG Ying-yue. Design, preparation and application of orthogonal excitation-emission upconversion nanomaterials[J]. Chinese Optics, 2023, 16(1): 76-93. doi: 10.37188/CO.2022-0134
Citation: JIA Heng, FENG Xiao-rui, LI Da-guang, QIN Wei-ping, YANG Long, HE Wei-yan, MA Hui-yan, TENG Ying-yue. Design, preparation and application of orthogonal excitation-emission upconversion nanomaterials[J]. Chinese Optics, 2023, 16(1): 76-93. doi: 10.37188/CO.2022-0134

Design, preparation and application of orthogonal excitation-emission upconversion nanomaterials

doi: 10.37188/CO.2022-0134
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)
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  • 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.


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  • [1]
    WANG F, LIU X G. Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals[J]. Chemical Society Reviews, 2009, 38(4): 976-989. doi: 10.1039/b809132n
    LIU X G, Yan CH H, CAPOBIANCO J A. Photon upconversion nanomaterials[J]. Chemical Society Reviews, 2015, 44(6): 1299-1301. doi: 10.1039/C5CS90009C
    ZHOU B, SHI B Y, JIN D Y, et al. Controlling upconversion nanocrystals for emerging applications[J]. Nature Nanotechnology, 2015, 10(11): 924-936. doi: 10.1038/nnano.2015.251
    AUZEL F. Upconversion and anti-Stokes processes with f and d Ions in solids[J]. Chemical Reviews, 2004, 104(1): 139-174. doi: 10.1021/cr020357g
    BLOEMBERGEN N. Solid State Infrared Quantum Counters[J]. Physical Review Letters, 1959, 2(3): 84-85. doi: 10.1103/PhysRevLett.2.84
    AUZEL F. Compteur quantique par transfert d'energie entre deux ions de terres rares dans un tungstate mixte et dans un verre[J]. Comptes Rendus de l'Académie des Sciences de Paris, 1966, 262: 1016-1019.
    WANG M, ABBINENI G, CLEVENGER A, et al. Upconversion nanoparticles: synthesis, surface modification and biological applications[J]. Nanomedicine:Nanotechnology,Biology and Medicine, 2011, 7(6): 710-729. doi: 10.1016/j.nano.2011.02.013
    HAASE M, SCHÄFER H. Upconverting Nanoparticles[J]. Angewandte Chemie International Edition, 2011, 50(26): 5808-5829. doi: 10.1002/anie.201005159
    LIU S B, YAN L, HUANG J SH, et al. Controlling upconversion in emerging multilayer core–shell nanostructures: from fundamentals to frontier applications[J]. Chemical Society Reviews, 2022, 51(5): 1729-1765. doi: 10.1039/D1CS00753J
    YAN CH L, ZHAO H G, PEREPICHKA D F, et al. Lanthanide ion doped upconverting nanoparticles: synthesis, structure and properties[J]. Small, 2016, 12(29): 3888-3907. doi: 10.1002/smll.201601565
    ZHU X H, ZHANG J, LIU J L, et al. Recent progress of rare-earth doped upconversion nanoparticles: synthesis, optimization, and applications[J]. Advanced Science, 2019, 6(22): 1901358. doi: 10.1002/advs.201901358
    ZHENG K ZH, LOH K Y, WANG Y, et al. Recent advances in upconversion nanocrystals: expanding the kaleidoscopic toolbox for emerging applications[J]. Nano Today, 2019, 29: 100797. doi: 10.1016/j.nantod.2019.100797
    QIN W P, Sin C, Liu ZH Y, et al. Theory on cooperative quantum transitions of three identical lanthanide ions[J]. Journal of the Optical Society of America B, 2015, 32(2): 303-308. doi: 10.1364/JOSAB.32.000303
    QIN W P, LIU ZH Y, SIN C N, et al. Multi-ion cooperative processes in Yb3+ clusters[J]. Light:Science &Applications, 2014, 3(8): e193-e193.
