Observation of Stepwise Ultrafast Crystallization Kinetics of Donor–Acceptor Conjugated Polymers and Correlation with Field Effect Mobility

The semicrystalline microstructures of donor–acceptor conjugated polymers strongly impact their optoelectronic properties. The control of the microstructure relies on the understandings of the crystallization processes in these polymers, from packing structures to crystallization kinetics. How fast these conjugated polymer chains crystallize and how their chemical structures and pre-existing microstructure history influence their crystallization have so far remained unclear, due to the fast crystallization rate caused by chain rigid structures and strong interactions. Here, ultrafast scanning calorimetry (FSC) is employed to reveal the crystallization behaviors of high performance diketopyrrolopyrrole (DPP)-based conjugated polymers with scanning rates up to 500 000 K/s. Through elaborately designed nonisothermal and isothermal crystallization studies, we probed the fast crystallization kinetics and extracted the two-step crystallization process of these polymers quantitatively. We found that both the rigidity of the chain backbones and the preinduced crystalline microstructures can influence the crystallization rate over an order of magnitude at the same degree of undercooling. We further demonstrated the manipulated crystallization kinetics in the DPP-based polymer films with different amounts of preinduced crystallites and correlate it to the polymers’ charge transport mobility.