Enrichment of molecular antenna triplets amplifies upconverting nanoparticle emission

Abstract

Efficient photon upconversion at low light intensities promises major advances in technologies spanning solar energy harvesting to deep-tissue biophotonics. Here, we discover the critical mechanisms that enable near-infrared dye antennas to significantly enhance performance in lanthanide-doped upconverting nanoparticle (UCNP) systems, and leverage these findings to design dye–UCNP hybrids with a 33,000-fold increase in brightness and a 100-fold increase in efficiency over bare UCNPs. We show that increasing the lanthanide content in the UCNPs shifts the primary energy donor from the dye singlet to its triplet, and the resultant triplet states then mediate energy transfer into the nanocrystals. Time-gated phosphorescence, density functional theory, singlet lifetimes and triplet-quenching experiments support these findings. This interplay between the excited-state populations in organic antennas and the composition of UCNPs presents new design rules that overcome the limitations of previous upconverting materials, enabling performances now relevant for photovoltaics, biophotonics and infrared detection.

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Fig. 1: Dye-functionalized UCNPs, their mechanism of energy transfer, and the larger effective absorption cross-section of dyes relative to UCNPs.
Fig. 2: Time-gated photoluminescence as evidence of resonant triplet states.
Fig. 3: Evidence of triplet energy transfer to UCNPs.
Fig. 4: Upconverted performance improvements by enhancing the dye triplet population and coupling pathways.

References

  1. 1.

    Zou, W., Visser, C., Maduro, J. A., Pshenichnikov, M. S. & Hummelen, J. C. Broadband dye-sensitized upconversion of near-infrared light. Nat. Photon. 6, 560–564 (2012).

    ADS  Article  Google Scholar 

  2. 2.

    Zhou, B., Shi, B., Jin, D. & Liu, X. Controlling upconversion nanocrystals for emerging applications. Nat. Nanotech. 10, 924–936 (2015).

    ADS  Article  Google Scholar 

  3. 3.

    Briggs, J. A., Atre, A. C. & Dionne, J. A. Narrow-bandwidth solar upconversion: case studies of existing systems and generalized fundamental limits. J. Appl. Phys. 113, 124509 (2013).

    ADS  Article  Google Scholar 

  4. 4.

    Park, Y. Il, Lee, K. T., Suh, Y. D. & Hyeon, T. Upconverting nanoparticles: a versatile platform for wide-field two-photon microscopy and multi-modal in vivo imaging. Chem. Soc. Rev. 44, 1302–1317 (2014).

    Article  Google Scholar 

  5. 5.

    Liu, Y. et al. Amplified stimulated emission in upconversion nanoparticles for super-resolution nanoscopy. Nature 543, 229–233 (2017).

    ADS  Article  Google Scholar 

  6. 6.

    Wang, C., Li, X. & Zhang, F. Bioapplications and biotechnologies of upconversion nanoparticle-based nanosensors. Analyst. 141, 3601–3620 (2016).

    ADS  Article  Google Scholar 

  7. 7.

    Wu, X. et al. Dye-sensitized core/active shell upconversion nanoparticles for optogenetics and bioimaging applications. ACS Nano 10, 1060–1066 (2016).

    Article  Google Scholar 

  8. 8.

    Hososhima, S. et al. Near-infrared (NIR) up-conversion optogenetics. Sci. Rep. 5, 16533 (2015).

    ADS  Article  Google Scholar 

  9. 9.

    Schmidt, T. W. & Castellano, F. N. Photochemical conversion: the primacy of kinetics. J. Phys. Chem. Lett. 5, 4062–4072 (2014).

    Article  Google Scholar 

  10. 10.

    Schulze, T. F. & Schmidt, T. W. Photochemical upconversion: present status and prospects for its application to solar energy conversion. Energy Environ. Sci. 8, 103–125 (2015).

    Article  Google Scholar 

  11. 11.

    Olivier, J. H. et al. Near-infrared-to-visible photon upconversion enabled by conjugated porphyrinic sensitizers under low-power noncoherent illumination. J. Phys. Chem. A 119, 5642–5649 (2015).

    Article  Google Scholar 

  12. 12.

    Gargas, D. J. et al. Engineering bright sub-10-nm upconverting nanocrystals for single-molecule imaging. Nat. Nanotech. 9, 300–305 (2014).

    ADS  Article  Google Scholar 

  13. 13.

    Wu, S. et al. Non-blinking and photostable upconverted luminescence from single lanthanide-doped nanocrystals. Proc. Natl Acad. Sci. USA 106, 10917–10921 (2009).

