Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer

One of the most inspiring and puzzling developments in the organic electronics community in the last few years has been the emergence of solution-processable semiconducting polymers that lack significant long-range order but outperform the best, high-mobility, ordered semiconducting polymers to date. Here we provide new insights into the charge-transport mechanism in semiconducting polymers and offer new molecular design guidelines by examining a state-of-the-art indacenodithiophene–benzothiadiazole copolymer having field-effect mobility of up to 3.6 cm2 V−1 s−1 with a combination of diffraction and polarizing spectroscopic techniques. Our results reveal that its conjugated planes exhibit a common, comprehensive orientation in both the non-crystalline regions and the ordered crystallites, which is likely to originate from its superior backbone rigidity. We argue that charge transport in high-mobility semiconducting polymers is quasi one-dimensional, that is, predominantly occurring along the backbone, and requires only occasional intermolecular hopping through short π-stacking bridges.