    TU L P, LIU X M, WU F, et al. Excitation energy migration dynamics in upconversion nanomaterials[J]. Chemical Society Reviews, 2015, 44(6): 1331-1345. doi: 10.1039/C4CS00168K
    DONG H, SUN L D, YAN CH H. Energy transfer in lanthanide upconversion studies for extended optical applications[J]. Chemical Society Reviews, 2015, 44(6): 1608-1634. doi: 10.1039/C4CS00188E
    DENG R R, QIN F, CHEN R F, et al. Temporal full-colour tuning through non-steady-state upconversion[J]. Nature Nanotechnology, 2015, 10(3): 237-242. doi: 10.1038/nnano.2014.317
    LI ZH Q, ZHANG Y, JIANG SH. Multicolor core/shell-structured upconversion fluorescent nanoparticles[J]. Advanced Materials, 2008, 20(24): 4765-4769. doi: 10.1002/adma.200801056
    WANG F, LIU X G. Multicolor tuning of lanthanide-doped nanoparticles by single wavelength excitation[J]. Accounts of Chemical Research, 2014, 47(4): 1378-1385. doi: 10.1021/ar5000067
    WU M, YAN L, WANG T, et al. Controlling red color–based multicolor upconversion through selective photon blocking[J]. Advanced Functional Materials, 2019, 29(25): 1804160. doi: 10.1002/adfm.201804160
    LI L L, ZHANG R B, YIN L L, et al. Biomimetic surface engineering of lanthanide-doped upconversion nanoparticles as versatile bioprobes[J]. Angewandte Chemie, 2012, 124(25): 6225-6229. doi: 10.1002/ange.201109156
    WÜRTH C, FISCHER S, GRAUEL B, et al. Quantum yields, surface quenching, and passivation efficiency for ultrasmall core/shell upconverting nanoparticles[J]. Journal of the American Chemical Society, 2018, 140(14): 4922-4928. doi: 10.1021/jacs.8b01458
    REN W, WEN SH H, TAWFIK S A, et al. Anisotropic functionalization of upconversion nanoparticles[J]. Chemical Science, 2018, 9(18): 4352-4358. doi: 10.1039/C8SC01023D
    FAN Y, LIU L, ZHANG F. Exploiting lanthanide-doped upconversion nanoparticles with core/shell structures[J]. Nano Today, 2019, 25: 68-84. doi: 10.1016/j.nantod.2019.02.009
    CHEN X, PENG D F, JU Q, et al. Photon upconversion in core–shell nanoparticles[J]. Chemical Society Reviews, 2015, 44(6): 1318-1330. doi: 10.1039/C4CS00151F
    YAO W J, TIAN Q Y, WU W. Tunable emissions of upconversion fluorescence for security applications[J]. Advanced Optical Materials, 2019, 7(6): 1801171. doi: 10.1002/adom.201801171
    TANG Y N, DI W H, ZHAI X S, et al. NIR-responsive photocatalytic activity and mechanism of NaYF4:Yb, Tm@TiO2 core–shell nanoparticles[J]. ACS Catalysis, 2013, 3(3): 405-412. doi: 10.1021/cs300808r
    CHEN G Y, ÅGREN H, OHULCHANSKYY T Y, et al. Light upconverting core–shell nanostructures: nanophotonic control for emerging applications[J]. Chemical Society Reviews, 2015, 44(6): 1680-1713. doi: 10.1039/C4CS00170B
    GAI SH L, YANG P P, LI CH X, et al. Synthesis of magnetic, up-conversion luminescent, and mesoporous core-shell-structured nanocomposites as drug carriers[J]. Advanced Functional Materials, 2010, 20(7): 1166-1172. doi: 10.1002/adfm.200902274
    ZHOU L, FAN Y, WANG R, et al. High-capacity upconversion wavelength and lifetime binary encoding for multiplexed biodetection[J]. Angewandte Chemie International Edition, 2018, 57(39): 12824-12829. doi: 10.1002/anie.201808209
