Structural properties, polymorphism, and multiscale disorder unravel energy transport limitations in perylene diimide semiconductors.

Smalley, Christopher J. H., Hughes, Colan E., Willhammar, Tom, Pandya, Raj, Saikin, Semion K., Johnstone, Duncan N., Gorman, Jeffrey, Sung, Jooyoung, Jacucci, Gianni, Midgley, Paul A., Kepaptsoglou, Demie M., Ramasse, Quentin M., Rao, Akshay, Harris, Kenneth D. M. ORCID: https://orcid.org/0000-0001-7855-8598 and Collins, Sean M. 2026. Structural properties, polymorphism, and multiscale disorder unravel energy transport limitations in perylene diimide semiconductors. Science Advances 12 (22) , eaed0037. 10.1126/sciadv.aed0037

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Abstract

Organic semiconductors continue to make substantial performance gains from photovoltaics to electronics. However, understanding how differences in solid-state structure give rise to large differences in energy transport properties remains unresolved. We report that microcrystals of two perylene diimide (PDI) derivatives differing only in their terminal groups [cyclohexyl (CH) and 4-heptyl (ST)] have exciton diffusion coefficients differing by more than two orders of magnitude. Applying state-of-the-art techniques for microcrystal structure determination, we report the crystal structures of CH-PDI and two polymorphs of ST-PDI. Scanning electron diffraction reveals a range of crystallographic defects in ST-PDI microcrystals, attributed to polymorph intergrowths, while electron energy loss spectroscopy links these defects to nanoscale electronic structure changes. Computational modeling demonstrates that rotational disorder explains the difference in exciton diffusion coefficients. Our observations establish the importance of defect-induced orientational disorder as a source of extrinsic energetic disorder, highlighting the need for defect management in organic semiconductor technologies.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Additional Information:	License information from Publisher: LICENSE 1: Title: cc by, Type: cc by
Publisher:	American Association for the Advancement of Science
Date of Acceptance:	23 April 2026
Last Modified:	02 Aug 2026 06:17
URI:	https://orca.cardiff.ac.uk/id/eprint/187482

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