Ultrasmall Lanthanide-doped NaMgF<sub>3</sub> Nanocrystals:Controlled Synthesis and Optical Properties

摘要
图/表
参考文献
相关文章 (4)

全文: PDF (900 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要 Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide (Ln3+)-doped luminescent nanocrystals (NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall (＜ 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ～10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation (e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence (UCL) ranging from ultraviolet (UV) to visible and to near-infrared (NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	李国炜
	刘永升
	江飞龙
	洪茂椿

关键词 ： NaMgF3, nanocrystals, lanthanide ion, upconversion luminescence, ultrasmall

Abstract：Orthorhombic-phase NaMgF3, composed of bio-friendly elements of Na, Mg and F, is considered to be an ideal host matrix for preparing trivalent lanthanide (Ln3+)-doped luminescent nanocrystals (NCs) with color-tunable emissions for diverse biological applications. However, the preparation and the survey on optical properties of ultrasmall (＜ 10 nm) Ln3+-doped NaMgF3 NCs remain nearly untouched to date. In this paper, we report a series of monodisperse Ln3+-doped orthorhombic-phase NaMgF3 NCs with an average size of ～10 nm that was synthesised by using a modified high-temperature co-precipitation method. Utilizing Eu3+ ion as an efficient optical/structural probe, the successful hetero-valence doping of Ln3+ ion into the lattice of NaMgF3 NCs is well-established irrespective of their different valences and radii between the host cation (e.g. Mg2+) and Ln3+ dopant. Benefiting from this, desirable upconversion luminescence (UCL) ranging from ultraviolet (UV) to visible and to near-infrared (NIR) spectral regions can be easily obtained after the doping of typical UCL couples of Yb3+/Er3+, Yb3+/Tm3+ and Yb3+/Ho3+ into the NaMgF3 NCs upon excitation by using a 980-nm diode laser.

Key words： NaMgF3 nanocrystals lanthanide ion upconversion luminescence ultrasmall

收稿日期: 2020-01-13 出版日期: 2020-11-09

基金资助:This work was supported by the Strategic Priority Research Program of Chinese Academy of Sciences (CAS, XDB20000000),the National Natural Science Foundation of China (NSFC, Nos. 21871256 and 21731006), the Key Research Program of Frontier Science CAS (QYZDY-SSW-SLH025) and the Outstanding Youth Innovation Promotion Association of CAS

通讯作者: liuysh@fjirsm.ac.cn E-mail: liuysh@fjirsm.ac.cn

引用本文:

李国炜;刘永升;江飞龙;洪茂椿. Ultrasmall Lanthanide-doped NaMgF₃ Nanocrystals:Controlled Synthesis and Optical Properties[J]. 结构化学, 2020, 39(11): 2001-2008.
LI Guo-Wei;LIU Yong-Sheng;JIANG Fei-Long;HONG Mao-Chun. Ultrasmall Lanthanide-doped NaMgF₃ Nanocrystals:Controlled Synthesis and Optical Properties. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(11): 2001-2008.

链接本文:

