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.
References
Auzel, F. Upconversion and anti-Stokes processes with f and d ions in solids. Chem. Rev. 104, 139–174 (2004).
Chen, G., Ågren, H., Ohulchanskyy, T. Y. & Prasad, P. N. Light upconverting core–shell nanostructures: nanophotonic control for emerging applications. Chem. Soc. Rev. 44, 1680–1713 (2015).
Xie, Y. et al. Lanthanide-doped heterostructured nanocomposites toward advanced optical anti-counterfeiting and information storage. Light Sci. Appl. 11, 150 (2022).
Francés-Soriano, L., Estebanez, N., Pérez-Prieto, J. & Hildebrandt, N. DNA-coated upconversion nanoparticles for sensitive nucleic acid FRET biosensing. Adv. Funct. Mater. 32, 2201541 (2022).
Fernandez-Bravo, A. et al. Continuous-wave upconverting nanoparticle microlasers. Nat. Nanotechnol. 13, 572–577 (2018).
Chen, G. et al. (α-NaYbF4:Tm3+)/CaF2 core/shell nanoparticles with efficient near-infrared to near-infrared upconversion for high-contrast deep tissue bioimaging. ACS Nano 6, 8280–8287 (2012).
Liu, Y. et al. Amplified stimulated emission in upconversion nanoparticles for super-resolution nanoscopy. Nature 543, 229–233 (2017).
Wu, X. et al. Dye-sensitized core/active shell upconversion nanoparticles for optogenetics and bioimaging applications. ACS Nano 10, 1060–1066 (2016).
Deng, R. et al. Temporal full-colour tuning through non-steady-state upconversion. Nat. Nanotechnol. 10, 237–242 (2015).
Richards, B. S., Hudry, D., Busko, D., Turshatov, A. & Howard, I. A. Photon upconversion for photovoltaics and photocatalysis: a critical review. Chem. Rev. 121, 9165–9195 (2021).
Krämer, K. W. et al. Hexagonal sodium yttrium fluoride based green and blue emitting upconversion phosphors. Chem. Mater. 16, 1244–1251 (2004).
Fan, Y., Liu, L. & Zhang, F. Exploiting lanthanide-doped upconversion nanoparticles with core/shell structures. Nano Today 25, 68–84 (2019).
Zhang, Y., Lei, P., Zhu, X. & Zhang, Y. Full shell coating or cation exchange enhances luminescence. Nat. Commun. 12, 6178 (2021).
Zhou, B. et al. Enhancing multiphoton upconversion through interfacial energy transfer in multilayered nanoparticles. Nat. Commun. 11, 1174 (2020).
Feng, W., Sun, L. D. & Yan, C. H. Ag nanowires enhanced upconversion emission of NaYF4:Yb,Er nanocrystals via a direct assembly method. Chem. Commun. 29, 4393–4395 (2009).
Zhan, Q., Zhang, X., Zhao, Y., Liu, J. & He, S. Tens of thousands-fold upconversion luminescence enhancement induced by a single gold nanorod. Laser Photonics Rev. 9, 479–487 (2015).
Meng, Y. J. et al. Bright single-nanocrystal upconversion at sub 0.5 W cm−2 irradiance via coupling to single nanocavity mode. Nat. Photonics 17, 73–81 (2023).
Chen, G. et al. Energy-cascaded upconversion in an organic dye-sensitized core/shell fluoride nanocrystal. Nano Lett. 15, 7400–7407 (2015).
Garfield, D. J. et al. Enrichment of molecular antenna triplets amplifies upconverting nanoparticle emission. Nat. Photonics 12, 402–407 (2018).
Zou, W., Visser, C., Maduro, J. A., Pshenichnikov, M. S. & Hummelen, J. C. Broadband dye-sensitized upconversion of near-infrared light. Nat. Photoncs 6, 560–564 (2012).
Homann, C. et al. NaYF4:Yb,Er/NaYF4 core/shell nanocrystals with high upconversion luminescence quantum yield. Angew. Chem. Int. Ed. 57, 8765–8769 (2018).
Feng, Y. et al. Internal OH− induced cascade quenching of upconversion luminescence in NaYF4:Yb/Er nanocrystals. Light Sci. Appl. 10, 105 (2021).
