Abstract
To improve the charge carrier mobility of diketopyrrolopyrrole donor–acceptor copolymer semiconductors, the length of the donor building block is controlled using vinylene moieties, and its effects on crystalline structure and charge transport are systematically studied. We synthesize P29-DPP-TBT with two vinylene linkages between thiophene units and compare it with P29-DPP-TVT with single vinylene linkage. Density functional theory calculations predict enhanced backbone planarity of P29-DPP-TBT compared to P29-DPP-TVT, which can be related to the increased conjugation length of P29-DPP-TBT as proved by the increased free exciton bandwidth extracted from UV–vis absorption spectra and the wavenumber shift of the C–C peaks to higher values in Raman spectra. From two-dimensional grazing incident X-ray diffraction studies, it is turned out that the paracrystalline disorder is lower in P29-DPP-TBT than in P29-DPP-TVT. Near-edge X-ray absorption fine structure spectroscopy reveal that more edge-on structure of ...
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