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Conductive polymer nanoantennas for dynamic organic plasmonics

Abstract

Being able to dynamically shape light at the nanoscale is one of the ultimate goals in nano-optics1. Resonant light–matter interaction can be achieved using conventional plasmonics based on metal nanostructures, but their tunability is highly limited due to a fixed permittivity2. Materials with switchable states and methods for dynamic control of light–matter interaction at the nanoscale are therefore desired. Here we show that nanodisks of a conductive polymer can support localized surface plasmon resonances in the near-infrared and function as dynamic nano-optical antennas, with their resonance behaviour tunable by chemical redox reactions. These plasmons originate from the mobile polaronic charge carriers of a poly(3,4-ethylenedioxythiophene:sulfate) (PEDOT:Sulf) polymer network. We demonstrate complete and reversible switching of the optical response of the nanoantennas by chemical tuning of their redox state, which modulates the material permittivity between plasmonic and dielectric regimes via non-volatile changes in the mobile charge carrier density. Further research may study different conductive polymers and nanostructures and explore their use in various applications, such as dynamic meta-optics and reflective displays.

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Fig. 1: Material properties of PEDOT:Sulf and simulated plasmonic response for PEDOT:Sulf nanodisks.
Fig. 2: Extinction spectra of PEDOT:Sulf nanodisk antennas.
Fig. 3: Geometry dependence of single PEDOT:Sulf nanodisk localized plasmons.
Fig. 4: Redox-state tunability of PEDOT:Sulf nanodisk antennas.

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.

    Shaltout, A. M., Shalaev, V. M. & Brongersma, M. L. Spatiotemporal light control with active metasurfaces. Science 364, eaat3100 (2019).

    CAS  Article  Google Scholar 

  2. 2.

    Maier, S. A. Plasmonics: Fundamentals and Applications (Springer Science & Business Media, 2007).

  3. 3.

    Massonnet, N., Carella, A., de Geyer, A., Faure-Vincent, J. & Simonato, J.-P. Metallic behaviour of acid doped highly conductive polymers. Chem. Sci. 6, 412–417 (2015).

    CAS  Article  Google Scholar 

  4. 4.

    Gueye, M. N. et al. Structure and dopant engineering in PEDOT thin films: practical tools for a dramatic conductivity enhancement. Chem. Mater. 28, 3462–3468 (2016).

    CAS  Article  Google Scholar 

  5. 5.

    Chen, S. et al. On the anomalous optical conductivity dispersion of electrically conducting polymers: ultra-wide spectral range ellipsometry combined with a Drude–Lorentz model. J. Mater. Chem. C 7, 4350–4362 (2019).

    CAS  Article  Google Scholar 

  6. 6.

    Aasmundtveit, K. E. et al. Structure of thin films of poly(3,4-ethylenedioxythiophene). Synth. Met. 101, 561–564 (1999).

    CAS  Article  Google Scholar 

  7. 7.

    Poddubny, A., Iorsh, I., Belov, P. & Kivshar, Y. Hyperbolic metamaterials. Nat. Photonics 7, 948 (2013).

    CAS  Article  Google Scholar 

  8. 8.

    Hanarp, P., Käll, M. & Sutherland, D. S. Optical properties of short range ordered arrays of nanometer gold disks prepared by colloidal lithography. J. Phys. Chem. B 107, 5768–5772 (2003).

    CAS  Article  Google Scholar 

  9. 9.

    Stete, F., Koopman, W. & Bargheer, M. Signatures of strong coupling on nanoparticles: revealing absorption anticrossing by tuning the dielectric environment. ACS Photonics 4, 1669–1676 (2017).

    CAS  Article  Google Scholar 

  10. 10.

    Chang, W.-S. et al. Tuning the acoustic frequency of a gold nanodisk through its adhesion layer. Nat. Commun. 6, 7022 (2015).

    CAS  Article  Google Scholar 

  11. 11.

    Fang, Z. et al. Active tunable absorption enhancement with graphene nanodisk arrays. Nano Lett. 14, 299–304 (2013).

    Article  Google Scholar 

  12. 12.

    Knight, M. W. et al. Aluminum for plasmonics. ACS Nano 8, 834–840 (2013).

    Article  Google Scholar 

  13. 13.

    Langhammer, C., Yuan, Z., Zorić, I. & Kasemo, B. Plasmonic properties of supported Pt and Pd nanostructures. Nano Lett. 6, 833–838 (2006).

    CAS  Article  Google Scholar 

  14. 14.

    Wokaun, A., Gordon, J. P. & Liao, P. F. Radiation damping in surface-enhanced Raman scattering. Phys. Rev. Lett. 48, 957 (1982).

    CAS  Article  Google Scholar 

  15. 15.

    Bredas, J. L. & Street, G. B. Polarons, bipolarons, and solitons in conducting polymers. Acc. Chem. Res. 18, 309–315 (1985).

    CAS  Article  Google Scholar 

  16. 16.

    Lee, S. H. et al. Switching terahertz waves with gate-controlled active graphene metamaterials. Nat. Mater. 11, 936 (2012).

    CAS  Article  Google Scholar 

  17. 17.

    Alam, M. Z., De Leon, I. & Boyd, R. W. Large optical nonlinearity of indium tin oxide in its epsilon-near-zero region. Science 352, 795–797 (2016).

    CAS  Article  Google Scholar 

  18. 18.