    ADS  Article  Google Scholar 

  14. 14.

    Park, Y. Il et al. Nonblinking and nonbleaching upconverting nanoparticles as an optical imaging nanoprobe and T1 magnetic resonance imaging contrast agent. Adv. Mater. 21, 4467–4471 (2009).

    Article  Google Scholar 

  15. 15.

    Chen, G. et al. Energy-cascaded upconversion in an organic dye-sensitized core/shell fluoride nanocrystal. Nano Lett. 15, 7400–7407 (2015).

    ADS  Article  Google Scholar 

  16. 16.

    Shao, W. et al. Tunable narrow band emissions from dye-sensitized core/shell/shell nanocrystals in the second near-infrared biological window. J. Am. Chem. Soc. 138, 16191–16195 (2016).

    Article  Google Scholar 

  17. 17.

    Chen, G. et al. Efficient broadband upconversion of near-infrared light in dye-sensitized core/shell nanocrystals. Adv. Opt. Mater. 4, 1760–1766 (2016).

    Article  Google Scholar 

  18. 18.

    Lee, J. et al. Ultra-wideband multi-dye-sensitized upconverting nanoparticles for information security application. Adv. Mater. 29, 1603169 (2017).

    Article  Google Scholar 

  19. 19.

    Du, C., Wang, H., Yang, F. & Hammel, P. C. Systematic variation of spin–orbit coupling with d-orbital filling: large inverse spin Hall effect in 3d transition metals. Phys. Rev. B 90, 140407(R) (2014).

    ADS  Article  Google Scholar 

  20. 20.

    Klink, S. I., Keizer, H. & van Veggel, F. C. J. M. Transition metal complexes as photosensitizers for near-infrared lanthanide luminescence. Angew. Chem. Int. Ed. 39, 4319–4321 (2000).

    Article  Google Scholar 

  21. 21.

    Beeby, A., Faulkner, S., Parker, D. & Williams, J. A. G. Sensitised luminescence from phenanthridine appended lanthanide complexes: analysis of triplet mediated energy transfer processes in terbium, europium and neodymium complexes. J. Chem. Soc. Perkin Trans. 2, 1268–1273 (2001).

    Article  Google Scholar 

  22. 22.

    Faulkner, S., Natrajan, L. S., Perry, W. S. & Sykes, D. Sensitised luminescence in lanthanide containing arrays and df hybrids. Dalton Trans. 3890–3899 (2009).

  23. 23.

    Klink, S. I. et al. A systematic study of the photophysical processes in polydentate triphenylene-functionalized Eu3+. J. Phys. Chem. A 104, 5457–5468 (2000).

    Article  Google Scholar 

  24. 24.

    Bunzli, J. G. & Piguet, C. Taking advantage of luminescent lanthanide ions. Chem. Soc. Rev. 34, 1048–1077 (2005).

    Article  Google Scholar 

  25. 25.

    Thompson, N. J. et al. Energy harvesting of non-emissive triplet excitons in tetracene by emissive PbS nanocrystals. Nat. Mater. 13, 1039–1043 (2014).

    ADS  Article  Google Scholar 

  26. 26.

    Cedric, M., Garakyaraghi, S., Razgoniaeva, N., Zamkov, M. & Castellano, F. N. Direct observation of triplet energy transfer from semiconductor nanocrystals. Science 351, 369–372 (2016).

    ADS  Article  Google Scholar 

  27. 27.

    Tabachnyk, M. et al. Resonant energy transfer of triplet excitons from pentacene to PbSe nanocrystals. Nat. Mater. 13, 1033–1038 (2014).

    ADS  Article  Google Scholar 

  28. 28.

    Agbo, P., Xu, T., Sturzbecher-Hoehne, M. & Abergel, R. J. Enhanced ultraviolet photon capture in ligand-sensitized nanocrystals. ACS Photon. 3, 547–552 (2016).

    Article  Google Scholar 

  29. 29.

    Huang, Z. et al. Hybrid molecule-nanocrystal photon upconversion across the visible and near-infrared. Nano. Lett. 15, 5552–5557 (2015).

    ADS  Article  Google Scholar 

  30. 30.

    Piland, G. B., Huang, Z., Lee Tang, M. & Bardeen, C. J. Dynamics of energy transfer from CdSe nanocrystals to triplet states of anthracene ligand molecules. J. Phys. Chem. C 120, 5883–5889 (2016).

    Article  Google Scholar 

  31. 31.

