Abstract
The applications of lanthanide-doped upconversionnanocrystals in biological imaging, photonics, photovoltaics and therapeutics have fuelled a growing demand for rational control over the emission profiles of the nanocrystals1,2,3,4,5,6,7,8,9,10,11,12,13,14. A common strategy for tuning upconversion luminescence is to control the doping concentration of lanthanide ions15,16. However, the phenomenon of concentration quenching of the excited state at high doping levels poses a significant constraint. Thus, the lanthanide ions have to be stringently kept at relatively low concentrations to minimize luminescence quenching17. Here we describe a new class of upconversion nanocrystals adopting an orthorhombic crystallographic structure in which the lanthanide ions are distributed in arrays of tetrad clusters. Importantly, this unique arrangement enables the preservation of excitation energy within the sublattice domain and effectively minimizes the migration of excitation energy to defects, even in stoichiometric compounds with a high Yb3+ content (calculated as 98 mol%). This allows us to generate an unusual four-photon-promoted violet upconversion emission from Er3+ with an intensity that is more than eight times higher than previously reported. Our results highlight that the approach to enhancing upconversion through energy clustering at the sublattice level may provide new opportunities for light-triggered biological reactions and photodynamic therapy.
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References
Haase, M. & Schäfer, H. Upconverting nanoparticles. Angew. Chem. Int. Ed. 50, 5808–5829 (2011).
Zou, W., Visser, C., Maduro, J. A., Pshenichnikov, M. S. & Hummelen, J. C. Broadband dye-sensitized upconversion of near-infrared light. Nature Photon. 6, 560–564 (2012).
Zhang, F. et al. Direct imaging the upconversion nanocrystal core/shell structure at the sub-nanometre level: Shell thickness dependence in upconverting optical properties. Nano. Lett. 12, 2852–2858 (2012).
Wang, F. et al. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping. Nature 463, 1061–1065 (2010).
Park, Y. I. et al. Comparative study of upconverting nanoparticles with various crystal structures, core/shell structures, and surface characteristics. J. Phys. Chem. C 117, 2239–2244 (2013).
Zhao, J. et al. Upconversion luminescence with tunable lifetime in NaYF4:Yb,Er nanocrystals: Role of nanocrystal size. Nanoscale 5, 944–952 (2013).
Hao, J., Zhang, Y. & Wei, X. Electric-induced enhancement and modulation of upconversion photoluminescence in epitaxial BaTiO3:Yb/Er thin films. Angew. Chem. Int. Ed. 50, 6876–6880 (2011).
Wang, F. et al. Tuning upconversion through energy migration in core–shell nanoparticles. Nature Mater. 10, 968–973 (2011).
Kolesov, R. et al. Optical detection of a single rare-earth ion in a crystal. Nature Commun. 3, 1029 (2012).
Liu, Y. et al. Amine-functionalized lanthanide-doped zirconia nanoparticles: Optical spectroscopy, time-resolved FRET biodetection and targeted imaging. J. Am. Chem. Soc. 134, 15083–15090 (2012).
Chen, D., Lei, L., Yang, A., Wang, Z. & Wang, Y. Ultra-broadband near-infrared excitable upconversion core/shell nanocrystals. Chem. Commun. 48, 5898–5900 (2012).
Ye, X. et al. Morphologically controlled synthesis of colloidal upconversion nanophosphors and their shape-directed self-assembly. Proc. Natl Acad. Sci. USA 107, 22430–22435 (2010).
Chen, G., Ohulchanskyy, T. Y., Kumar, R., Agren, H. & Prasad, P. N. Ultrasmall monodisperse NaYF4:Yb3+/Tm3+ nanocrystals with enhanced near-infrared to near-infrared upconversion photoluminescence. ACS Nano 4, 3163–3168 (2010).
Gorris, H. H. & Wolfbeis, O. S. Photon-upconverting nanoparticles for optical encoding and multiplexing of cells, biomolecules, and microspheres. Angew. Chem. Int. Ed. 52, 3584–3600 (2013).
Chan, E. M. et al. Combinatorial discovery of lanthanide-doped nanocrystals with spectrally pure upconverted emission. Nano Lett. 12, 3839–3845 (2012).
Wang, F. & Liu, X. Upconversion multicolor fine-tuning: Visible to near-infrared emission from lanthanide-doped NaYF4 nanoparticles. J. Am. Chem. Soc. 130, 5642–5643 (2009).
Vetrone, F., Boyer, J-C., Capobianco, J. A., Speghini, A. & Bettinelli, M. Significance of Yb3+ concentration on the upconversion mechanisms in codoped Y2O3:Er3+, Yb3+ nanocrystals. J. Appl. Phys. 96, 661–667 (2004).
