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Multi-scale ordering in highly stretchable polymer semiconducting films

Nature Materials volume 18, pages 594–601 (2019)Cite this article

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Abstract

Stretchable semiconducting polymers have been developed as a key component to enable skin-like wearable electronics, but their electrical performance must be improved to enable more advanced functionalities. Here, we report a solution processing approach that can achieve multi-scale ordering and alignment of conjugated polymers in stretchable semiconductors to substantially improve their charge carrier mobility. Using solution shearing with a patterned microtrench coating blade, macroscale alignment of conjugated-polymer nanostructures was achieved along the charge transport direction. In conjunction, the nanoscale spatial confinement aligns chain conformation and promotes short-range π–π ordering, substantially reducing the energetic barrier for charge carrier transport. As a result, the mobilities of stretchable conjugated-polymer films have been enhanced up to threefold and maintained under a strain up to 100%. This method may also serve as the basis for large-area manufacturing of stretchable semiconducting films, as demonstrated by the roll-to-roll coating of metre-scale films.

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Fig. 1: Achieving multiple length scale ordering of conjugated polymers in stretchable semiconductors through a combination of the patterned-blade solution-shearing method and the nanoconfinement effect.
Fig. 2: Characterization of the electrical performance of the semiconducting films fabricated using different processes.
Fig. 3: Measurements of bandgap energies and activation energies for charge transport.
Fig. 4: Fully stretchable transistors fabricated from the SS-CONPHINE film.
Fig. 5: Large-area roll-to-roll coating of aligned, stretchable CONPHINE film.

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Data availability

The authors declare that all data supporting the findings of this study are available within the paper and its Supplementary Information. Other supporting data are available from the corresponding author upon request.

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Acknowledgements

This work is supported by the US Department of Energy, Office of Science, Basic Energy Sciences, under award DE-SC0016523 (material characterization) and by Samsung Electronics (device fabrication and characterization). G.-J.N.W. was supported by the Air Force Office of Scientific Research (grant no. FA9550-18-1-0143). Y.-H.K. acknowledges support from the NRF Korea (2018R1A2A105078734). L.S. acknowledges support from the Kodak Graduate Fellowship. The GIXD measurements were made at beamlines 11-3 and 7-2 of the Stanford Synchrotron Radiation Light Source, which are supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152.

Author information

Author notes

  1. Jie Xu

    Present address: Nanoscience and Technology Division, Argonne National Laboratory, Lemont, IL, USA

  2. Sihong Wang

    Present address: Institute for Molecular Engineering, University of Chicago, Chicago, IL, USA

  3. Francisco Molina-Lopez

    Present address: Department of Materials Engineering, KU Leuven, Belgium

  4. Xiaodan Gu

    Present address: School of Polymer Science and Engineering, University of Southern Mississippi, Hattiesburg, MS, USA

  5. These authors contributed equally: J. Xu, H.-C. Wu.

Authors and Affiliations

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

    Jie Xu, Hung-Chin Wu, Anatol Ehrlich, Leo Shaw, Mark Nikolka, Sihong Wang, Francisco Molina-Lopez, Xiaodan Gu, Ging-Ji Nathan Wang, Kevin Gu, Shucheng Chen, Toru Katsumata, Yu-Qing Zheng, Jong Won Chung, Jeffrey Lopez & Zhenan Bao

  2. Department of Electrical Engineering, Stanford University, Stanford, CA, USA

    Chenxin Zhu, Yeongin Kim & Boris Murmann

  3. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, USA

    Xiaodan Gu

  4. Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, China

    Shaochuan Luo & Dongshan Zhou

  5. Department of Chemistry and RINS, Gyeongsang National University, Jinju, South Korea

    Yun-Hi Kim

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

    Vivian Rachel Feig

  7. Corporate Research and Development, Performance Materials Technology Center, Asahi Kasei Corporation, Fuji, Shizuoka, Japan

    Toru Katsumata

  8. Department of Chemistry and Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Kowloon, Hong Kong, China

    He Yan

  9. Material Research Center, Samsung Advanced Institute of Technology Yeongtong-gu, Suwon-si, Gyeonggi-do, South Korea

    Jong Won Chung

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Contributions

J.X. and Z.B. conceived and designed the experiments; J.X., H.-C.W., A.E. and K.G. fabricated the films; J.X., H.-C.W., C.Z., A.E. and M.N. fabricated the transistor devices and made the measurements; J.X. and L.S. carried out the flow simulations; X.G., F.M.-L. and H.-C.W. did the GIXD characterizations; S.C. and V.R.F. carried out the XPS and SEM characterizations; S.W., Y.K. and Y.-Q.Z. fabricated the micro-structured blades; G.-J.N.W., T.K., Y.-H.K., and H.Y. provided the conjugated polymers; S.L., D.Z. and J.L. contributed to the initial design of the printing ink. J.W.C. and B.M. advised on the discussion of results. J.X. organized the data and wrote the first draft of the manuscript. All authors reviewed and commented on the manuscript. Z.B. directed the project.

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Correspondence to Zhenan Bao.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–29, Supplementary Tables 1–6, Supplementary Video Legend 1, Supplementary References

Supplementary Video 1

Roll-to-roll coating of a large-area stretchable semiconducting film.

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Xu, J., Wu, HC., Zhu, C. et al. Multi-scale ordering in highly stretchable polymer semiconducting films. Nat. Mater. 18, 594–601 (2019). https://doi.org/10.1038/s41563-019-0340-5

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