    ZHOU B, YAN L, HUANG J SH, et al. NIR II-responsive photon upconversion through energy migration in an ytterbium sublattice[J]. Nature Photonics, 2020, 14(12): 760-766. doi: 10.1038/s41566-020-00714-6
    ZHANG ZH, ZHANG Y. Orthogonal emissive upconversion nanoparticles: material design and applications[J]. Small, 2021, 17(11): 2004552. doi: 10.1002/smll.202004552
    LAI J P, ZHANG Y X, PASQUALE N, et al. An upconversion nanoparticle with orthogonal emissions using dual NIR excitations for controlled two-way photoswitching[J]. Angewandte Chemie International Edition, 2014, 53(52): 14419-14423. doi: 10.1002/anie.201408219
    LIU L, YAN D, XU L, et al. Intense and color-tunable upconversion through 980 and 1530 nm excitations[J]. Journal of Luminescence, 2020, 224: 117306. doi: 10.1016/j.jlumin.2020.117306
    QUINTANILLA M, REN F Q, MA D L, et al. Light management in upconverting nanoparticles: ultrasmall core/shell architectures to tune the emission color[J]. ACS Photonics, 2014, 1(8): 662-669. doi: 10.1021/ph500208q
    LIU S B, YAN L, LI Q Q, et al. Tri-channel photon emission of lanthanides in lithium-sublattice core-shell nanostructures for multiple anti-counterfeiting[J]. Chemical Engineering Journal, 2020, 397: 125451. doi: 10.1016/j.cej.2020.125451
    WANG F, DENG R R, WANG J, et al. Tuning upconversion through energy migration in core–shell nanoparticles[J]. Nature Materials, 2011, 10(12): 968-973. doi: 10.1038/nmat3149
    CHEN D Q, LEI L, YANG A P, et al. Ultra-broadband near-infrared excitable upconversion core/shell nanocrystals[J]. Chemical Communications, 2012, 48(47): 5898-5900. doi: 10.1039/c2cc32102e
    XU M, CHEN D Q, HUANG P, et al. A dual-functional upconversion core@shell nanostructure for white-light-emission and temperature sensing[J]. Journal of Materials Chemistry C, 2016, 4(27): 6516-6524. doi: 10.1039/C6TC02218A
    FISCHER S, BRONSTEIN N D, SWABECK J K, et al. Precise tuning of surface quenching for luminescence enhancement in core–shell lanthanide-doped nanocrystals[J]. Nano Letters, 2016, 16(11): 7241-7247. doi: 10.1021/acs.nanolett.6b03683
    WEN H L, ZHU H, CHEN X, et al. Upconverting near-infrared light through energy management in core-shell-shell nanoparticles[J]. Angewandte Chemie International Edition, 2013, 52(50): 13419-13423. doi: 10.1002/anie.201306811
    LI X M, GUO ZH ZH, ZHAO T C, et al. Filtration shell mediated power density independent orthogonal excitations-emissions upconversion luminescence[J]. Angewandte Chemie International Edition, 2016, 55(7): 2464-2469. doi: 10.1002/anie.201510609
    DONG H, SUN L D, FENG W, et al. Versatile spectral and lifetime multiplexing nanoplatform with excitation orthogonalized upconversion luminescence[J]. ACS Nano, 2017, 11(3): 3289-3297. doi: 10.1021/acsnano.7b00559
    ZHENG K ZH, HAN S Y, ZENG X, et al. Rewritable optical memory through high-registry orthogonal upconversion[J]. Advanced Materials, 2018, 30(30): 1801726. doi: 10.1002/adma.201801726
