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The proper domain size of the active layer plays a key role in determining the exciton dissociation and charge transport in all-polymer solar cells (all-PSCs). However, fine-tuning the domain size remains challenging due to low glass transition temperature and negligible mixing entropy in polymer blends. Herein, we systematically studied the influence of "crystallization kinetics" on the domain size and proposed that if the donor and acceptor crystallize simultaneously, they are prone to form a large domain, while if sequential crystallization of the donor