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Authors
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Shivhare, R. R. ; Erdmann, T. ; Hörmann, U. ; Collado-Fregoso, E. ; Zeiske, S. ; Benduhn, J. ; Ullbrich, S. ; Hübner, R. ; Hambsch, M. ; Kiriy, A. ; Voit, B. ; Neher, D. ; Vandewal, K. ; Mannsfeld, S.
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Title
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Alkyl branching position in diketopyrrolopyrrole polymers: Interplay between fibrillar morphology and crystallinity and their effect on photogeneration and recombination in bulk-heterojunction solar cells
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Date
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28.09.2018
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Number
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55896
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Abstract
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Diketopyrrolopyrrole (DPP)-based donor–acceptor copolymers have gained a significant amount of research interest in the organic electronics community because of their high charge carrier mobilities in organic field-effect transistors (OFETs) and their ability to harvest near-infrared (NIR) photons in solar cells. In this study, we have synthesized four DPP-based donor–acceptor copolymers with variations in the donor unit and the branching point of the solubilizing alkyl chains (at the second or sixth carbon position). Grazing incidence wide-angle X-ray scattering (GIWAXS) results suggest that moving the branching point further away from the polymer backbone increases the tendency for aggregation and yields polymer phases with a higher degree of crystallinity (DoC). The polymers were blended with PC70BM and used as active layers in solar cells. A careful analysis of the energetics of the neat polymer and blend films reveals that the charge-transfer state energy (ECT) of the blend films lies exceptionally close to the singlet energy of the donor (ED*), indicating near zero electron transfer losses. The difference between the optical gap and open-circuit voltage (VOC) is therefore determined to be due to rather high nonradiative (˜ 418 ± 13 mV) and unavoidable radiative voltage losses (˜ 255 ± 8 mV). Even though the four materials have similar optical gaps, the short-circuit current density (JSC) covers a vast span from 7 to 18 mA cm–2 for the best performing system. Using photoluminescence (PL) quenching and transient charge extraction techniques, we quantify geminate and nongeminate losses and find that fewer excitons reach the donor–acceptor interface in polymers with further away branching points due to larger aggregate sizes. In these material systems, the photogeneration is therefore mainly limited by exciton harvesting efficiency.
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Publisher
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Chemistry of Materials
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Wikidata
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Citation
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Chemistry of Materials 30 (2018) 6801-6809
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DOI
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https://doi.org/10.1021/acs.chemmater.8b02739
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