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Long-lived modulation of plasmonic absorption by ballistic thermal injection

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.

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.

References

  1. 1.

    Serpone, N. & Emeline, A. V. Semiconductor photocatalysis—past, present, and future outlook. J. Phys. Chem. Lett. 3, 673–677 (2012).

    CAS  Article  Google Scholar 

  2. 2.

    Kim, S. M., Hyosun, L. & Park, J. Y. Charge transport in metal-oxide interfaces: genesis and detection of hot electron flow and its role in heterogeneous catalysis. Catal. Lett. 145, 299–308 (2015).

    CAS  Article  Google Scholar 

  3. 3.

    Clavero, C. Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices. Nat. Photon. 8, 95–103 (2014).

    CAS  Article  Google Scholar 

  4. 4.

    Knight, M. W., Sobhani, H., Nordlander, P. & Halas, N. J. Photodetection with active optical antennas. Science 332, 702–704 (2011).

    CAS  Article  Google Scholar 

  5. 5.

    Asapu, R. et al. Electron transfer and near-field mechanisms in plasmonic gold-nanoparticle-modified TiO2 photocatalytic systems. ACS Appl. Nano Mater. 2, 4067–4074 (2019).

    CAS  Article  Google Scholar 

  6. 6.

    Chen, J. J., Wu, J. C., Wu, P. C. & Tsai, D. P. Improved photocatalytic activity of shell-isolated plasmonic photocatalyst Au@SiO2/TiO2 by promoted LSPR. J. Phys. Chem. C 116, 26535–26542 (2012).

    CAS  Article  Google Scholar 

  7. 7.

    Priebe, J. B. et al. Water reduction with visible light: synergy between optical transitions and electron transfer in Au–TiO2 catalysts visualized by in situ EPR spectroscopy. Angew. Chem. Int. Ed. 52, 11420–11424 (2013).

    CAS  Article  Google Scholar 

  8. 8.

    Yu, Y., Sundaresan, V. & Willets, K. A. Hot carriers versus thermal effects: resolving the enhancement mechanisms for plasmon-mediated photoelectrochemical reactions. J. Phys. Chem. C 122, 5040–5048 (2018).

    CAS  Article  Google Scholar 

  9. 9.

    Narang, P., Sundararaman, R. & Atwater, H. A. Plasmonic hot carrier dynamics in solid-state and chemical systems for energy conversion. Nanophotonics 5, 96–111 (2016).

    CAS  Article  Google Scholar 

  10. 10.

    Brongersma, M. L., Halas, N. J. & Nordlander, P. Plasmon-induced hot carrier science and technology. Nat. Nanotechnol. 10, 25–34 (2015).

    CAS  Article  Google Scholar 

  11. 11.

    Sundararaman, R., Narang, P., Jermyn, A. S., Iii, W. A. G. & Atwater, H. A. Theoretical predictions for hot-carrier generation from surface plasmon decay. Nat. Commun. 5, 5788 (2014).

    CAS  Article  Google Scholar 

  12. 12.

    Wu, K., Chen, J., McBride, J. R. & Lian, T. Efficient hot-electron transfer by a plasmon-induced interfacial charge-transfer transition. Science 349, 632–635 (2015).

    CAS  Article  Google Scholar 

  13. 13.

    Lin, Z., Zhigilei, L. V. & Celli, V. Electron–phonon coupling and electron heat capacity of metals under conditions of strong electron–phonon nonequilibrium. Phys. Rev. B 77, 075133 (2008).

    Article  Google Scholar 

  14. 14.

    Sachet, E. et al. Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics. Nat. Mater. 14, 414–420 (2015).

    CAS  Article  Google Scholar 

  15. 15.

    Runnerstrom, E. L., Kelley, K. P., Sachet, E., Shelton, C. T. & Maria, J. P. Epsilon-near-zero modes and surface plasmon resonance in fluorine-doped cadmium oxide thin films. ACS Photon. 4, 1885–1892 (2017).

    CAS  Article  Google Scholar 

  16. 16.

    Runnerstrom, E. L. et al. Polaritonic hybrid-epsilon-near-zero modes: beating the plasmonic confinement vs propagation-length trade-off with doped cadmium oxide bilayers. Nano Lett. 19, 948–957 (2019).

    Article  Google Scholar 

  17. 17.

    Choi, G.-M., Wilson, R. B. & Cahill, D. G. Indirect heating of Pt by short-pulse laser irradiation of Au in a nanoscale Pt/Au bilayer. Phys. Rev. B 89, 064307 (2014).

    Article  Google Scholar 

  18. 18.

    Radue, E. L. et al. Hot electron thermoreflectance coefficient of gold during electron–phonon nonequilibrium. ACS Photon. 5, 4880–4887 (2018).

    CAS  Article  Google Scholar 

  19. 19.

    Giri, A. et al. Mechanisms of nonequilibrium electron–phonon coupling and thermal conductance at interfaces. J. Appl. Phys. 117, 105105 (2015).

    Article  Google Scholar 

  20. 20.

    Zhou, X. et al. Thin Ti adhesion layer breaks bottleneck to hot hole relaxation in Au films. J. Chem. Phys. 150, 184701 (2019).

    Article  Google Scholar 

  21. 21.

    Yang, Y. et al. Femtosecond optical polarization switching using a cadmium oxide-based perfect absorber. Nat. Photon. 11, 390–395 (2017).

    CAS  Article  Google Scholar 

  22. 22.

    Liu, C. P. et al. Effects of free carriers on the optical properties of doped CdO for full-spectrum photovoltaics. Phys. Rev. Appl. 6, 064018 (2016).

    Article  Google Scholar 

  23. 23.

    Nolen, J. R. et al. Ultraviolet to far-infrared dielectric function of n-doped cadmium oxide thin films. Phys. Rev. Mater. 4, 02520 (2020).

    Google Scholar 

  24. 24.

    Giannozzi, P. et al. Quantum Espresso: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

    Article  Google Scholar 

  25. 25.

    Giannozzi, P. et al. Advanced capabilities for materials modelling with Quantum Espresso. J. Phys. Condens. Matter 29, 465901 (2017).

    CAS  Article  Google Scholar 

  26. 26.

    Akimov, A. V. & Prezhdo, O. V. The PYXAID program for non-adiabatic molecular dynamics in condensed matter systems. J. Chem. Theory Comput. 9, 4959–4972 (2013).

    CAS  Article  Google Scholar 

  27. 27.

    Akimov, A. V. & Prezhdo, O. V. Advanced capabilities of the PYXAID program: integration schemes, decoherence effects, multiexcitonic states, and field-matter interaction. J. Chem. Theory Comput. 10, 789–804 (2014).

    CAS  Article  Google Scholar 

Download references

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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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.

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Correspondence to Patrick E. Hopkins.

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The authors declare no competing interests.

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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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