Letter | Published:

Amplified stimulated emission in upconversion nanoparticles for super-resolution nanoscopy

Nature volume 543, pages 229233 (09 March 2017) | Download Citation

Abstract

Lanthanide-doped glasses and crystals are attractive for laser applications because the metastable energy levels of the trivalent lanthanide ions facilitate the establishment of population inversion and amplified stimulated emission at relatively low pump power1,2,3. At the nanometre scale, lanthanide-doped upconversion nanoparticles (UCNPs) can now be made with precisely controlled phase, dimension and doping level4,5. When excited in the near-infrared, these UCNPs emit stable, bright visible luminescence at a variety of selectable wavelengths6,7,8,9, with single-nanoparticle sensitivity10,11,12,13, which makes them suitable for advanced luminescence microscopy applications. Here we show that UCNPs doped with high concentrations of thulium ions (Tm3+), excited at a wavelength of 980 nanometres, can readily establish a population inversion on their intermediate metastable 3H4 level: the reduced inter-emitter distance at high Tm3+ doping concentration leads to intense cross-relaxation, inducing a photon-avalanche-like effect that rapidly populates the metastable 3H4 level, resulting in population inversion relative to the 3H6 ground level within a single nanoparticle. As a result, illumination by a laser at 808 nanometres, matching the upconversion band of the 3H4 → 3H6 transition, can trigger amplified stimulated emission to discharge the 3H4 intermediate level, so that the upconversion pathway to generate blue luminescence can be optically inhibited. We harness these properties to realize low-power super-resolution stimulated emission depletion (STED) microscopy and achieve nanometre-scale optical resolution (nanoscopy), imaging single UCNPs; the resolution is 28 nanometres, that is, 1/36th of the wavelength. These engineered nanocrystals offer saturation intensity two orders of magnitude lower than those of fluorescent probes currently employed in stimulated emission depletion microscopy, suggesting a new way of alleviating the square-root law that typically limits the resolution that can be practically achieved by such techniques.

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Acknowledgements

This project was primarily supported by the Australian Research Council (ARC) Future Fellowship Scheme (D.J., FT 130100517), the ARC Centre of Excellence for Nanoscale BioPhotonics (CE140100003), the Natural Science Foundation of China (61428501, 31327901, 61475010), and the National Instrumentation Project of China (2013YQ03065102). Y. Lu acknowledges support from a Macquarie University Research Fellowship.

Author information

Author notes

    • Yujia Liu
    • , Yiqing Lu
    •  & Xusan Yang

    These authors contributed equally to this work.

Affiliations

  1. Advanced Cytometry Laboratories, ARC Centre of Excellence for Nanoscale BioPhotonics (CNBP), Macquarie University, Sydney, New South Wales 2109, Australia

    • Yujia Liu
    • , Yiqing Lu
    • , Xianlin Zheng
    • , Shihui Wen
    • , Fan Wang
    • , Xavier Vidal
    • , Jiangbo Zhao
    • , Deming Liu
    • , Zhiguang Zhou
    • , Chenshuo Ma
    • , James A. Piper
    • , Peng Xi
    •  & Dayong Jin
  2. Department of Physics and Astronomy, Macquarie University, Sydney, New South Wales 2109, Australia

    • Yujia Liu
    • , Yiqing Lu
    • , Xianlin Zheng
    • , Fan Wang
    • , Xavier Vidal
    • , Jiangbo Zhao
    • , Deming Liu
    • , James A. Piper
    •  & Dayong Jin
  3. Department of Biomedical Engineering, College of Engineering, Peking University, Beijing 100871, China

    • Yujia Liu
    • , Xusan Yang
    •  & Peng Xi
  4. School of Life Sciences and Biotechnology, Shanghai Jiao Tong University, Shanghai 200241, China

    • Yujia Liu
  5. Institute for Biomedical Materials and Devices (IBMD), Faculty of Science, University of Technology Sydney, Sydney, New South Wales 2007, Australia

    • Shihui Wen
    • , Fan Wang
    • , Zhiguang Zhou
    • , Jiajia Zhou
    •  & Dayong Jin

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Contributions

D.J. and P.X. conceived the project. D.J., P.X. and J.A.P. supervised the research. Y. Liu, X.Y., F.W., X.Z. and Z.Z. conducted the optical experiments. S.W., J. Zhao, D.L., J. Zhou, and C.M. synthesized the upconversion nanoparticles. Y. Lu carried out the modelling. Y. Lu, Y. Liu, X.Y., X.Z., X.V., P.X. and D.J. analysed the results, prepared the figures and wrote the manuscript. All authors participated in discussion and editing of the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Yiqing Lu or Peng Xi or Dayong Jin.

Reviewer Information Nature thanks Y. D. Suh and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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DOI

https://doi.org/10.1038/nature21366

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