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Environmentally stable and stretchable polymer electronics enabled by surface-tethered nanostructured molecular-level protection

Nature Nanotechnology volume 18, pages 1175–1184 (2023)Cite this article

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Abstract

Stretchable polymer semiconductors (PSCs) are essential for soft stretchable electronics. However, their environmental stability remains a longstanding concern. Here we report a surface-tethered stretchable molecular protecting layer to realize stretchable polymer electronics that are stable in direct contact with physiological fluids, containing water, ions and biofluids. This is achieved through the covalent functionalization of fluoroalkyl chains onto a stretchable PSC film surface to form densely packed nanostructures. The nanostructured fluorinated molecular protection layer (FMPL) improves the PSC operational stability over an extended period of 82 days and maintains its protection under mechanical deformation. We attribute the ability of FMPL to block water absorption and diffusion to its hydrophobicity and high fluorination surface density. The protection effect of the FMPL (~6 nm thickness) outperforms various micrometre-thick stretchable polymer encapsulants, leading to a stable PSC charge carrier mobility of ~1 cm2 V−1 s−1 in harsh environments such as in 85–90%-humidity air for 56 days or in water or artificial sweat for 42 days (as a benchmark, the unprotected PSC mobility degraded to 10−6 cm2 V−1 s−1 in the same period). The FMPL also improved the PSC stability against photo-oxidative degradation in air. Overall, we believe that our surface tethering of the nanostructured FMPL is a promising approach to achieve highly environmentally stable and stretchable polymer electronics.

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Fig. 1: Achieving long-term environmental stability in stretchable polymer electronics through dense surface fluorination.
Fig. 2: Surface fluorination on crosslinked composite semiconductor films.
Fig. 3: Morphological characterizations.
Fig. 4: Mechanical properties and electrical performance of transistors.
Fig. 5: Environmental and operational stability in air.
Fig. 6: Long-term water, sweat and photochemical stability.

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Acknowledgements

This work was supported by the Office of Navy Research under award no. N00014-23-1-2446. L.M. gratefully acknowledges funding through the Walter Benjamin Fellowship Programme by the Deutsche Forschungsgemeinschaft (DFG 456522816). Q.L. was supported by the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. N.P. and X.G. thank the US Army Engineer Research and Development Center (ERDC) for providing facilities access to the AFM-IR tool under contract no. W912HZ-18-C-0022. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. The grazing-incidence X-ray diffraction measurements were performed at Beamline 11-3 of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-76SF00515. J.K. acknowledges support from the National Research Foundation of Korea through grant nos. 2021R1C1C1011116 and 2022R1A5A6000846. Y.W. acknowledges financial support from the Office of Naval Research (award no. N00014-19-1-2453).

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Authors and Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Yu Zheng, Lukas Michalek, Qianhe Liu, Yilei Wu, Weilai Yu, Donglai Zhong, Chuanzhen Zhao, Zhiao Yu, Jerika A. Chiong, Huaxin Gong, Xiaozhou Ji, Deyu Liu, Song Zhang, Zhitao Zhang, Weichen Wang, Jeffrey B.-H. Tok & Zhenan Bao

  2. Department of Chemistry, Stanford University, Stanford, CA, USA

    Yu Zheng, Philaphon Sayavong, Zhiao Yu & Jerika A. Chiong

  3. Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea

    Hyunjun Kim & Jiheong Kang

  4. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Philaphon Sayavong, Weichen Wang & Yi Cui

  5. School of Polymer Science and Engineering, The University of Southern Mississippi, Hattiesburg, MS, USA

    Nathaniel Prine & Xiaodan Gu

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Contributions

Y.Z. and Z.B. designed the project and experiments. Y.Z. developed the modification procedures and conducted the materials characterization, transistor fabrication and testing. L.M., Y.W., H.K., P.S., W.Y., J.A.C., H.G., S.Z., N.P., X.G., Y.C. and J.K. performed the materials characterizations and rationales. Q.L., D.Z. and C.Z. designed and fabricated the transistors. Z.Y., X.J. and D.L. performed the synthesis. Z.Z., W.W. and J.K. helped with the rationales and discussions. Y.Z., L.M., J.B.-H.T. and Z.B. co-wrote and revised the manuscript.

Corresponding author

Correspondence to Zhenan Bao.

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Competing interests

Z.B. and Y.Z. declare that this work has been filed as US provisional patent no. 63/389,304. The remaining authors declare no competing interests.

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Zheng, Y., Michalek, L., Liu, Q. et al. Environmentally stable and stretchable polymer electronics enabled by surface-tethered nanostructured molecular-level protection. Nat. Nanotechnol. 18, 1175–1184 (2023). https://doi.org/10.1038/s41565-023-01418-y

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