Isothermal Crystallization Kinetics and Time–Temperature–Transformation of the Conjugated Polymer: Poly(3-(2′-ethyl)hexylthiophene)

[Image: see text] Thermal annealing strongly impacts the nano- and microstructure of conjugated polymers. Despite the fundamental importance for the resulting optoelectronic behavior of this class of materials, the underlying crystallization processes have not received the same attention that is encountered in other disciplines of materials science. The question arises whether classical treatment of nucleation and growth phenomena is truly applicable to conjugated polymers? Here, the isothermal crystallization behavior of the conjugated polymer poly(3-(2′-ethyl)hexylthiophene) (P3EHT) is monitored with differential scanning calorimetry (DSC). Avrami analysis reveals growth- and nucleation-limited temperature regimes that are separated by the maximum rate of crystallization. The molecular weight of the polymer is found to strongly influence the absolute rate of crystallization at the same degree of undercooling relative to the melting temperature. A combination of optical microscopy and grazing-incidence wide-angle X-ray scattering (GIWAXS) confirms that the resulting nano- and microstructure strongly correlate with the selected isothermal annealing temperature. Hence, this work establishes that classical nucleation and growth theory can be applied to describe the solidification behavior of the semicrystalline conjugated polymer P3EHT.