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How annealing influences the morphology of a highly regioregular poly(3‐hexylthiophene) (RR‐P3HT) film at the substrate interface as well as the lateral inhomogeneity in the electronic structure of the film are elucidated. Whereas previous studies have reported that high‐molecular‐weight (MW) RR‐P3HT films tend to show low crystallinity even after annealing, it is found that high‐MW RR‐P3HT does show...
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