http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2020/V39/I11/2001

REFERENCES
(1) Ding, Q.; Zhao, S.; Li, L.; Shen, Y.; Shan, P.; Wu, Z.; Li, X.; Li, Y.; Liu, S.; Luo, J. Abrupt structural transformation in asymmetric ABPO4F (A = K, Rb, Cs). Inorg. Chem. 2019, 58, 1733-1737.
(2) Fu, H.; Peng, P.; Li, R.; Liu, C.; Liu, Y.; Jiang, F.; Hong, M.; Chen, X. A general strategy for tailoring upconversion luminescence in lanthanide-doped inorganic nanocrystals through local structure engineering. Nanoscale 2018, 10, 9353-9359.
(3) Li, Y.; Liang, F.; Zhao, S.; Li, L.; Wu, Z.; Ding, Q.; Liu, S.; Lin, Z.; Hong, M.; Luo, J. Two non--conjugated deep-UV nonlinear optical sulfates. J. Am. Chem. Soc. 2019, 141, 3833-3837.
(4) Hehlen, M. P.; Brik, M. G.; Krämer, K. W. 50th anniversary of the Judd-Ofelt theory: an experimentalist's view of the formalism and its application. J. Lumin. 2013, 136, 221-239.
(5) Bettinelli, M.; Carlos, L. D.; Liu, X. G. Lanthanide-doped upconversion nanoparticles. Phys. Today 2015, 68, 38-43.
(6) Qin, X.; Liu, X.; Huang, W.; Bettinelli, M.; Liu, X. Lanthanide-activated phosphors based on 4f-5d optical transitions: theoretical and experimental aspects. Chem. Rev. 2017, 117, 4488-4527.
(7) Wang, R.; Guo, Q.; Qian, Y.; Xing, L.; Xu, Y. Upconversion properties of LiNbO3 single crystals co-doped with Ho and Yb. Chin. J. Struct. Chem. 2011, 30, 1597-1603.
(8) Back, M.; Ueda, J.; Ambrosi, E.; Cassandro, L.; Cristofori, D.; Ottini, R.; Riello, P.; Sponchia, G.; Asami, K.; Tanabe, S.; Trave, E. Lanthanide-doped bismuth-based fluoride nanocrystalline particles: formation, spectroscopic investigation, and chemical stability. Chem. Mater. 2019, 31, 8504-8514.
(9) Bian, W.; Lin, Y.; Wang, T.; Yu, X.; Qiu, J.; Zhou, M.; Luo, H.; Yu, S. F.; Xu, X. Direct identification of surface defects and their influence on the optical characteristics of upconversion nanoparticles. ACS Nano 2018, 12, 3623-3628.
(10) Chen, B.; Kong, W.; Liu, Y.; Lu, Y.; Li, M.; Qiao, X.; Fan, X.; Wang, F. Crystalline hollow microrods for site-selective enhancement of nonlinear photoluminescence. Angew. Chem. Int. Ed. 2017, 56, 10383-10387.
(11) Chen, B.; Kong, W.; Wang, N.; Zhu, G.; Wang, F. Oleylamine-mediated synthesis of small NaYbF4 nanoparticles with tunable size. Chem. Mater. 2019, 4779-4786.
(12) Ding, S.; Yang, X. F.; Song, E. H.; Liang, C. L.; Zhou, B.; Wu, M. M.; Zhou, W. Z.; Zhang, Q. Y. An efficient synthetic strategy for uniform perovskite core-shell nanocubes NaMgF3:Mn2+,Yb3+@NaMgF3:Yb3+ with enhanced near infrared upconversion luminescence. J. Mater. Chem. C 2018, 6, 2342-2350.
(13) Fischer, S.; Swabeck, J. K.; Alivisatos, A. P. Controlled isotropic and anisotropic shell growth in beta-NaLnF4 nanocrystals induced by precursor injection rate. J. Am. Chem. Soc. 2017, 139, 12325-12332.
(14) Huang, P.; Zheng, W.; Gong, Z.; You, W.; Wei, J.; Chen, X. Rare earth ion- and transition metal ion-doped inorganic luminescent nanocrystals: from fundamentals to biodetection. Mater. Today Nano 2019, 5, 100031-23.
(15) Liu, M.; Shi, Z.; Wang, X.; Zhang, Y.; Mo, X.; Jiang, R.; Liu, Z.; Fan, L.; Ma, C. G.; Shi, F. Simultaneous enhancement of red upconversion luminescence and CT contrast of NaGdF4:Yb,Er nanoparticles via Lu3+ doping. Nanoscale 2018, 10, 20279-20288.
(16) Pang, M.; Zhai, X.; Feng, J.; Song, S.; Deng, R.; Wang, Z.; Yao, S.; Ge, X.; Zhang, H. One-step synthesis of water-soluble hexagonal NaScF4:Yb/Er nanocrystals with intense red emission. Dalton Trans. 2014, 43, 10202-10207.