    Wang, F. et al. Tuning upconversion through energy migration in core–shell nanoparticles. Nat. Mater. 10, 968–973 (2011).

    ADS  Article  Google Scholar 

  32. 32.

    Marling, J. B., Gregg, D. W. & Wood, L. Chemical quenching of the triplet state in flashlamp-excited liquid organic lasers. Appl. Phys. Lett. 17, 527–530 (1970).

    ADS  Article  Google Scholar 

  33. 33.

    Pappalardo, R., Samelson, H. & Lempicki, A. Long pulse laser emission from rhodamine 6G using cyclooctatetraene. Appl. Phys. Lett. 16, 267–269 (1970).

    ADS  Article  Google Scholar 

  34. 34.

    Schols, S., Kadashchuk, A., Heremans, P., Helfer, A. & Scherf, U. Triplet excitation scavenging in films of conjugated polymers. ChemPhysChem 10, 1071–1076 (2009).

    Article  Google Scholar 

  35. 35.

    Schaap, A. P. Singlet Molecular Oxygen (Dowden, Hutchinson, & Ross: Stroudsburg, PA, 1976).

    Google Scholar 

  36. 36.

    Gorka, A. P., Nani, R. R., Zhu, J., Mackem, S. & Schnermann, M. J. A near-IR uncaging strategy based on cyanine photochemistry. J. Am. Chem. Soc. 136, 14153–14159 (2014).

    Article  Google Scholar 

  37. 37.

    Han, Y. et al. Degradation observations of encapsulated planar CH3NH3PbI3 perovskite solar cells at high temperatures and humidity. J. Mater. Chem. A 3, 8139–8147 (2015).

    Article  Google Scholar 

  38. 38.

    Ow, H. et al. Bright and stable core–shell fluorescent silica nanoparticles. Nano Lett. 5, 113–117 (2005).

    ADS  Article  Google Scholar 

  39. 39.

    Pokhrel, M., Kumar, G. A. & Sardar, D. K. Highly efficient NIR to NIR and VIS upconversion in Er3+ and Yb3+ doped in M2O2S (M = Gd, La, Y). J. Mater. Chem. A 1, 11595–11606 (2013).

    Article  Google Scholar 

  40. 40.

    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).

    ADS  Article  Google Scholar 

  41. 41.

    Johnson, N. J. J. et al. Direct evidence for coupled surface and concentration quenching dynamics in lanthanide-doped nanocrystals. J. Am. Chem. Soc. 139, 3275–3282 (2017).

    Article  Google Scholar 

  42. 42.

    Chan, E. M., Levy, E. S. & Cohen, B. E. Rationally designed energy transfer in upconverting nanoparticles. Adv. Mater. 27, 5753–5761 (2015).

    Article  Google Scholar 

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Acknowledgements

The authors thank S. Fischer, K. Raymond and K. Yao for helpful discussions, and T. Chen for her invaluable experimental assistance. This work was supported by the National Science Foundation SAGE IGERT fellowship (to D.J.G.) and the Chinese Scholarship Council fellowship (B.T.). Portions of this research were supported by the Global Research Laboratory (GRL) Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (no. 2016911815). This work was performed at the Molecular Foundry and was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy (contract no. DE-AC02-05CH11231). The computational work performed here was supported by the Director, Office of Science, Chemical Sciences, Geosciences and Biosciences Division of the US Department of Energy, under contract no. DEAC02-05CH1123.

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The scientific concepts, ideas and experimental designs were the result of interactions and discussions between D.J.G., P.J.S., B.E.C., N.J.B., E.M.C. and Y.D.S. D.J.G., E.M.C., N.A.T., C.A.T. and B.T. synthesized the nanoparticles. D.J.G., N.J.B. and E.S.B. conducted the spectroscopic measurements. D.J.G. and E.M.C. conducted the QY measurements. S.M.H. and J.B.N. performed the theoretical modelling. B.S. and S.A. conducted the electron microscopy. D.J.G., N.J.B., E.M.C., B.E.C. and P.J.S. wrote the paper, in coordination with all the authors.

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Correspondence to Emory M. Chan or Bruce E. Cohen or P. James Schuck.

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Supplementary Methods; Supplementary Figures 1–16; Supplementary Table 1; Supplementary discussion; and Supplementary references.

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Garfield, D.J., Borys, N.J., Hamed, S.M. et al. Enrichment of molecular antenna triplets amplifies upconverting nanoparticle emission. Nature Photon 12, 402–407 (2018). https://doi.org/10.1038/s41566-018-0156-x

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