Activation of the surface dark-layer to enhance upconversion in a thermal field

Abstract

Thermal quenching, in which light emission experiences a loss with increasing temperature, broadly limits luminescent efficiency at higher temperature in optical materials, such as lighting phosphors1,2,3 and fluorescent probes4,5,6. Thermal quenching is commonly caused by the increased activity of phonons that leverages the non-radiative relaxation pathways. Here, we report a kind of heat-favourable phonons existing at the surface of lanthanide-doped upconversion nanomaterials to combat thermal quenching. It favours energy transfer from sensitizers to activators to pump up the intermediate excited-state upconversion process. We identify that the oxygen moiety chelating Yb3+ ions, [Yb···O], is the key underpinning this enhancement. We demonstrate an approximately 2,000-fold enhancement in blue emission for 9.7 nm Yb3+-Tm3+ co-doped nanoparticles at 453 K. This strategy not only provides a powerful solution to illuminate the dark layer of ultra-small upconversion nanoparticles, but also suggests a new pathway to build high-efficiency upconversion systems.

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Fig. 1: Schematic illustration of the surface-phonon-enhanced upconversion process.
Fig. 2: Surface-phonon-enhanced upconversion in different sensitizer−activator systems.
Fig. 3: Surface engineering to investigate surface-phonon-enhanced upconversion.
Fig. 4: Surface phonons significantly enhance the brightness of ultra-small upconversion nanoparticles.

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Acknowledgements

This project is primarily supported by the Australian Research Council (ARC) Discovery Early Career Researcher Award Scheme (J.Z., DE180100669), Chancellor’s Postdoctoral Fellowship Scheme at the University of Technology Sydney (J.Z.), and ARC Future Fellowship Scheme (D.J., FT 130100517).

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Contributions

J.Z. and D.J. conceived the project and designed the experiments; S.W., J.L., and J.Z. conducted synthesis; C.C. and J.Z. performed the security ink printing and imaging; S.A.T. carried out simulation work; W.R. conducted the surface modification; C.M. and F.W. built the optical testing system; J.Z. conducted the spectroscopic characterization; J.Z. and D.J. prepared the figures, data analysis, supplementary information sections, and wrote the manuscript with input from other authors.

Corresponding authors

Correspondence to Jiajia Zhou or Dayong Jin.

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Supplementary Information

Supplementary Data; Supplementary Figures 1–7; Supplementary Tables 1–2; Supplementary Reference 1.

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Zhou, J., Wen, S., Liao, J. et al. Activation of the surface dark-layer to enhance upconversion in a thermal field. Nature Photon 12, 154–158 (2018). https://doi.org/10.1038/s41566-018-0108-5

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