Liu, ZhenZhenLiuVanderspikken, JochenJochenVanderspikkenVandewal, KoenKoenVandewalMaes, WouterWouterMaesGoderis, BartBartGoderisNies, ErikErikNiesVan Den Brande NikoVan Mele Bruno2025-03-092025-03-0920251613-6810WOS:001434603600001https://imec-publications.be/handle/20.500.12860/45365Double binary state diagrams of the benchmark semi-crystalline conjugated polymer PBTTT and its alkoxy derivatives PBTTT-OR-R and PBTTT-(OR)2, mixed with PC61BM, are constructed using Rapid Heat-Cool Differential Scanning Calorimetry and T-resolved synchrotron X-Ray Diffraction. The polymerization method is adapted to ensure the absence of homocouplings and obtain reliable state diagrams, supported by Flory-Huggins calculations. Co-crystallization always occurs at a 45:55 w/w% polymer:PC61BM mixing ratio. All co-crystals remain stable up to 260‒280 °C in a wide composition range, and for the first time, it is proven that they show incongruent (peritectic) melting. The three state diagrams show one eutectic, i.e., between polymer and co-crystal in the case of PBTTT and PBTTT-OR-R, and between polymer and PC61BM for PBTTT-(OR)2. The latter eutectic beyond 280 °C leads to a reversible “solid-solid” transformation with the corresponding co-crystal. Isothermal treatments, at the onset temperature of co-crystallization during non-isothermal cooling, show no loss of co-crystal quality in combination with PC61BM perfectioning for fullerene-rich PBTTT:PC61BM and PBTTT-OR-R:PC61BM mixtures, whereas PBTTT-(OR)2:PC61BM, as well as Stille-polymerized PBTTT-OR-R:PC61BM with homocouplings, show suppression of co-crystallization with the formation of separate crystals of polymer and PC61BM. These opposing effects are explained by the state diagrams, showcasing their substantial value in selecting efficient annealing conditions.Journal article10.1002/smll.202410993WOS:001434603600001SPECTROSCOPYMISCIBILITYPOLYMERSMEDLINE:40018855