Abstract
Optical upconversion from lanthanide-doped nanoparticles is promising for a variety of applications ranging from bioimaging, optogenetics, nanothermometry, super-resolution nanoscopy and volumetric displays to solar cells. Despite remarkable progress made in enhancing upconversion to fuel these applications, achieving luminescence of upconversion nanoparticles (UCNPs) that is comparable to or higher than the bulk counterparts has been challenging due to nanoscale-induced quenching effects. Here we demonstrate a size-dependent lanthanide energy transfer effect in a conceptual design of hexagonal sodium yttrium fluoride (NaYF4) core–shell–shell NaYF4@NaYF4:Yb/Tm@NaYF4 UCNPs with depleted surface quenching. We show that precise control over the domain size (or the thickness of the middle shell doped with ytterbium (Yb) and thulium (Tm) from 1.2 to 13 nm) increases the lanthanide energy transfer efficiency (from 30.2 to 50.4%) and amplifies the upconversion quantum yield to a high value of 13.0 ± 1.3% in sub-50 nm UCNPs (excitation: 980 nm, 100 W cm−2), which is around fourfold higher than the micrometre-scale hexagonal NaYF4:Yb/Tm bulk counterparts. Spectroscopic studies and theoretical microscopic modelling reveal that long-range lanthanide energy transfer (>9.5 nm) takes place and underlies the observed size-dependent phenomena. Demonstration of size-dependent lanthanide energy transfer and upconversion quantum yields at the nanoscale transforms our long-existing conceptual understanding of lanthanide energy transfer (size independence), thereby having important implications for applications of lanthanide nanophotonics and biophotonics.
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Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.
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All codes used in this paper are available from the corresponding author upon reasonable request.
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Acknowledgements
This work is supported by the National Natural Science Foundation of China (52272270 and 51972084 to G.C.) and the Fundamental Research Funds for the Central Universities, China (AUGA5710052614 to G.C.).
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G.C. conceived the research; F.L. and Y.Z. prepared the UCNPs; K.W.K. synthesized the bulk upconverting materials; L.T. performed the Monte Carlo simulations; F.L. collected most of the experimental data, with contributions from X.Z., J.D., X.L., D.H. and R.F.; F.L., G.C. and L.T. discussed and interpreted the collected data; C.Y. provided valuable discussions and experimental supports; all authors contributed to the data analysis; the manuscript was written by F.L., L.T. and G.C., with comments from J.M.-H. and K.W.K.; and G.C. directed the research.
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Experimental procedures, instruments, measurement of UCQYs, Monte Carlo simulation, calculation of the brightness of UCNPs, supplementary figures and tables.
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Li, F., Tu, L., Zhang, Y. et al. Size-dependent lanthanide energy transfer amplifies upconversion luminescence quantum yields. Nat. Photon. (2024). https://doi.org/10.1038/s41566-024-01393-3
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DOI: https://doi.org/10.1038/s41566-024-01393-3
