AbstractC14‐alkoxy/alkyl PBTTT‐OR‐R, a derivative of the prototype PBTTT polymer, is relevant for optoelectronic applications because it combines PBTTT‐like intercalation behavior with enhanced charge‐transfer absorption at longer wavelengths. Additionally, fundamental insights are achieved by comparing this alternating conjugated polymer in the presence and absence of homocoupling defects. While the homocoupling‐free oxidative variant, PBTTT‐OR‐R(O), as well as the Stille polymer with 19% homocoupling defects, PBTTT‐OR‐R(S), can both form co‐crystals when stoichiometrically mixed with PC61BM, the co‐crystal of the latter shows properties which are highly dependent on the thermal processing conditions because of the presence of these defects. The PBTTT‐OR‐R(S):PC61BM co‐crystal shows a low thermal stability and PC61BM can progressively be expelled upon heating. In cooling from the melt and depending on the cooling rate, mixtures of PBTTT‐OR‐R(S) and PC61BM show a competition between co‐crystallization (fast cooling) and separate crystallization (slow cooling). The PBTTT‐OR‐R(O):PC61BM co‐crystal is much more stable up to at least 260 °C and is not influenced by the applied cooling rate. These findings also translate to the device level. The performance of PBTTT‐OR‐R:PC61BM photodiodes is severely deteriorated after isothermal annealing in case of PBTTT‐OR‐R(S), whereas the thermally robust co‐crystals of PBTTT‐OR‐R(O) allow a more flexible design of optimized devices.
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