Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Conductive polymer nanoantennas for dynamic organic plasmonics

Nature Nanotechnology volume 15, pages 35–40 (2020)Cite this article

Subjects

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.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

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.

Similar content being viewed by others

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

    Article  CAS  Google Scholar 

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

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  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).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

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

  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).

    Article  CAS  Google Scholar 

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

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

  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).

    Article  CAS  Google Scholar 

  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).

    Article  CAS  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).

Author information

Authors and Affiliations

  1. Laboratory of Organic Electronics, Department of Science and Technology (ITN), Linköping University, Norrköping, Sweden

    Shangzhi Chen, Evan S. H. Kang, Mina Shiran Chaharsoughi, Hengda Sun, Chuanfei Wang, Mats Fahlman, Simone Fabiano & Magnus P. Jonsson

  2. Terahertz Materials Analysis Center (THeMAC) and Center for III-N Technology, C3NiT—Janzèn, Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping, Sweden

    Vallery Stanishev, Philipp Kühne & Vanya Darakchieva

Authors
  1. Shangzhi Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Evan S. H. Kang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mina Shiran Chaharsoughi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Vallery Stanishev
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Philipp Kühne
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hengda Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chuanfei Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Mats Fahlman
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Simone Fabiano
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Vanya Darakchieva
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Magnus P. Jonsson
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-019-0583-y

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing