Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation

Sri Harish Kumar Paleti; Shuichi Haraguchi; Zhiqiang Cao; Mariavittoria Craighero; Joost Kimpel; Zijin Zeng; Przemyslaw Sowinski; Di Zhu; Judith Pons i Tarrés; Youngseok Kim; Qifan Li; Junda Huang; Alexei Kalaboukhov; Besira Mihiretie; Simone Fabiano; Xiaodan Gu; Christian Müller

doi:10.1021/acs.macromol.4c03081

Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation

Sri Harish Kumar Paleti, Shuichi Haraguchi, Zhiqiang Cao, Mariavittoria Craighero, Joost Kimpel, Zijin Zeng, Przemyslaw Sowinski, Di Zhu, Judith Pons i Tarrés, Youngseok Kim, Qifan Li, Junda Huang, Alexei Kalaboukhov, Besira Mihiretie, Simone Fabiano, Xiaodan Gu, Christian Müller

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Abstract

The elastic modulus is a critical parameter for the design of conjugated polymers for wearable electronics and correlates with electrical and thermal transport. Yet, widely different values have been reported for the same material because of the influence of processing and measurement conditions, including the temperature, mode, direction, and time scale of deformation. Thus, results obtained via different methods are usually not considered to be comparable. Here, disparate techniques from nanoindentation to tensile testing of free-standing films or films on water, buckling analysis, dynamic mechanical thermal analysis, oscillatory shear rheometry, and atomic force microscopy are compared. Strikingly, elastic modulus values obtained for the same batch of regioregular poly(3-hexylthiophene) differ by a factor of less than four, which suggests that an approximate comparison is possible. Considering the small amount of material that is typically available, nanoindentation in combination with creep analysis is identified as a reliable method for probing the elastic modulus of films with widely different elastic moduli ranging from less than 0.1 GPa in the case of a polythiophene with oligoether side chains to several GPa for polymers without side chains. Since films can display anisotropic elastic modulus values, it is proposed that nanoindentation is complemented with an in-plane technique such as tensile testing to ensure a full characterization using different modes of deformation.

Original language	English
Pages (from-to)	3578-3588
Number of pages	11
Journal	Macromolecules
Volume	58
Issue number	7
DOIs	https://doi.org/10.1021/acs.macromol.4c03081
State	Published - Apr 8 2025

Funding

We gratefully acknowledge financial support from the European Union’s Horizon 2020 research and innovation programme through the Marie Skłodowska-Curie grant agreement no. 955837 (HORATES), the Knut and Alice Wallenberg Foundation (grant agreement nos. 2020.0187 and 2022.0034) and the European Research Council (ERC) under grant agreement no. 101043417. Support from the Swedish Research Infrastructure for Micro and Nano Fabrication (Myfab) is acknowledged. Z.C. and X.G. thank the National Science Foundation for providing funding resources for the FOW mechanical property study under award number DMR-2047689.

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10.1021/acs.macromol.4c03081

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Paleti, S. H. K., Haraguchi, S., Cao, Z., Craighero, M., Kimpel, J., Zeng, Z., Sowinski, P., Zhu, D., Pons i Tarrés, J., Kim, Y., Li, Q., Huang, J., Kalaboukhov, A., Mihiretie, B., Fabiano, S., Gu, X., & Müller, C. (2025). Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation. Macromolecules, 58(7), 3578-3588. https://doi.org/10.1021/acs.macromol.4c03081

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title = "Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation",

abstract = "The elastic modulus is a critical parameter for the design of conjugated polymers for wearable electronics and correlates with electrical and thermal transport. Yet, widely different values have been reported for the same material because of the influence of processing and measurement conditions, including the temperature, mode, direction, and time scale of deformation. Thus, results obtained via different methods are usually not considered to be comparable. Here, disparate techniques from nanoindentation to tensile testing of free-standing films or films on water, buckling analysis, dynamic mechanical thermal analysis, oscillatory shear rheometry, and atomic force microscopy are compared. Strikingly, elastic modulus values obtained for the same batch of regioregular poly(3-hexylthiophene) differ by a factor of less than four, which suggests that an approximate comparison is possible. Considering the small amount of material that is typically available, nanoindentation in combination with creep analysis is identified as a reliable method for probing the elastic modulus of films with widely different elastic moduli ranging from less than 0.1 GPa in the case of a polythiophene with oligoether side chains to several GPa for polymers without side chains. Since films can display anisotropic elastic modulus values, it is proposed that nanoindentation is complemented with an in-plane technique such as tensile testing to ensure a full characterization using different modes of deformation.",

