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.

  • Article
  • Published:

An n-doped capacitive transparent conductor for all-polymer electrochromic displays

Nature Electronics volume 7, pages 1158–1169 (2024)Cite this article

Subjects

Abstract

Non-emissive transmissive displays—such as see-through electrochromic displays—regulate natural light instead of emitting light, resulting in low energy consumption, reduced eye strain and outdoor applications in daytime. However, the fabrication of electrochromic displays is complex due to the integration of several layers with different manufacturing requirements. Here we show that a transparent conducting polymer, n-doped poly(3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione) (n-PBDF), can be used as both a transparent conductor and ion-storage material to make all-polymer electrochromic displays. The polymer has similar electrical properties as conventional transparent conductors while also being flexible and solution processable. The n-PBDF layer can serve dual roles in the display because of its high mixed ionic and electronic conductivity, which simplifies the device and allows for precise display pixel activation and control. By combining the minimally colour-changing n-PBDF with a patternable solid-state electrolyte, we created a non-emissive, flexible, all-polymer electrochromic display with low power consumption, bistability and full-colour capability.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

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

Fig. 1: n-PBDF as a capacitive transparent electrode for transmissive ECDs.
Fig. 2: Electrochromic behaviour of transmissive ECDs using solid electrolyte and n-PBDF.
Fig. 3: Patterning and optical properties of all-polymer components for a see-through electrochromic display.
Fig. 4: Passive-matrix-based, all-polymer electrochromic display using in situ patterned solid-electrolyte localization.
Fig. 5: Flexible application of a see-through, full-colour, all-polymer electrochromic display.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  1. Keene, S. T. et al. Exploiting mixed conducting polymers in organic and bioelectronic devices. Phys. Chem. Chem. Phys. 24, 19144–19163 (2022).

    Google Scholar 

  2. Berggren, M. & Malliaras, G. G. How conducting polymer electrodes operate. Science 364, 233–234 (2019).

    Google Scholar 

  3. Ke, Z. et al. Highly conductive and solution-processable n-doped transparent organic conductor. J. Am. Chem. Soc. 145, 3706–3715 (2023).

    Google Scholar 

  4. Tang, H. et al. A solution-processed n-type conducting polymer with ultrahigh conductivity. Nature 611, 271–277 (2022).

    Google Scholar 

  5. Li, X. et al. Stabilizing hybrid electrochromic devices through pairing electrochromic polymers with minimally color-changing ion-storage materials having closely matched electroactive voltage windows. ACS Appl. Mater. Interfaces 13, 5312–5318 (2021).

    Google Scholar 

  6. He, J., You, L., Tran, D. T. & Mei, J. Low-temperature thermally annealed niobium oxide thin films as a minimally color changing ion storage layer in solution-processed polymer electrochromic devices. ACS Appl. Mater. Interfaces 11, 4169–4177 (2019).

    Google Scholar 

  7. Hassab, S. & Padilla, J. Using WO3 as a transparent, optically-passive counter electrode in an unbalanced electrochromic configuration. Electrochem. Commun. 72, 87–90 (2016).

    Google Scholar 

  8. Song, I., You, L., Chen, K., Lee, W.-J. & Mei, J. Chiroptical switching of electrochromic polymer thin films. Adv. Mater. 36, 2307057 (2024).

    Google Scholar 

  9. Zhang, S. et al. Dual-band electrochromic devices with a transparent conductive capacitive charge-balancing anode. ACS Appl. Mater. Interfaces 11, 48062–48070 (2019).

    Google Scholar 

  10. Maho, A. et al. Aqueous processing and spray deposition of polymer-wrapped tin-doped indium oxide nanocrystals as electrochromic thin films. Chem. Mater. 32, 8401–8411 (2020).

    Google Scholar 

  11. Senthilkumar, S. T., Selvan, R. K., Lee, Y. S. & Melo, J. S. Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte. J. Mater. Chem. A 1, 1086–1095 (2013).

    Google Scholar 

  12. De Keersmaecker, M., Lang, A. W., Österholm, A. M. & Reynolds, J. R. All polymer solution processed electrochromic devices: a future without indium tin oxide? ACS Appl. Mater. Interfaces 10, 31568–31579 (2018).

    Google Scholar 

  13. Volkov, A. V. et al. Understanding the capacitance of PEDOT:PSS. Adv. Funct. Mater. 27, 1700329 (2017).

    Google Scholar 

  14. Argun, A. A., Cirpan, A. & Reynolds, J. R. The first truly all-polymer electrochromic devices. Adv. Mater. 15, 1338–1341 (2003).

    Google Scholar 

  15. Shi, P. et al. Broadly absorbing black to transmissive switching electrochromic polymers. Adv. Mater. 22, 4949–4953 (2010).

    Google Scholar 

  16. Bulloch, R. H., Kerszulis, J. A., Dyer, A. L. & Reynolds, J. R. An electrochromic painter’s palette: color mixing via solution co-processing. ACS Appl. Mater. Interfaces 7, 1406–1412 (2015).

