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Competing influences of cooling rate and diluent concentration on crystallization of poly(3-hexylthiophene)

Mina Alizadehaghdam, Farhang Abbasi, Günter Reiter. J. Phys. Chem. C 128 (2024) 4757–4765

Crystallization of poly(3-hexylthiophene) (P3HT) was studied in mixtures of different concentrations of 3-hexylthiophene (3HT) as a diluent. Two coexisting crystal populations, socalled “thin” and “thick” crystals, with melting temperatures differing by more than 10 °C were observed in these mixtures. Intriguingly, the “thick” crystals represented transient unstable structures, with a mass fraction that was the highest ФH for rapidly crystallized P3HT in presence of significant amount of diluent. Reflecting its dependence on growth kinetics, ФH decreased with increasing crystallization temperature, extended crystallization time or lower cooling rate. The presence of a diluent led to a “depression” of the melting temperature, described by Raoult’s law and the Flory equation, which was similar for P3HT samples crystallized in various ways. A kinetically controlled “enhancement” of the melting temperature caused by the presence of the diluent depended sensitively on the cooling rates.

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