Krämer, K. W., Biner, D., Frei, G., Güdel, H. U., Hehlen, M. P. & Lüthi, S. R. Hexagonal sodium yttrium fluoride based green and blue emitting upconversion phosphors. Chem. Mater. 16, 1244–1251 (2004).
Mai, H., Zhang, Y., Si, R., Yan, Z., Sun, L., You, L. & Yan, C. High-quality sodium rare-earth fluoride nanocrystals: Controlled synthesis and optical properties. J. Am. Chem. Soc. 128, 6426–6436 (2006).
Wang, G., Peng, Q. & Li, Y. Upconversion luminescence of monodisperse CaF2:Yb3+/Er3+ nanocrystals. J. Am. Chem. Soc. 131, 14200–14201 (2009).
Berdowski, P. & Blasse, G. Luminescence and energy migration in a two-dimensional system–NaEuTiO4 . J. Lumin. 29, 243–260 (1984).
Buijs, M. & Blasse, G. Luminescence and energy migration in a one-dimensional system–EuMgB5O10 . J. Lumin. 34, 263–278 (1986).
Danielson, E. et al. A rare-earth phosphor containing one-dimensional chains identified through combinatorial methods. Science 279, 837–839 (1998).
Ananias, D. et al. Molecule-like Eu3+-dimers embedded in an extended system exhibit unique photoluminescence properties. J. Am. Chem. Soc. 131, 8620–8626 (2009).
Waber, J. T. & Cromer, D. T. Orbital radii of atoms and ions. J. Chem. Phys. 42, 4116–4123 (1965).
Malta, O. L. Mechanisms of non-radiative energy transfer involving lanthanide ions revisited. J. Non-Cryst. Solids. 354, 4770–4776 (2008).
Debasu, M. L., Ananias, D., Rocha, J., Malta, O. L. & Carlos, L. D. Energy-transfer from Gd(III) to Tb(III) in (Gd,Yb,Tb)PO4 nanocrystals. Phys. Chem. Chem. Phys. 15, 15565–15571 (2013).
Coleman, J. E. Structure and mechanism of alkaline phosphatase. Annu. Rev. Biophys. Biomol. Struct. 21, 441–483 (1992).
Kamiya, M., Urano, Y., Ebata, N., Yamamoto, M., Kosuge, J. & Nagano, T. Extension of the applicable range of fluorescein: A fluorescein-based probe for western blot analysis. Angew. Chem. Int. Ed. 44, 5439–5441 (2005).
Jia, L., Xu, J., Li, D., Pang, S., Fang, Y., Song, Z. & Ji, J. Fluorescence detection of alkaline phosphatase activity with β-cyclodextrin-modified quantum dots. Chem. Commun. 46, 7166–7168 (2010).
Zhou, J., Liu, Z. & Li, F. Upconversion nanophosphors for small-animal imaging. Chem. Soc. Rev. 41, 1323–1349 (2012).
Wang, J. et al. Lanthanide-doped LiYF4 nanoparticles: Synthesis and multicolor upconversion tuning. C. R. Chim. 13, 731–736 (2010).
Acknowledgements
The bulk of the work was supported by the Institute of Materials Research and Engineering (IMRE/12-8C0101) and the Singapore Ministry of Education (MOE2010-T2-1-083). Y.H. is grateful to KAUST Global Collaborative Research for the Academic Excellence Alliance (AEA) fund and P.Z. acknowledges the financial support from NSERC Canada. The PNC/XSD facilities at the Advanced Photon Source are supported by the US Department of Energy (DOE)-Basic Energy Sciences, a Major Resources Support grant from NSERC, the University of Washington, the Canadian Light Source, and the Advanced Photon Source. Use of the Advanced Photon Source was supported by the US DOE under contract no. DE-AC02-06CH11357. We thank PNC/XSD staff beamline scientist R. Gordon for synchrotron technical support. The authors thank H. Zhu, S. Animesh and R. Chen for technical assistance.
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J.W., R.D. and X.L. conceived the project, performed the nanocrystal synthesis, and wrote the paper. M.A.M. and P.Z. performed the synchrotron experiments. Y.H. contributed to the high-resolution TEM imaging and analysis. B.C., J.Y., F.W., D.C., T.S.A.H. and G.L. provided input into the design of the experiments and the preparation of the manuscript.
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Wang, J., Deng, R., MacDonald, M. et al. Enhancing multiphoton upconversion through energy clustering at sublattice level. Nature Mater 13, 157–162 (2014). https://doi.org/10.1038/nmat3804
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DOI: https://doi.org/10.1038/nmat3804
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