Zhao, J. et al. Single-nanocrystal sensitivity achieved by enhanced upconversion luminescence. Nat. Nanotechnol. 8, 729–734 (2013).
García de Arquer, F. P. et al. Semiconductor quantum dots: technological progress and future challenges. Science 373, eaaz8541 (2021).
Dreaden, E. C., Alkilany, A. M., Huang, X., Murphy, C. J. & El-Sayed, M. A. The golden age: gold nanoparticles for biomedicine. Chem. Soc. Rev. 41, 2740–2779 (2012).
Liu, G. Advances in the theoretical understanding of photon upconversion in rare-earth activated nanophosphors. Chem. Soc. Rev. 44, 1635–1652 (2015).
Macedo, A. G. et al. Effects of phonon confinement on anomalous thermalization, energy transfer, and upconversion in Ln3+-doped Gd2O3 nanotubes. Adv. Funct. Mater. 20, 624–634 (2010).
Liu, G. K., Zhuang, H. Z. & Chen, X. Y. Restricted phonon relaxation and anomalous thermalization of rare earth ions in nanocrystals. Nano Lett. 2, 535–539 (2002).
Chen, X. et al. Confining energy migration in upconversion nanoparticles towards deep ultraviolet lasing. Nat. Commun. 7, 10304 (2016).
Quintanilla, M. et al. Cubic versus hexagonal-phase, size and morphology effects on the photoluminescence quantum yield of NaGdF4:Er3+/Yb3+ upconverting nanoparticles. Nanoscale 14, 1492–1504 (2022).
Wang, F., Wang, J. & Liu, X. Direct evidence of a surface quenching effect on size-dependent luminescence of upconversion nanoparticles. Angew. Chem. Int. Ed. 49, 7456–7460 (2010).
Johnson, N. J. et al. Direct evidence for coupled surface and concentration quenching dynamics in lanthanide-doped nanocrystals. J. Am. Chem. Soc. 139, 3275–3282 (2017).
Boyer, J. C. & van Veggel, F. C. Absolute quantum yield measurements of colloidal NaYF4: Er3+, Yb3+ upconverting nanoparticles. Nanoscale 2, 1417–1419 (2010).
Fischer, S., Bronstein, N. D., Swabeck, J. K., Chan, E. M. & Alivisatos, A. P. Precise tuning of surface quenching for luminescence enhancement in core–shell lanthanide-doped nanocrystals. Nano Lett. 16, 7241–7247 (2016).
Würth, C., Fischer, S., Grauel, B., Alivisatos, A. P. & Resch-Genger, U. Quantum yields, surface quenching, and passivation efficiency for ultrasmall core/shell upconverting nanoparticles. J. Am. Chem. Soc. 140, 4922–4928 (2018).
Jones, C. M. S., Gakamsky, A. & Marques-Hueso, J. The upconversion quantum yield (UCQY): a review to standardize the measurement methodology, improve comparability, and define efficiency standards. Sci. Technol. Adv. Mater. 22, 810–848 (2021).
Würth, C., Grabolle, M., Pauli, J., Spieles, M. & Resch-Genger, U. Relative and absolute determination of fluorescence quantum yields of transparent samples. Nat. Protoc. 8, 1535–1550 (2013).
Förster, T. 10th Spiers Memorial Lecture. Transfer mechanisms of electronic excitation. Discuss. Faraday Soc. 27, 7–17 (1959).
Förster, T. Zwischenmolekulare energiewanderung und fluoreszenz. Ann. Phys. 437, 55–75 (1948).
Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 21, 836–850 (2004).
Zuo, J. et al. Precisely tailoring upconversion dynamics via energy migration in core–shell nanostructures. Angew. Chem. Int. Ed. 57, 3054–3058 (2018).
Hossan, M. Y. et al. Explaining the nanoscale effect in the upconversion dynamics of β-NaYF4:Yb3+, Er3+ core and core–shell nanocrystals. J. Phys. Chem. C 121, 16592–16606 (2017).
Wang, F. & Liu, X. Upconversion multicolor fine-tuning: visible to near-infrared emission from lanthanide-doped NaYF4 nanoparticles. J. Am. Chem. Soc. 130, 5642–5643 (2008).
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