    Google Scholar 

  17. Chen, K. et al. Printing dynamic color palettes and layered textures through modeling-guided stacking of electrochromic polymers. Mater. Horiz. 9, 425–432 (2022).

    Google Scholar 

  18. Tybrandt, K., Zozoulenko, I. V. & Berggren, M. Chemical potential–electric double layer coupling in conjugated polymer–polyelectrolyte blends. Sci. Adv. 3, eaao3659 (2017).

    Google Scholar 

  19. Österholm, A. M. et al. Disentangling redox properties and capacitance in solution-processed conjugated polymers. Chem. Mater. 31, 2971–2982 (2019).

    Google Scholar 

  20. Sivachidambaram, M. et al. Preparation and characterization of activated carbon derived from the Borassus flabellifer flower as an electrode material for supercapacitor applications. New J. Chem. 41, 3939–3949 (2017).

    Google Scholar 

  21. Bianchi, M. et al. Scaling of capacitance of PEDOT:PSS: volume vs. area. J. Mater. Chem. C 8, 11252–11262 (2020).

  22. Liu, J., Jiang, J., Bosman, M. & Fan, H. J. Three-dimensional tubular arrays of MnO2–NiO nanoflakes with high areal pseudocapacitance. J. Mater. Chem. 22, 2419–2426 (2012).

    Google Scholar 

  23. Jiang, J. et al. CNT/Ni hybrid nanostructured arrays: synthesis and application as high-performance electrode materials for pseudocapacitors. Energy Environ. Sci. 4, 5000–5007 (2011).

    Google Scholar 

  24. Liu, J. et al. Advanced energy storage devices: basic principles, analytical methods, and rational materials design. Adv. Sci. 5, 1700322 (2018).

    Google Scholar 

  25. Phan, G. T. et al. Fast-switching electrochromic smart windows based on NiO-nanorods counter electrode. Sol. Energy Mater. Sol. Cells 231, 111306 (2021).

    Google Scholar 

  26. Wang, Z. et al. Towards full-colour tunability of inorganic electrochromic devices using ultracompact Fabry-Perot nanocavities. Nat. Commun. 11, 302 (2020).

    Google Scholar 

  27. Chen, J., Wang, Z., Chen, Z., Cong, S. & Zhao, Z. Fabry–Perot cavity-type electrochromic supercapacitors with exceptionally versatile color tunability. Nano Lett. 20, 1915–1922 (2020).

    Google Scholar 

  28. Cheng, W. et al. Photodeposited amorphous oxide films for electrochromic windows. Chem 4, 821–832 (2018).

    Google Scholar 

  29. Shao, Z. et al. All-solid-state proton-based tandem structures for fast-switching electrochromic devices. Nat. Electron. 5, 45–52 (2022).

    Google Scholar 

  30. Wu, C. et al. Electrochromic conjugated polymers containing benzotriazole and thiophene performing sub-second response time and 916 cm2 C−1 superb coloration efficiency. Sol. Energy Mater. Sol. Cells 257, 112355 (2023).

    Google Scholar 

  31. He, J., You, L. & Mei, J. Self-bleaching behaviours in black-to-transmissive electrochromic polymer thin films. ACS Appl. Mater. Interfaces 9, 34122–34130 (2017).

    Google Scholar 

  32. Shin, H. et al. Energy saving electrochromic windows from bistable low-HOMO level conjugated polymers. Energy Environ. Sci. 9, 117–122 (2016).

    Google Scholar 

  33. Li, X., Wang, X., You, L., Zhao, K. & Mei, J. Improving electrochemical cycling stability of conjugated yellow-to-transmissive electrochromic polymers by regulating effective overpotentials. ACS Mater. Lett. 4, 336–342 (2022).

    Google Scholar 

  34. Park, C. et al. Switchable silver mirrors with long memory effects. Chem. Sci. 6, 596–602 (2015).

    Google Scholar 

  35. Silvester, D. S. et al. Electrical double layer structure in ionic liquids and its importance for supercapacitor, battery, sensing, and lubrication applications. J. Phys. Chem. C 125, 13707–13720 (2021).

    Google Scholar 

  36. Png, R.-Q. et al. High-performance polymer semiconducting heterostructure devices by nitrene-mediated photocrosslinking of alkyl side chains. Nat. Mater. 9, 152–158 (2010).

    Google Scholar 

  37. Zhong, Y., Nguyen, G. T. M., Plesse, C., Vidal, F. & Jager, E. W. H. Highly conductive, photolithographically patternable ionogels for flexible and stretchable electrochemical devices. ACS Appl. Mater. Interfaces 10, 21601–21611 (2018).

    Google Scholar 

  38. Pritchard, C. D. et al. An injectable thiol-acrylate poly(ethylene glycol) hydrogel for sustained release of methylprednisolone sodium succinate. Biomaterials 32, 587–597 (2011).