    Kim, N. et al. in Conjugated Polymers: Properties, Processing, and Applications (eds Reynolds, J. R., Thompson, B. C. & Skotheim, T. A.) 44–127 (CRC, 2019).

  19. 19.

    Fabiano, S. et al. Poly(ethyleneimine) impurities induce n‐doping reaction in organic (semi)conductors. Adv. Mater. 26, 6000–6006 (2014).

    CAS  Article  Google Scholar 

  20. 20.

    Jiang, N., Shao, L. & Wang, J. Gold nanorod core)/(polyaniline shell) plasmonic switches with large plasmon shifts and modulation depths. Adv. Mater. 26, 3282–3289 (2014).

    CAS  Article  Google Scholar 

  21. 21.

    Jung, I. et al. Surface plasmon resonance extension through two-block metal-conducting polymer nanorods. Nat. Commun. 9, 1010 (2018).

    Article  Google Scholar 

  22. 22.

    Li, S. Q. et al. Infrared plasmonics with indium–tin-oxide nanorod arrays. ACS Nano 5, 9161–9170 (2011).

    CAS  Article  Google Scholar 

  23. 23.

    Lauchner, A. et al. Molecular plasmonics. Nano Lett. 15, 6208–6214 (2015).

    CAS  Article  Google Scholar 

  24. 24.

    Rodrigo, D. et al. Mid-infrared plasmonic biosensing with graphene. Science 349, 165–168 (2015).

    CAS  Article  Google Scholar 

  25. 25.

    Mitraka, E. et al. Oxygen-induced doping on reduced PEDOT. J. Mater. Chem. A 5, 4404–4412 (2017).

    CAS  Article  Google Scholar 

  26. 26.

    Mei, J. & Bao, Z. Side chain engineering in solution-processable conjugated polymers. Chem. Mater. 26, 604–615 (2013).

    Article  Google Scholar 

  27. 27.

    Xu, J. et al. Multi-scale ordering in highly stretchable polymer semiconducting films. Nat. Mater. 18, 594–601 (2019).

    CAS  Article  Google Scholar 

  28. 28.

    Vijayakumar, V. et al. Bringing conducting polymers to high order: toward conductivities beyond 105 S cm−1 and thermoelectric power factors of 2 mW m−1 K−2. Adv. Energy Mater. 9, 1900266 (2019).

    Article  Google Scholar 

  29. 29.

    Larkin, P. Infrared and Raman Spectroscopy: Principles and Spectral Interpretation (Elsevier, 2017).

  30. 30.

    Brooke, R. et al. Vapor phase synthesized poly (3,4-ethylenedioxythiophene)-trifluoromethanesulfonate as a transparent conductor material. J. Mater. Chem. A 6, 21304–21312 (2018).

    CAS  Article  Google Scholar 

  31. 31.

    Kühne, P. et al. Advanced terahertz frequency-domain ellipsometry instrumentation for in situ and ex situ applications. IEEE Trans. Terahertz Sci. Technol. 8, 257–270 (2018).

    Article  Google Scholar 

  32. 32.

    Tompkins, H. & Irene, E. A. Handbook of Ellipsometry (William Andrew, 2005).

  33. 33.

    Weaver, J. H. & Frederikse, H. P. R. in CRC Handbook of Chemistry and Physics 74th edn (ed. Lide, D. R.) 1993–1994 (1993).

  34. 34.

    Philipp, H. R. in Handbook of Optical Constants of Solids Vol. 1 (ed. Palik, E.) 749–763 (Elsevier, 1997).

  35. 35.

    Tsuda, S., Yamaguchi, S., Kanamori, Y. & Yugami, H. Spectral and angular shaping of infrared radiation in a polymer resonator with molecular vibrational modes. Opt. Express 26, 6899–6915 (2018).

    CAS  Article  Google Scholar 

  36. 36.

    Beadie, G., Brindza, M., Flynn, R. A., Rosenberg, A. & Shirk, J. S. Refractive index measurements of poly(methyl methacrylate) (PMMA) from 0.4–1.6 μm. Appl. Opt. 54, F139–F143 (2015).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

The authors thankfully acknowledge financial support from the Swedish Research Council, the Swedish Foundation for Strategic Research, the Wenner-Gren Foundation and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009 00971).

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Contributions

M.P.J. conceived and supervised the project. S.C., V.S., P.K. and V.D. performed the ellipsometry measurements and data analysis. S.C. and M.S.C. fabricated the nanostructures. S.C., M.P.J. and E.S.H.K. performed numerical simulations. H.S. and S.C. performed PEI vapour treatments supervised by S.F. C.W. and M.F. performed the XPS measurements and analysis. S.C. performed all the other characterizations. S.C. and M.P.J. organized the data and wrote the manuscript. All the authors reviewed and commented on the manuscript.

Corresponding author

Correspondence to Magnus P. Jonsson.

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The authors declare no competing interests.

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Peer review information Nature Nanotechnology thanks Drew Evans and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

Supplementary Section A: Discussion and Tables 1–2., Supplementary Section B: Discussion and Figs. 1–16, and refs. 1–5.

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Chen, S., Kang, E.S.H., Shiran Chaharsoughi, M. et al. Conductive polymer nanoantennas for dynamic organic plasmonics. Nat. Nanotechnol. 15, 35–40 (2020). https://doi.org/10.1038/s41565-019-0583-y

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