    HUANG B R, WU Q SH, PENG X Y, et al. One-scan fluorescence emission difference nanoscopy developed with excitation orthogonalized upconversion nanoparticles[J]. Nanoscale, 2018, 10(45): 21025-21030. doi: 10.1039/C8NR07017B
    ZUO J, TU L P, LI Q Q, et al. Near infrared light sensitive ultraviolet–blue nanophotoswitch for imaging-guided “off–on” therapy[J]. ACS Nano, 2018, 12(4): 3217-3225. doi: 10.1021/acsnano.7b07393
    MEI Q S, BANSAL A, JAYAKUMAR M K G, et al. Manipulating energy migration within single lanthanide activator for switchable upconversion emissions towards bidirectional photoactivation[J]. Nature Communications, 2019, 10(1): 4416. doi: 10.1038/s41467-019-12374-4
    GUO X R, YUAN Y, LIU J L, et al. Single-line flow assay platform based on orthogonal emissive upconversion nanoparticles[J]. Analytical Chemistry, 2021, 93(5): 3010-3017. doi: 10.1021/acs.analchem.0c05061
    LEI ZH D, LING X, MEI Q S, et al. An excitation navigating energy migration of lanthanide ions in upconversion nanoparticles[J]. Advanced Materials, 2020, 32(9): 1906225. doi: 10.1002/adma.201906225
    DI ZH H, LIU B, ZHAO J, et al. An orthogonally regulatable DNA nanodevice for spatiotemporally controlled biorecognition and tumor treatment[J]. Science Advances, 2020, 6(25): eaba9381. doi: 10.1126/sciadv.aba9381
    HUANG J SH, YAN L, LIU S B, et al. Dynamic control of orthogonal upconversion in migratory core–shell nanostructure toward information security[J]. Advanced Functional Materials, 2021, 31(14): 2009796. doi: 10.1002/adfm.202009796
    JIA H, LI D G, ZHANG D, et al. High color-purity red, green, and blue-emissive core–shell upconversion nanoparticles using ternary near-infrared quadrature excitations[J]. ACS Applied Materials &Interfaces, 2021, 13(3): 4402-4409.
    秦伟平, 贾恒, 张丹, 等. 具有三元正交激发响应三基色上转换发光性能的五层核壳结构纳米材料: 中国, 202010685751. 7[p]. 2022–05-31.

    QIN W P, JIA H, ZHANG D, et al. . Core/quintuple-shell nanomaterials with ternary orthogonal excitation-responsive three-primary-color upconversion luminescence property: CN, 202010685751. 7[p]. 2022–05-31. (in Chinese)
    秦伟平, 贾恒, 董妍惠, 等. 一种制备正交激发-发射响应的三基色上转换发光材料的方法: 中国, 202010685752. 1[p]. 2022–05-31.

    QIN W P, JIA H, DONG Y H, et al. . A method for preparing orthogonal excitation-emission-responsive three-primary-color upconversion luminescencet materials: CN, 202010685752. 1[p]. 2022–05-31. (in Chinese)
    秦伟平, 贾恒, 崔珈豪, 等. 一种基于δ-MnO2纳米片修饰正交三基色上转换发光纳米晶的加密墨水及其制备方法: 中国, 202010685712. 7[p]. 2021–08-27.

    QIN W P, JIA H, CUI J H, et al. . An encryption ink based on orthogonal three-primary-color upconversion luminescence nanocrystals modified by δ-MnO2 nanosheets and its preparation method: CN, 202010685712. 7[p]. 2021–08-27. (in Chinese)
    秦伟平, 贾恒, 李大光, 等. 一种红绿蓝三基色正交上转换荧光安全墨水的制备方法: 中国, 202010685263. 6[p]. 2021–09-24.

    QIN W P, JIA H, LI D G, et al. . A preparation method of red, green and blue tri-color orthogonal upconversion fluorescence security ink: CN, 202010685263. 6[p]. 2021–09-24. (in Chinese)
    秦伟平, 贾恒, 周敏, 等. 一种具有三基色正交上转换荧光特性的多级防伪材料及应用: 中国, 202010685713. 1[p]. 2021–08-17.