(17) Zheng, W.; Zhou, S.; Chen, Z.; Hu, P.; Liu, Y.; Tu, D.; Zhu, H.; Li, R.; Huang, M.; Chen, X. Sub-10 nm lanthanide-doped CaF2 nanoprobes for time-resolved luminescent biodetection. Angew. Chem. Int. Ed. 2013, 52, 6671-6676.
(18) Huang, Q.; Yu, H.; Ma, E.; Zhang, X.; Cao, W.; Yang, C.; Yu, J. Upconversion effective enhancement by producing various coordination surroundings of rare-earth ions. Inorg. Chem. 2015, 54, 2643-2651.
(19) Gu, Y.; Guo, Z.; Yuan, W.; Kong, M.; Liu, Y.; Liu, Y.; Gao, Y.; Feng, W.; Wang, F.; Zhou, J.; Jin, D.; Li, F. High-sensitivity imaging of time-domain near-infrared light transducer. Nat. Photon. 2019, 13, 525-531.
(20) Li, L.; Yu, Y.; Zhou, Z.; Li, Q. PEG assisted hydrothermal synthesis of -NaYF4:Yb3+,Er3+ microrods for upconversion photoluminescence display. Chin. J. Struct. Chem. 2014, 33, 1865-1874.
(21) Liu, Q.; Feng, W.; Yang, T.; Yi, T.; Li, F. Upconversion luminescence imaging of cells and small animals. Nat. Protoc. 2013, 8, 2033-2044.
(22) Song, X.; Li, S.; Guo, H.; You, W.; Shang, X.; Li, R.; Tu, D.; Zheng, W.; Chen, Z.; Yang, H.; Chen, X. Graphene-oxide-modified lanthanide nanoprobes for tumor-targeted visible/NIR-II luminescence imaging. Angew. Chem. Int. Ed. 2019, 58, 18981-18986.
(23) Wang, J.; Lin, H.; Cheng, Y.; Cui, X.; Gao, Y.; Ji, Z.; Xu, J.; Wang, Y. A novel high-sensitive upconversion thermometry strategy: utilizing synergistic effect of dual-wavelength lasers excitation to manipulate electron thermal distribution. Sens. Actuators B-Chem. 2019, 278, 165-171.
(24) Xu, M.; Zou, X.; Su, Q.; Yuan, W.; Cao, C.; Wang, Q.; Zhu, X.; Feng, W.; Li, F. Ratiometric nanothermometer in vivo based on triplet sensitized upconversion. Nat. Commun. 2018, 9, 2698-7.
(25) Yu, L.; Liu, Y.; Chen, X. Lanthanide-doped upconversion nano-bioprobes for in-vitro detection of tumor marker. Chin. J. Lumin. 2018, 39, 27-49.
(26) Zhang, M.; Zhai, X.; Lei, P.; Yao, S.; Xu, X.; Dong, L.; Du, K.; Li, C.; Feng, J.; Zhang, H. Selective enhancement of green upconversion luminescence from NaYF4:Yb, Er microparticles through Ga3+ doping for sensitive temperature sensing. J. Lumin. 2019, 215, 116632-116639.
(27) Zhou, L.; Fan, Y.; Wang, R.; Li, X.; Fan, L.; Zhang, F. High-capacity upconversion wavelength and lifetime binary encoding for multiplexed biodetection. Angew. Chem. Int. Ed. 2018, 57, 12824-12829.
(28) Zhuo, Z.; Liu, Y.; Liu, D.; Huang, P.; Jiang, F.; Chen, X.; Hong, M. Manipulating energy transfer in lanthanide-doped single nanoparticles for highly enhanced upconverting luminescence. Chem. Sci. 2017, 8, 5050-5056.
(29) Wang, Y.; Wei, T.; Cheng, X.; Ma, H.; Pan, Y.; Xie, J.; Su, H.; Xie, X.; Huang, L.; Huang, W. Insights into Li+-induced morphology evolution and upconversion luminescence enhancement of KSc2F7:Yb/Er nanocrystals. J. Mater. Chem. C 2017, 5, 3503-3508.
(30) Wu, Y.; Sun, Y.; Zhu, X.; Liu, Q.; Cao, T.; Peng, J.; Yang, Y.; Feng, W.; Li, F. Lanthanide-based nanocrystals as dual-modal probes for SPECT and X-ray CT imaging. Biomaterials 2014, 35, 4699-4705.
(31) Dong, H.; Sun, L. D.; Li, L. D.; Si, R.; Liu, R.; Yan, C. H. Selective cation exchange enabled growth of lanthanide core/shell nanoparticles with dissimilar structure. J. Am. Chem. Soc. 2017, 139, 18492-18495.
(32) Liu, H.; Xu, H.; Huang, Q.; Cao, W.; Yu, H.; Yu, Y. Upconversion luminescence properties of NaY0.92Yb0.05Er0.03F4 enhanced by Zr4+ codoping. Chin. J. Struct. Chem. 2017, 36, 1743-1751.
