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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The datasets generated and/or analysed during the current study are available in the Zenodo repository, https://zenodo.org/record/8109807. The full data for this study total a couple of terabytes and are in cold storage accessible by the corresponding authors and available upon reasonable request.
The custom FOB-SH code for non-adiabatic molecular dynamics, the python code used for the DA analysis and other post-processing tools used for this study are available from the corresponding authors upon request.
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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.
The authors declare no competing interests.
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Giannini, S., Di Virgilio, L., Bardini, M. et al. Transiently delocalized states enhance hole mobility in organic molecular semiconductors. Nat. Mater. (2023). https://doi.org/10.1038/s41563-023-01664-4