Transiently delocalized states enhance hole mobility in organic molecular semiconductors

Samuele Giannini; Lucia Di Virgilio; Marco Bardini; Julian Hausch; Jaco J. Geuchies; Wenhao Zheng; Martina Volpi; Jan Elsner; Katharina Broch; Yves H. Geerts; Frank Schreiber; Guillaume Schweicher; Hai I. Wang; Jochen Blumberger; Mischa Bonn; David Beljonne

doi:10.1038/s41563-023-01664-4

Transiently delocalized states enhance hole mobility in organic molecular semiconductors

Samuele Giannini^*, Lucia Di Virgilio, Marco Bardini, Julian Hausch, Jaco J. Geuchies, Wenhao Zheng, Martina Volpi, Jan Elsner, Katharina Broch, Yves H. Geerts, Frank Schreiber, Guillaume Schweicher, Hai I. Wang^*, Jochen Blumberger, Mischa Bonn^*, David Beljonne^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (μ) with temperature (T) following μ ∝ T ⁻ⁿ, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.

Original language	English
Pages (from-to)	1361-1369
Number of pages	9
Journal	Nature Materials
Volume	22
Issue number	11
Early online date	14 Sept 2023
DOIs	https://doi.org/10.1038/s41563-023-01664-4
Publication status	Published - Nov 2023

Bibliographical note

Publisher Copyright:
© 2023, The Author(s), under exclusive licence to Springer Nature Limited.

Funding

S.G. and M. Bardini acknowledge C. Quarti for useful discussions. We are grateful to H. Burg and R. Berger for conducting scanning force microscopy measurements. This work received funding from the European Union’s Horizon 2020 research and innovation programme under Marie Sklodowska-Curie grant no. 811284. J.H., K.B. and F.S. acknowledge funding by the German Research Foundation (BR4869/4-1 and SCHR 700/40-1). G.S. acknowledges financial support from the Francqui Foundation (Francqui Start-Up Grant) and the Belgian National Fund for Scientific Research (FNRS) for financial support through research project COHERENCE2 (N°F.4536.23). Y.H.G. is thankful to the FNRS for financial support through research projects Pi-Fast (no. T.0072.18) and Pi-Chir (no. T.0094.22). J.J.G. gratefully acknowledges support from the Alexander von Humboldt Foundation. The work in Mons has been funded by the Fund for Scientific Research (FRS) of FNRS within the Consortium des Équipements de Calcul Intensif (CÉCI) under grant 2.5020.11, and by the Walloon Region (ZENOBE Tier-1 supercomputer) under grant 1117545. G.S. is a FNRS Research Associate. D.B. is a FNRS research director.

Funders	Funder number
Francqui Foundation
Alexander von Humboldt Stiftung	2.5020.11
Horizon 2020 Framework Programme	811284
Waalse Gewest	1117545
the Deutsche Forschungsgemeinschaft	BR4869/4-1, SCHR 700/40-1
Fonds De La Recherche Scientifique - FNRS	F.4536.23

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10.1038/s41563-023-01664-4

s41563-023-01664-4Final published version, 2.64 MBLicence: Taverne

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Giannini, S., Di Virgilio, L., Bardini, M., Hausch, J., Geuchies, J. J., Zheng, W., Volpi, M., Elsner, J., Broch, K., Geerts, Y. H., Schreiber, F., Schweicher, G., Wang, H. I., Blumberger, J., Bonn, M., & Beljonne, D. (2023). Transiently delocalized states enhance hole mobility in organic molecular semiconductors. Nature Materials, 22(11), 1361-1369. https://doi.org/10.1038/s41563-023-01664-4

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abstract = "Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (μ) with temperature (T) following μ ∝ T −n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.",

author = "Samuele Giannini and {Di Virgilio}, Lucia and Marco Bardini and Julian Hausch and Geuchies, {Jaco J.} and Wenhao Zheng and Martina Volpi and Jan Elsner and Katharina Broch and Geerts, {Yves H.} and Frank Schreiber and Guillaume Schweicher and Wang, {Hai I.} and Jochen Blumberger and Mischa Bonn and David Beljonne",

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Giannini, S, Di Virgilio, L, Bardini, M, Hausch, J, Geuchies, JJ, Zheng, W, Volpi, M, Elsner, J, Broch, K, Geerts, YH, Schreiber, F, Schweicher, G, Wang, HI, Blumberger, J, Bonn, M & Beljonne, D 2023, 'Transiently delocalized states enhance hole mobility in organic molecular semiconductors', Nature Materials, vol. 22, no. 11, pp. 1361-1369. https://doi.org/10.1038/s41563-023-01664-4

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AU - Giannini, Samuele

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AU - Bardini, Marco

AU - Hausch, Julian

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AU - Zheng, Wenhao

AU - Volpi, Martina

AU - Elsner, Jan

AU - Broch, Katharina

AU - Geerts, Yves H.

AU - Schreiber, Frank

AU - Schweicher, Guillaume

AU - Wang, Hai I.

AU - Blumberger, Jochen

AU - Bonn, Mischa

AU - Beljonne, David

PY - 2023/11

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N2 - Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (μ) with temperature (T) following μ ∝ T −n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.

AB - Evidence shows that charge carriers in organic semiconductors self-localize because of dynamic disorder. Nevertheless, some organic semiconductors feature reduced mobility at increasing temperature, a hallmark for delocalized band transport. Here we present the temperature-dependent mobility in two record-mobility organic semiconductors: dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]-thiophene (DNTT) and its alkylated derivative, C8-DNTT-C8. By combining terahertz photoconductivity measurements with atomistic non-adiabatic molecular dynamics simulations, we show that while both crystals display a power-law decrease of the mobility (μ) with temperature (T) following μ ∝ T −n, the exponent n differs substantially. Modelling reveals that the differences between the two chemically similar semiconductors can be traced to the delocalization of the different states that are thermally accessible by charge carriers, which in turn depends on their specific electronic band structure. The emerging picture is that of holes surfing on a dynamic manifold of vibrationally dressed extended states with a temperature-dependent mobility that provides a sensitive fingerprint for the underlying density of states.

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ER -

Transiently delocalized states enhance hole mobility in organic molecular semiconductors

Abstract

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