Structural properties, polymorphism, and multiscale disorder unravel energy transport limitations in perylene diimide semiconductors
File(s)
Published version
Author(s)
Type
Journal Article
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 micro-crystals of two perylene diimide (PDI) derivatives differing only in their terminal groups [cyclohexyl (CH) and 4-heptyl (ST)] have exciton diffusion coefficients differing by over two orders of magnitude. Applying state-of-the-art techniques for micro-crystal 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 micro-crystals, attributed to polymorph intergrowths, while electron energy loss spectroscopy links these defects to nanoscale electronic
structure changes. Computational modelling 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.
structure give rise to large differences in energy transport properties remains unresolved. We report that micro-crystals of two perylene diimide (PDI) derivatives differing only in their terminal groups [cyclohexyl (CH) and 4-heptyl (ST)] have exciton diffusion coefficients differing by over two orders of magnitude. Applying state-of-the-art techniques for micro-crystal 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 micro-crystals, attributed to polymorph intergrowths, while electron energy loss spectroscopy links these defects to nanoscale electronic
structure changes. Computational modelling 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.
Date Issued
2026-05-01
Date Acceptance
2026-04-23
Citation
Science Advances, 2026, 12 (22)
ISSN
2375-2548
Publisher
American Association for the Advancement of Science (AAAS)
Journal / Book Title
Science Advances
Volume
12
Issue
22
Copyright Statement
© 2026 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution License 4.0 (CC BY). https://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution license, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
License URL
Publication Status
Published
Article Number
eaed0037
Date Publish Online
2026-05-27