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doi = "10.1021/acs.macromol.4c03081",

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Paleti, SHK, Haraguchi, S, Cao, Z, Craighero, M, Kimpel, J, Zeng, Z, Sowinski, P, Zhu, D, Pons i Tarrés, J, Kim, Y, Li, Q, Huang, J, Kalaboukhov, A, Mihiretie, B, Fabiano, S, Gu, X & Müller, C 2025, 'Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation', Macromolecules, vol. 58, no. 7, pp. 3578-3588. https://doi.org/10.1021/acs.macromol.4c03081

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AU - Paleti, Sri Harish Kumar

AU - Haraguchi, Shuichi

AU - Cao, Zhiqiang

AU - Craighero, Mariavittoria

AU - Kimpel, Joost

AU - Zeng, Zijin

AU - Sowinski, Przemyslaw

AU - Zhu, Di

AU - Pons i Tarrés, Judith

AU - Kim, Youngseok

AU - Li, Qifan

AU - Huang, Junda

AU - Kalaboukhov, Alexei

AU - Mihiretie, Besira

AU - Fabiano, Simone

AU - Gu, Xiaodan

AU - Müller, Christian

PY - 2025/4/8

Y1 - 2025/4/8

N2 - The elastic modulus is a critical parameter for the design of conjugated polymers for wearable electronics and correlates with electrical and thermal transport. Yet, widely different values have been reported for the same material because of the influence of processing and measurement conditions, including the temperature, mode, direction, and time scale of deformation. Thus, results obtained via different methods are usually not considered to be comparable. Here, disparate techniques from nanoindentation to tensile testing of free-standing films or films on water, buckling analysis, dynamic mechanical thermal analysis, oscillatory shear rheometry, and atomic force microscopy are compared. Strikingly, elastic modulus values obtained for the same batch of regioregular poly(3-hexylthiophene) differ by a factor of less than four, which suggests that an approximate comparison is possible. Considering the small amount of material that is typically available, nanoindentation in combination with creep analysis is identified as a reliable method for probing the elastic modulus of films with widely different elastic moduli ranging from less than 0.1 GPa in the case of a polythiophene with oligoether side chains to several GPa for polymers without side chains. Since films can display anisotropic elastic modulus values, it is proposed that nanoindentation is complemented with an in-plane technique such as tensile testing to ensure a full characterization using different modes of deformation.

AB - The elastic modulus is a critical parameter for the design of conjugated polymers for wearable electronics and correlates with electrical and thermal transport. Yet, widely different values have been reported for the same material because of the influence of processing and measurement conditions, including the temperature, mode, direction, and time scale of deformation. Thus, results obtained via different methods are usually not considered to be comparable. Here, disparate techniques from nanoindentation to tensile testing of free-standing films or films on water, buckling analysis, dynamic mechanical thermal analysis, oscillatory shear rheometry, and atomic force microscopy are compared. Strikingly, elastic modulus values obtained for the same batch of regioregular poly(3-hexylthiophene) differ by a factor of less than four, which suggests that an approximate comparison is possible. Considering the small amount of material that is typically available, nanoindentation in combination with creep analysis is identified as a reliable method for probing the elastic modulus of films with widely different elastic moduli ranging from less than 0.1 GPa in the case of a polythiophene with oligoether side chains to several GPa for polymers without side chains. Since films can display anisotropic elastic modulus values, it is proposed that nanoindentation is complemented with an in-plane technique such as tensile testing to ensure a full characterization using different modes of deformation.

UR - https://www.scopus.com/pages/publications/105002317681

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DO - 10.1021/acs.macromol.4c03081

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AN - SCOPUS:105002317681

SN - 0024-9297

VL - 58

SP - 3578

EP - 3588

JO - Macromolecules

JF - Macromolecules

IS - 7

ER -

Benchmarking the Elastic Modulus of Conjugated Polymers with Nanoindentation

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