Effect of Alkyl Side Chains on Intercrystallite Ordering in Semiconducting Polymers

Kathryn O’Hara, Christopher J. Takacs, Shengjian Liu, Federico Cruciani, Pierre Beaujuge, Craig J. Hawker, Michael L. Chabinyc

Research output: Contribution to journalArticlepeer-review

15 Scopus citations


The connectivity between ordered domains in semiconducting polymers has been implicated as a bottleneck to charge transport. Crystallites in stiff-chain polymers have been shown to have ordered quasi-epitaxial domain boundaries using electron microscopy, but the factors affecting their formation have not been elucidated. A series of poly(benzo[1,2-b:4,5-b′]dithiophene-thieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) polymers with varying side chains were studied to determine the role of molecular structure on the formation of domain boundaries. Grazing incidence wide-angle X-ray scattering revealed the texture of ordered domains in these polymers as a function of thickness and thermal processing. High-resolution transmission electron microscopy (HRTEM) of thin films revealed that crystallites overlapped in an ordered fashion based on a geometric rule for the length of the crystallographic repeat length and the separation of the backbone by the side chains. All of the PBDTTPD polymers had polymorphic crystallites due to differences in alkyl stacking that behaved differently depending on their orientation to the substrate during thermal annealing. These results show the importance of domain orientation and boundaries on the morphology of semiconducting polymers.
Original languageEnglish (US)
Pages (from-to)2853-2862
Number of pages10
Issue number7
StatePublished - Mar 22 2019

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was also supported through the NSF DMREF program (DMR 1436263). Polymer synthesis was funded by Baseline Research Funding from King Abdullah University of Science and Technology (KAUST). The MRL Shared Experimental Facilities are supported by the MRSEC Program of the NSF under Award DMR 1720256. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-76SF00515.


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