    Google Scholar 

  39. Zhong, Y., Nguyen, G. T. M., Plesse, C., Vidal, F. & Jager, E. W. H. Tailorable, 3D structured and micro-patternable ionogels for flexible and stretchable electrochemical devices. J. Mater. Chem. C 7, 256–266 (2019).

    Google Scholar 

  40. Zhang, W. et al. Bio-inspired ultra-high energy efficiency bistable electronic billboard and reader. Nat. Commun. 10, 1559 (2019).

    Google Scholar 

  41. Wang, Y. et al. A multicolour bistable electronic shelf label based on intramolecular proton-coupled electron transfer. Nat. Mater. 18, 1335–1342 (2019).

    Google Scholar 

  42. Gu, C. et al. Transparent and energy-efficient electrochromic AR display with minimum crosstalk using the pixel confinement effect. Device 1, 100126 (2023).

    Google Scholar 

  43. Fei, P. F. et al. Review of paper-like display technologies. Prog. Electromagn. Res. 147, 95–116 (2014).

    Google Scholar 

  44. Graham-Rowe, D. Electronic paper rewrites the rulebook for displays. Nat. Photonics 1, 248–251 (2007).

    Google Scholar 

  45. Tung, Y.-J. et al. 49.3: A 200-dpi transparent a-Si TFT active-matrix phosphorescent OLED display. SID Symp. Dig. Tech. Pap. 36, 1546–1549 (2005).

    Google Scholar 

  46. Fernández, M. R., Casanova, E. Z. & Alonso, I. G. Review of display technologies focusing on power consumption. Sustainability 7, 10854–10875 (2015).

    Google Scholar 

  47. Aliev, A. E. & Shin, H. W. Image diffusion and cross-talk in passive matrix electrochromic displays. Displays 23, 239–247 (2002).

    Google Scholar 

  48. Chen, B.-H. et al. Printed multicolor high-contrast electrochromic devices. ACS Appl. Mater. Interfaces 7, 25069–25076 (2015).

    Google Scholar 

  49. Soboleva, T. et al. Investigation of the through-plane impedance technique for evaluation of anisotropy of proton conducting polymer membranes. J. Electroanal. Chem. 622, 145–152 (2008).

    Google Scholar 

  50. Wang, Y. et al. Solid-state rigid-rod polymer composite electrolytes with nanocrystalline lithium ion pathways. Nat. Mater. 20, 1255–1263 (2021).

    Google Scholar 

Download references

Acknowledgements

We are grateful for financial support from Ambilight Inc. under contract 4000187.02.

Author information

Authors and Affiliations

  1. Tarpo Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Inho Song, Won-June Lee, Zhifan Ke, Liyan You, Ke Chen, Sumon Naskar, Palak Mehra & Jianguo Mei

  2. Department of Chemical Engineering, Chung-Ang University (CAU), Seoul, Republic of Korea

    Inho Song

Authors
  1. Inho Song
    View author publications

    Search author on:PubMed Google Scholar

  2. Won-June Lee
    View author publications

    Search author on:PubMed Google Scholar

  3. Zhifan Ke
    View author publications

    Search author on:PubMed Google Scholar

  4. Liyan You
    View author publications

    Search author on:PubMed Google Scholar

  5. Ke Chen
    View author publications

    Search author on:PubMed Google Scholar

  6. Sumon Naskar
    View author publications

    Search author on:PubMed Google Scholar

  7. Palak Mehra
    View author publications

    Search author on:PubMed Google Scholar

  8. Jianguo Mei
    View author publications

    Search author on:PubMed Google Scholar

Contributions

J.M. conceived the project. I.S. performed the instrumental analyses and device characterization. W.-J.L. conducted the instrumental electrochemical investigations and synthesized the ion-storage materials. Z.K. and L.Y. synthesized the polymer conductors and ECPs. K.C. and S.N. assisted in fabricating the ECDs. P.M. conducted electrochemical investigation to measure ionic conductivity. I.S. and J.M. drafted the paper, and all authors contributed to writing the paper and providing feedback on the paper.

Corresponding author

Correspondence to Jianguo Mei.

Ethics declarations

Competing interests

J.M. is a co-founder of Ambilight, which financially sponsors this research. The other authors declare no competing interests.

Peer review

Peer review information

Nature Electronics thanks Haizeng Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Notes 1–6, Figs. 1–50, Tables 1 and 2, and Videos 1–3.

Supplementary Video 1

Recorded video of a passive-matrix electrochromic display with 8 × 8 matrix. Initially, all pixels were fully bleached with a positive voltage (+1.0 V).

Supplementary Video 2

Recorded video of an all-polymer full-colour electrochromic display with 64 colours represented by 40 μm subpixels in a lateral arrangement.

Supplementary Video 3

Recorded video of a segmented all-polymer electrochromic display with two 7-segment displays to represent all numbers.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Song, I., Lee, WJ., Ke, Z. et al. An n-doped capacitive transparent conductor for all-polymer electrochromic displays. Nat Electron 7, 1158–1169 (2024). https://doi.org/10.1038/s41928-024-01293-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41928-024-01293-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