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Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping

Nature volume 463, pages 1061–1065 (2010)Cite this article

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Abstract

Doping is a widely applied technological process in materials science that involves incorporating atoms or ions of appropriate elements into host lattices to yield hybrid materials with desirable properties and functions. For nanocrystalline materials, doping is of fundamental importance in stabilizing a specific crystallographic phase1, modifying electronic properties2,3,4, modulating magnetism5 as well as tuning emission properties6,7,8,9. Here we describe a material system in which doping influences the growth process to give simultaneous control over the crystallographic phase, size and optical emission properties of the resulting nanocrystals. We show that NaYF4 nanocrystals can be rationally tuned in size (down to ten nanometres), phase (cubic or hexagonal) and upconversion10,11,12 emission colour (green to blue) through use of trivalent lanthanide dopant ions introduced at precisely defined concentrations. We use first-principles calculations to confirm that the influence of lanthanide doping on crystal phase and size arises from a strong dependence on the size and dipole polarizability of the substitutional dopant ion. Our results suggest that the doping-induced structural and size transition, demonstrated here in NaYF4 upconversion nanocrystals, could be extended to other lanthanide-doped nanocrystal systems for applications ranging from luminescent biological labels12 to volumetric three-dimensional displays13.

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Figure 1: Phase transformation in NaREF 4 structures by lanthanide doping.
Figure 2: TEM characterization of NaYF 4 :Yb/Er (18/2 mol%) nanocrystals doped with various concentrations of Gd 3+ ions.
Figure 3: Photoluminescence studies of NaYF4:Yb/Er (18/2 mol%) nanocrystals with varying dopant concentration of Gd3+.
Figure 4: Photoluminescence studies of NaYF 4 nanocrystals dispersed in solutions and embedded in PDMS composite materials.

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Acknowledgements

We thank G. A. Ozin, X. Chen, F. Stellacci, C. Yan, Y. Xia, L. Cademartiri, T. Nann, Y. Li and Y. C. Cao for discussions. This study was supported in part by the National University of Singapore (NUS), the Ministry of Education of Singapore, the Singapore-MIT Alliance, and the Agency for Science, Technology and Research (A*STAR). X.L. is grateful to the NUS for a Young Investigator Award.

Author Contributions F.W. and X.L. conceived the experiments and wrote the paper. F.W. and J.W. were primarily responsible for the experiments. Y.H., J.X. and H.C. performed the TEM characterization. C.S.L. and M.H. contributed to the volumetric 3D display studies. Y.L. and C.Z. performed theoretical calculations. All authors contributed to the analysis of this manuscript.

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Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, 117543, Singapore

    Feng Wang, Juan Wang, Chun Zhang & Xiaogang Liu

  2. Division of Chemical and Life Science and Engineering, Membrane Research Centre, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia

    Yu Han

  3. Optical Materials and Systems Division, Data Storage Institute, A*STAR, 117608, Singapore,

    Chin Seong Lim & Minghui Hong

  4. Department of Physics, National University of Singapore, 117543, Singapore

    Yunhao Lu & Chun Zhang

  5. Division of Chemistry and Biological Chemistry, Nanyang Technological University, 637371 Singapore

    Jun Xu & Hongyu Chen

  6. Department of Electrical and Computer Engineering, National University of Singapore, 117543, Singapore

    Minghui Hong

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Wang, F., Han, Y., Lim, C. et al. Simultaneous phase and size control of upconversion nanocrystals through lanthanide doping. Nature 463, 1061–1065 (2010). https://doi.org/10.1038/nature08777

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