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Efficient photon upconversion enabled by strong coupling between silicon quantum dots and anthracene

Nature Chemistry volume 15, pages 1172–1178 (2023)Cite this article

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Abstract

Hybrid structures formed between organic molecules and inorganic quantum dots can accomplish unique photophysical transformations by taking advantage of their disparate properties. The electronic coupling between these materials is typically weak, leading photoexcited charge carriers to spatially localize to the dot or to a molecule at its surface. However, we show that by converting a chemical linker that covalently binds anthracene molecules to silicon quantum dots from a carbon–carbon single bond to a double bond, we access a strong coupling regime where excited carriers spatially delocalize across both anthracene and silicon. By pushing the system to delocalize, we design a photon upconversion system with a higher efficiency (17.2%) and lower threshold intensity (0.5 W cm–2) than that of a corresponding weakly coupled system. Our results show that strong coupling between molecules and nanostructures achieved through targeted linking chemistry provides a complementary route for tailoring properties in materials for light-driven applications.

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Fig. 1: Structure and absorption spectra of Si QDs.
Fig. 2: State energies and upconversion emission spectra of Si:9VA.
Fig. 3: Computed electronic structure of Si:9EA and Si:9VA.
Fig. 4: Photoexcited kinetics of Si:9EA and Si:9VA.
Fig. 5: Controlling the energy of Si:9VA’s T1 state via strong coupling.

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Source data are provided with this paper. Additional source data for figures contained in the Supplementary Information are available from the authors upon request.

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Acknowledgements

This work was supported by National Science Foundation grant CMMI-2053567. Work at the University of Texas at Austin was additionally supported by the Welch Foundation (grant F-1885). Aspects of this work undertaken at the University of Colorado Boulder and the University of Texas at Austin were supported by the W. M. Keck Foundation (grant 22605). Work at the University of California, Riverside was also supported by Air Force Office of Scientific Research grant FA9550-20-1-0112. This work used the Summit supercomputer, which is supported by the National Science Foundation (awards ACI-1532235 and ACI-1532236), the University of Colorado Boulder and Colorado State University. The Summit supercomputer is a joint effort of the University of Colorado Boulder and Colorado State University.

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Author notes

  1. These authors contributed equally: Kefu Wang, R. Peyton Cline, Joseph Schwan.

Authors and Affiliations

  1. Department of Chemistry, University of Utah, Salt Lake City, UT, USA

    Kefu Wang & Ming Lee Tang

  2. Department of Chemistry, University of California, Riverside, Riverside, CA, USA

    Kefu Wang & Ming Lee Tang

  3. Department of Chemistry, University of Colorado Boulder, Boulder, CO, USA

    R. Peyton Cline & Joel D. Eaves

  4. Department of Mechanical Engineering, University of California, Riverside, Riverside, CA, USA

    Joseph Schwan & Lorenzo Mangolini

  5. Department of Chemistry, The University of Texas at Austin, Austin, TX, USA

    Jacob M. Strain & Sean T. Roberts

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  1. Kefu Wang
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Contributions

K.W. conducted the nanocrystal functionalization, photon upconversion and nanosecond TA experiments. R.P.C. performed the electronic structure calculations; J.S., the non-thermal plasma synthesis; and J.M.S. the subnanosecond TA. K.W., J.S., L.M. and M.L.T. conceived of the project. R.P.C. and J.D.E. designed the electronic structure calculations. S.T.R. composed the manuscript with substantial contributions from all authors.

Corresponding authors

Correspondence to Sean T. Roberts, Lorenzo Mangolini, Joel D. Eaves or Ming Lee Tang.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–13, Tables 1–3 and discussion.

Source data

Source Data Fig. 1

Absorption spectra of chemically functionalized silicon QDs.

Source Data Fig. 2

Upconversion emission spectra of photon upconversion systems based on Si:9VA.

Source Data Fig. 3

Triplet exciton DOS computed for Si:9EA and Si:9VA.

Source Data Fig. 4

TA spectra of Si:9EA and Si:9VA.

Source Data Fig. 5

Changes in TA signals and upconversion emission spectra of Si:9EA and Si:9VA systems with changing anthracene surface concentration.

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Wang, K., Cline, R.P., Schwan, J. et al. Efficient photon upconversion enabled by strong coupling between silicon quantum dots and anthracene. Nat. Chem. 15, 1172–1178 (2023). https://doi.org/10.1038/s41557-023-01225-x

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