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Enhancing multiphoton upconversion through energy clustering at sublattice level

Nature Materials volume 13, pages 157–162 (2014)Cite this article

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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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Figure 1: Schematic representation showing the topological energy migration pathways in different types of crystal sublattice.
Figure 2: Structural characterization of the as-synthesized KYb2F7:Er (2 mol%) nanocrystals.
Figure 3: Optical characterization of the as-synthesized KYb2F7:Er nanocrystals.
Figure 4: Enzyme activity screening using the KYb2F7:Er (2 mol%) nanocrystals.

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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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Author notes

  1. Juan Wang and Renren Deng: These authors contributed equally to this work

Authors and Affiliations

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

    Juan Wang, Renren Deng, Tzi Sum Andy Hor & Xiaogang Liu

  2. Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4J3, Canada

    Mark A. MacDonald & Peng Zhang

  3. Department of Applied Physics, The Hong Kong Polytechnic University, Kowloon, Hong Kong

    Bolei Chen & Jikang Yuan

  4. Institute of Materials Research and Engineering, Agency for Science, Technology and Research, Singapore 117602, Singapore

    Feng Wang, Dongzhi Chi, Tzi Sum Andy Hor & Xiaogang Liu

  5. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Guokui Liu

  6. Physical Science and Engineering Division, Advanced Membrane and Porous Materials Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia

    Yu Han

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Contributions

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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Correspondence to Xiaogang Liu.

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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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