(33) Xu, J.; Tu, D.; Zheng, W.; Shang, X.; Huang, P.; Cheng, Y.; Wang, Y.; Chen, X. Interfacial defects dictated in situ fabrication of yolk-shell upconversion nanoparticles by electron-beam irradiation. Adv. Sci. 2018, 5, 1800766-9.
(34) Wang, M.; Tian, Y.; Zhao, F.; Li, R.; You, W.; Fang, Z.; Chen, X.; Huang, W.; Ju, Q. Alleviating the emitter concentration effect on upconversion nanoparticles via an inert shell. J. Mater. Chem. C 2017, 5, 1537-1543.
(35) Xiang, J.; Ge, F.; Yu, B.; Yan, Q.; Shi, F.; Zhao, Y. Nanocomplexes of photolabile polyelectrolyte and upconversion nanoparticles for near-infrared light-triggered payload release. ACS Appl. Mater. Interfaces 2018, 10, 20790-20800.
(36) Ju, D.; Song, F.; Khan, A.; Song, F.; Zhou, A.; Gao, X.; Hu, H.; Sang, X.; Zadkov, V. Simultaneous dual-mode emission and tunable multicolor in the time domain from lanthanide-doped core-shell microcrystals. Nanomaterials 2018, 8, 1023-11.
(37) Liu, X.; Wang, Y.; Li, X.; Yi, Z.; Deng, R.; Liang, L.; Xie, X.; Loong, D. T. B.; Song, S.; Fan, D.; All, A. H.; Zhang, H.; Huang, L.; Liu, X. Binary temporal upconversion codes of Mn2+-activated nanoparticles for multilevel anti-counterfeiting. Nat. Commun. 2017, 8, 899-7.
(38) Lei, P.; An, R.; Yao, S.; Wang, Q.; Dong, L.; Xu, X.; Du, K.; Feng, J.; Zhang, H. Ultrafast synthesis of novel hexagonal phase NaBiF4 upconversion nanoparticles at room temperature. Adv. Mater. 2017, 29, 1700505-4.
(39) Sun, Y.; Feng, W.; Yang, P.; Huang, C.; Li, F. The biosafety of lanthanide upconversion nanomaterials. Chem. Soc. Rev. 2015, 44, 1509-1525.
(40) Du, Y. P.; Zhang, Y. W.; Yan, Z. G.; Sun, L. D.; Gao, S.; Yan, C. H. Single-crystalline and near-monodispersed NaMF3 (M = Mn, Co, Ni, Mg) and LiMAlF6 (M = Ca, Sr) nanocrystals from cothermolysis of multiple trifluoroacetates in solution. Chem. Asian J. 2007, 2, 965-974.
(41) Wang, J.; Zhang, J.; Xie, J.; Li, Y.; Wang, L.; Zhang, Q. Phase controllable synthesis of NaMgF3:Yb3+, Er3+ nanocrystals with effective red upconversion luminescence. J. Mater. Sci.: Mater. Electron. 2018, 29, 18320-18330.
(42) Liu, L.; Wang, S.; Zhao, B.; Pei, P.; Fan, Y.; Li, X.; Zhang, F. Er3+ sensitized 1530 to 1180 nm second near-infrared window upconversion nanocrystals for in vivo biosensing. Angew. Chem. Int. Ed. 2018, 57, 7518-7522.
(43) Wang, J.; Wang, F.; Wang, C.; Liu, Z.; Liu, X. Single-band upconversion emission in lanthanide-doped KMnF3 nanocrystals. Angew. Chem. Int. Ed. 2011, 50, 10369-10372.
(44) Zhong, Y.; Ma, Z.; Wang, F.; Wang, X.; Yang, Y.; Liu, Y.; Zhao, X.; Li, J.; Du, H.; Zhang, M.; Cui, Q.; Zhu, S.; Sun, Q.; Wan, H.; Tian, Y.; Liu, Q.; Wang, W.; Garcia, K. C.; Dai, H. In vivo molecular imaging for immunotherapy using ultra-bright near-infrared-IIb rare-earth nanoparticles. Nat. Biotechnol. 2019, 37, 1322-1331.
(45) Pischedda, V.; Ferraris, G.; Raade, G. Single-crystal X-ray diffraction study on neighborite (NaMgF3) from Gjerdingselva, Norway. N. Jb. Miner. Abh. 2005, 182, 23-29.
(46) Fu, H.; Liu, Y.; Jiang, F.; Hong, M. Controlled synthesis and optical properties of lanthanide-doped Na3ZrF7 nanocrystals. Chin. J. Struct. Chem. 2018, 37, 1737-1748.
(47) Yu, L.; Li, G.; Liu, Y.; Jiang, F.; Hong, M. Lanthanide-doped KGd2F7 nanocrystals: controlled synthesis, optical properties, and spectroscopic identification of the optimum core/shell architecture for highly enhanced upconverting luminescence. Cryst. Growth Des. 2019, 19, 2340-2349.
(48) Liu, Y.; Tu, D.; Zhu, H.; Chen, X. Lanthanide-doped luminescent nanoprobes: controlled synthesis, optical spectroscopy, and bioapplications. Chem. Soc. Rev. 2013, 42, 6924-6958.