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Long-lived modulation of plasmonic absorption by ballistic thermal injection

Nature Nanotechnology volume 16, pages 47–51 (2021)Cite this article

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Abstract

Light–matter interactions that induce charge and energy transfer across interfaces form the foundation for photocatalysis1,2, energy harvesting3 and photodetection4, among other technologies. One of the most common mechanisms associated with these processes relies on carrier injection. However, the exact role of the energy transport associated with this hot-electron injection remains unclear. Plasmon-assisted photocatalytic efficiencies can improve when intermediate insulation layers are used to inhibit the charge transfer5,6 or when off-resonance excitations are employed7, which suggests that additional energy transport and thermal effects could play an explicit role even if the charge transfer is inhibited8. This provides an additional interfacial mechanism for the catalytic and plasmonic enhancement at interfaces that moves beyond the traditionally assumed physical charge injection9,10,11,12. In this work, we report on a series of ultrafast plasmonic measurements that provide a direct measure of electronic distributions, both spatially and temporally, after the optical excitation of a metal/semiconductor heterostructure. We explicitly demonstrate that in cases of strong non-equilibrium, a novel energy transduction mechanism arises at the metal/semiconductor interface. We find that hot electrons in the metal contact transfer their energy to pre-existing free electrons in the semiconductor, without an equivalent spatiotemporal transfer of charge. Further, we demonstrate that this ballistic thermal injection mechanism can be utilized as a unique means to modulate plasmonic interactions. These experimental results are well-supported by both rigorous multilayer optical modelling and first-principle ab initio calculations.

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Fig. 1: Proposed mechanism of interfacial energy transfer and experimental schematic.
Fig. 2: Interpreting subsurface heat deposition with ab initio calculations.
Fig. 3: Ultrafast plasmonic modulation through BTI.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge funding from the US Department of Defense, Multidisciplinary University Research Initiative through the Army Research Office, Grant no. W911NF-16-1-0406. J.R.N. and J.D.C. appreciate support from the Office of Naval Research, Grant no. N00014-18-1-2107.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA, USA

    John A. Tomko & Patrick E. Hopkins

  2. Army Research Office, CCDC US Army Research Laboratory, Research Triangle Park, NC, USA

    Evan L. Runnerstrom

  3. Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC, USA

    Evan L. Runnerstrom, Kyle P. Kelley & Jon-Paul Maria

  4. Department of Chemistry, University of Southern California, Los Angeles, CA, USA

    Yi-Siang Wang, Weibin Chu & Oleg V. Prezhdo

  5. Department of Physics and Astronomy, University of Southern California, Los Angeles, CA, USA

    Yi-Siang Wang, Weibin Chu & Oleg V. Prezhdo

  6. Institute of Nanoscale Science and Engineering, Vanderbilt University, Nashville, TN, USA

    Joshua R. Nolen & Joshua D. Caldwell

  7. Department of Mechanical and Aerospace Engineering, University of Virginia, Charlottesville, VA, USA

    David H. Olson & Patrick E. Hopkins

  8. Department of Materials Science and Engineering, Pennsylvania State University, State College, PA, USA

    Angela Cleri, Josh Nordlander & Jon-Paul Maria

  9. Department of Physics, University of Virginia, Charlottesville, VA, USA

    Patrick E. Hopkins

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Contributions

P.E.H. and J.-P.M. conceived the idea and supervised the project; J.A.T. performed the TDTR and infrared pump–probe measurements and corresponding analysis; E.L.R., K.P.K., J.N. and A.C. grew and characterized the CdO films; Y.-S.W., W.C. and O.V.P. performed the ab initio calculations; J.A.T. and D.H.O. performed the two-temperature model (TTM) calculations; J.A.T., J.R.N. and J.D.C. performed the transfer matrix method (TMM) calculations and provided insight on the dispersion relations. J.A.T. wrote the manuscript with input from all the authors; all the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Patrick E. Hopkins.

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The authors declare no competing interests.

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Peer review information Nature Nanotechnology thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Discussion and Figs. 1–9.

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Tomko, J.A., Runnerstrom, E.L., Wang, YS. et al. Long-lived modulation of plasmonic absorption by ballistic thermal injection. Nat. Nanotechnol. 16, 47–51 (2021). https://doi.org/10.1038/s41565-020-00794-z

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