Article | Published:

Multi-scale ordering in highly stretchable polymer semiconducting films

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

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.

Additional information

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

References

  1. 1.

    Chu, B., Burnett, W., Chung, J. W. & Bao, Z. Bring on the bodyNET. Nat. News 549, 328–330 (2017).

  2. 2.

    Wang, S., Oh, J. Y., Xu, J., Tran, H. & Bao, Z. Skin-inspired electronics: an emerging paradigm. Acc. Chem. Res. 51, 1033–1045 (2018).

  3. 3.

    Someya, T., Bao, Z. & Malliaras, G. G. The rise of plastic bioelectronics. Nature 540, 379–385 (2016).

  4. 4.

    Wang, S. et al. Skin electronics from scalable fabrication of an intrinsically stretchable transistor array. Nature 555, 83–88 (2018).

  5. 5.

    Wang, N. G. J., Gasperini, A. & Bao, Z. Stretchable polymer semiconductors for plastic electronics. Adv. Electron. Mater. 4, 1700429 (2018).

  6. 6.

    Root, S. E., Savagatrup, S., Printz, A. D., Rodriquez, D. & Lipomi, D. J. Mechanical properties of organic semiconductors for stretchable, highly flexible, and mechanically robust electronics. Chem. Rev. 117, 6467–6499 (2017).

  7. 7.

    International Technology Roadmap for Semiconductors (ITRS, 2012).

  8. 8.

    Oh, J. Y. et al. Intrinsically stretchable and healable semiconducting polymer for organic transistors. Nature 539, 411–415 (2016).

  9. 9.

    Müller, C. et al. Tough, semiconducting polyethylene‐poly(3‐hexylthiophene) diblock copolymers. Adv. Funct. Mater. 17, 2674–2679 (2007).

  10. 10.

    Xu, J. et al. Highly stretchable polymer semiconductor films through the nanoconfinement effect. Science 355, 59–64 (2017).

  11. 11.

    Napolitano, S., Glynos, E. & Tito, N. B. Glass transition of polymers in bulk, confined geometries, and near interfaces. Rep. Prog. Phys. 80, 036602 (2017).

  12. 12.

    Lee, Y. et al. Deformable organic nanowire field‐effect transistors. Adv. Mater. 30, 1704401 (2018).

  13. 13.

    Eunjoo, S. et al. Stretchable and transparent organic semiconducting thin film with conjugated polymer nanowires embedded in an elastomeric matrix. Adv. Electron. Mater. 2, 1500250 (2016).

  14. 14.

    Venkateshvaran, D. et al. Approaching disorder-free transport in high-mobility conjugated polymers. Nature 515, 384–388 (2014).

  15. 15.

    Jackson, N. E. et al. Conformational order in aggregates of conjugated polymers. J. Am. Chem. Soc. 137, 6254–6262 (2015).

  16. 16.

    Wang, G. et al. Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport. Proc. Natl Acad. Sci. USA 114, E10066–E10073 (2017).

  17. 17.

    Dai, L., Renner, C. B. & Doyle, P. S. The polymer physics of single DNA confined in nanochannels. Adv. Colloid. Interface Sci. 232, 80–100 (2016).

  18. 18.

    Tseng, H.-R. et al. High mobility field effect transistors based on macroscopically oriented regioregular copolymers. Nano Lett. 12, 6353–6357 (2012).

  19. 19.

    Mohammadi, E. et al. Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films. Nat. Commun. 8, 16070 (2017).

  20. 20.

    Persson, N. E., Chu, P.-H., McBride, M., Grover, M. & Reichmanis, E. Nucleation, growth, and alignment of poly(3-hexylthiophene) nanofibers for high-performance OFETs. Acc. Chem. Res. 50, 932–942 (2017).

  21. 21.

    Chang, M., Su, Z. & Egap, E. Alignment and charge transport of one-dimensional conjugated polymer nanowires in insulating polymer blends. Macromolecules 49, 9449–9456 (2016).

  22. 22.

    Kang, I., Yun, H.-J., Chung, D. S., Kwon, S.-K. & Kim, Y.-H. Record high hole mobility in polymer semiconductors via side-chain engineering. J. Am. Chem. Soc. 135, 14896–14899 (2013).

  23. 23.

    Zheng, Z. et al. Uniaxial alignment of liquid-crystalline conjugated polymers by nanoconfinement. Nano Lett. 7, 987–992 (2007).

  24. 24.

    Zhang, G. et al. Versatile interpenetrating polymer network approach to robust stretchable electronic devices. Chem. Mater. 29, 7645–7652 (2017).

  25. 25.

    Schott, S. et al. Charge‐transport anisotropy in a uniaxially aligned diketopyrrolopyrrole‐based copolymer. Adv. Mater. 27, 7356–7364 (2015).

  26. 26.

    Shaw, L. et al. Direct uniaxial alignment of a donor–acceptor semiconducting polymer using single-step solution shearing. ACS Appl. Mater. Interfaces 8, 9285–9296 (2016).

  27. 27.

    McCulloch, I., Salleo, A. & Chabinyc, M. Avoid the kinks when measuring mobility. Science 352, 1521–1522 (2016).

  28. 28.

    Choi, H. H., Cho, K., Frisbie, C. D., Sirringhaus, H. & Podzorov, V. Critical assessment of charge mobility extraction in FETs. Nat. Mater. 17, 2–7 (2017).

  29. 29.

    Bittle, E. G., Basham, J. I., Jackson, T. N., Jurchescu, O. D. & Gundlach, D. J. Mobility overestimation due to gated contacts in organic field-effect transistors. Nat. Commun. 7, 10908 (2016).

  30. 30.

    Phan, H. et al. Electrical double‐slope nonideality in organic field‐effect transistors. Adv. Funct. Mater. 28, 1707221 (2018).

  31. 31.

    Nikolka, M. et al. Correlation of disorder and charge transport in a range of indacenodithiophene‐based semiconducting polymers. Adv. Electron. Mater. 3, 1700410 (2017).

  32. 32.

    Liu, Y. et al. Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells. Nat. Commun. 5, 5293 (2014).

  33. 33.

    Chortos, A. et al. Highly stretchable transistors using a microcracked organic semiconductor. Adv. Mater. 26, 4253–4259 (2014).

  34. 34.

    Nikiforov, O. G. et al. Current-induced Joule heating and electrical field effects in low temperature measurements on TIPS pentacene thin film transistors. Adv. Electron. Mater. 2, 1600163 (2016).

Download references

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

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.

Competing interests

The authors declare no competing interests.

Correspondence to Zhenan Bao.

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.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark
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.