Abstract
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...
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