Frontier orbitals control dynamical disorder in molecular semiconductors

Neef, A.; Hammer, S.; Yao, Y.; Sharma, S.; Beaulieu, S.; Dong, S.; Pincelli, T.; Frank, M.; Wolf, M.; Rossi, M.; Oberhofer, H.; Rettig, L.; Pflaum, J.; Ernstorfer, R.

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Frontier orbitals control dynamical disorder in molecular semiconductors

MPS-Authors

Neef, A.
Department of Physical Chemistry, Fritz Haber Institute of the Max Planck Society;

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Sharma, S.
Simulations from Ab Initio Approaches, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Pincelli, T.
Department of Physical Chemistry, Fritz Haber Institute of the Max Planck Society;
Institut für Optik und Atomare Physik, Technical University;

Wolf, M.
Department of Physical Chemistry, Fritz Haber Institute of the Max Planck Society;

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Rossi, M.
Simulations from Ab Initio Approaches, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

Rettig, L.
Department of Physical Chemistry, Fritz Haber Institute of the Max Planck Society;

Ernstorfer, R.
Department of Physical Chemistry, Fritz Haber Institute of the Max Planck Society;
Institut für Optik und Atomare Physik, Technical University;

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https://arxiv.org/abs/2412.06030
(Preprint)

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2412.06030.pdf
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Citation

Neef, A., Hammer, S., Yao, Y., Sharma, S., Beaulieu, S., Dong, S., et al. (2024). Frontier orbitals control dynamical disorder in molecular semiconductors.

Cite as: https://hdl.handle.net/21.11116/0000-0010-4FB0-F

Abstract

Charge transport in organic semiconductors is limited by dynamical disorder. Design rules for new high-mobility materials have therefore focused on limiting its two foundations: structural fluctuations and the transfer integral gradient. However, it has remained unclear how these goals should be translated into molecular structures. Here we show that a specific shape of the frontier orbital, with a lack of nodes along the long molecular axis, reduces the transfer integral gradient and therefore the dynamical disorder. We investigated single crystals of the prototypical molecular semiconductors pentacene and picene by angle-resolved photoemission spectroscopy and dynamical disorder calculations. We found that picene exhibits a remarkably low dynamical disorder. By separating in- and out-of-plane components of dynamical disorder, we identify the reason as a reduced out-of-plane disorder from a small transfer integral derivative. Our results demonstrate that molecules with an armchair π-electron topology and same-phase frontier orbitals like picene are promising molecular building blocks for the next generation of organic semiconductors.