Interplay between Intrachain and Interchain Excited States in Donor-Acceptor Copolymers.

Recently, rapid progress in the power conversion efficiency for organic solar cells (OSCs) is achieved due to the phenomenal development of the nonfullerene electron acceptors. In addition to the pairing electron donors, conjugated donor-acceptor copolymers are another key player in the high-efficiency OSCs. Here, the temporal evolution of excited states in a typical copolymer, PM6, was traced by transient absorption spectroscopy. The spectroscopic result implies the formation of two kinetically correlated intrachain species, polaron excitons and intrachain polaron pairs. In the presence of the interchain interaction, these intrachain species quickly convert into interchain polaron pairs on a time scale of few picoseconds. Our findings reveal that the electron transfer mechanisms in PM6-based OSCs substantially depend on the PM6 environment in the bulk heterojunction blends.