    QIN W P, JIA H, ZHOU M, et al. . A multi-level anticounterfeiting material with three-primary-color orthogonal upconversion fluorescence property and its application: CN, 202010685713. 1[p]. 2021–08-17. (in Chinese)
    JIA H, TENG Y Y, LI N, et al. Dual stimuli-responsive inks based on orthogonal upconversion three-primary-color luminescence for advanced anticounterfeiting applications[J]. ACS Materials Letters, 2022, 4(7): 1306-1313. doi: 10.1021/acsmaterialslett.2c00328
    HONG A R, KYHM J H, KANG G M, et al. Orthogonal R/G/B upconversion luminescence-based full-color tunable upconversion nanophosphors for transparent displays[J]. Nano Letters, 2021, 21(11): 4838-4844. doi: 10.1021/acs.nanolett.1c01510
    LIU X, CHEN H M, WANG Y T, et al. Near-infrared manipulation of multiple neuronal populations via trichromatic upconversion[J]. Nature Communications, 2021, 12(1): 5662. doi: 10.1038/s41467-021-25993-7
    CHEN T, SHANG Y F, HAO SH W, et al. Reproducible single-droplet multiplexed detection through excitation-encoded tri-mode upconversion solid sensors[J]. Chemical Engineering Journal, 2022, 430: 131242. doi: 10.1016/j.cej.2021.131242
    HU P, ZHOU SH, WANG Y, et al. Printable, room-temperature self-healing and full-color-tunable emissive composites for transparent panchromatic display and flexible high-level anti-counterfeiting[J]. Chemical Engineering Journal, 2022, 431: 133728. doi: 10.1016/j.cej.2021.133728
    BOYER J C, CARLING C J, GATES B D, et al. Two-way photoswitching using one type of near-infrared light, upconverting nanoparticles, and changing only the light intensity[J]. Journal of the American Chemical Society, 2010, 132(44): 15766-15772. doi: 10.1021/ja107184z
    SHAO Q Y, ZHANG G T, OUYANG L L, et al. Emission color tuning of core/shell upconversion nanoparticles through modulation of laser power or temperature[J]. Nanoscale, 2017, 9(33): 12132-12141. doi: 10.1039/C7NR03682E
    WANG Y, ZHENG K ZH, SONG SH Y, et al. Remote manipulation of upconversion luminescence[J]. Chemical Society Reviews, 2018, 47(17): 6473-6485. doi: 10.1039/C8CS00124C
    ZHANG C, YANG L, ZHAO J, et al. White-light emission from an integrated upconversion nanostructure: toward multicolor displays modulated by laser power[J]. Angewandte Chemie, 2015, 127(39): 11693-11697. doi: 10.1002/ange.201504518
    HU M, MA D D, LIU CH CH, et al. Intense white emission from a single-upconversion nanoparticle and tunable emission colour with laser power[J]. Journal of Materials Chemistry C, 2016, 4(29): 6975-6981. doi: 10.1039/C6TC01437B
    CHEN B, LIU Y, XIAO Y, et al. Amplifying excitation-power sensitivity of photon upconversion in a NaYbF4:Ho nanostructure for direct visualization of electromagnetic hotspots[J]. The Journal of Physical Chemistry Letters, 2016, 7(23): 4916-4921. doi: 10.1021/acs.jpclett.6b02210
    ZHAO F F, YIN D G, WU CH L, et al. Huge enhancement of upconversion luminescence by dye/Nd3+ sensitization of quenching-shield sandwich structured upconversion nanocrystals under 808 nm excitation[J]. Dalton Transactions, 2017, 46(46): 16180-16189. doi: 10.1039/C7DT03383D
    XIONG W, LIN SH K, XIE Y P. Growth and spectral properties of Er3+:GdVO4 crystal[J]. Journal of Crystal Growth, 2004, 263(1–4): 353–357.
    YIN X M, WANG H, TIAN Y, et al. Three primary color emissions from single multilayered nanocrystals[J]. Nanoscale, 2018, 10(20): 9673-9678. doi: 10.1039/C8NR01752B
    TANG M, ZHU X H, ZHANG Y H, et al. Near-infrared excited orthogonal emissive upconversion nanoparticles for imaging-guided on-demand therapy[J]. ACS Nano, 2019, 13(9): 10405-10418. doi: 10.1021/acsnano.9b04200
    SUO H, Zhu Q, Zhang X, et al. High-security anti-counterfeiting through upconversion luminescence[J]. Materials Today Physics, 2021, 21: 100520. doi: 10.1016/j.mtphys.2021.100520
    DOWNING E, HESSELINK L, RALSTON J, et al. A three-color, solid-state, three-dimensional display[J]. Science, 1996, 273(5279): 1185-1189. doi: 10.1126/science.273.5279.1185
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