Structure-Function Relationships in PMA and PMAT Series Copolymers for Polymer Solar Cells

Two series (PMA and PMAT) of two-dimensional donor-acceptor copolymers consisting of a 3,4-bis(4-bromophenyl)maleimide derivative and triphenylamine with a conjugated side chain were designed and synthesized to probe their structure-function relationships for use in bulk heterojunction (BHJ) polymer solar cells (PSCs). The difference between PMA- and PMAT-series is the conjugated side chain length on the triphenylamine unit. By extending the side chain length, and by attaching various acceptor end groups to the side chain, the electronic and photophysical properties of these copolymers, as well as subsequent device performance, were significantly affected. Two series of copolymers showed broad absorption in the visible region with two obvious peaks. With increasing electron-withdrawing strength of the acceptor end groups, the intramolecular charge transfer peak becomes progressively red-shifted. Highest occupied molecular orbital (HOMO) levels in each copolymer series are similar, but lowest unoccupied molecular orbital (LUMO) levels are dictated by the acceptors. BHJ PSCs composed of the copolymers as a donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC₇₁BM) as an acceptor in 1:2 weight ratio were fabricated and characterized. PSCs based on PMA- and PMAT-series copolymers had power conversion efficiencies (PCEs) ranging from 2.05⁻2.16% and 3.14⁻4.01%, respectively. These results indicate that subtle tuning of the chemical structure can significantly influence PSC device performance.