Comparative Study of Selenophene- and Thiophene-Containing n‑Type Semiconducting Polymers for High Performance All-Polymer Solar Cells

Effects of the donor moiety substitution on the intrinsic and photovoltaic blend properties of n-type semiconducting naphthalene diimide-arylene copolymers with donor–acceptor structure were investigated. The alternating naphthalene diimide-thiophene copolymer, PNDIT-hd, and naphthalene diimide-selenophene copolymer, PNDIS-hd, were found to have identical electrochemically derived electronic structures and similar bulk electron mobility; however, PNDIS-hd has an optical bandgap of 1.70 eV, which is 0.07 eV narrower relative to that of PNDIT-hd. All-polymer solar cells incorporating the donor polymer, PBDB-T, and PNDIS-hd were found to combine a high power conversion efficiency of 8.4% with high external quantum efficiency (86%) and a high fill factor of 0.71, which are significantly enhanced compared to the corresponding PBDB-T:PNDIT-hd devices with 6.7% power conversion efficiency and 73% external quantum efficiency. The improved photovoltaic properties of the selenophene-containing acceptor copolymer relative to the thiophene counterpart originate from enhanced light harvesting, more favorable molecular packing in blends, and reduced charge recombination losses in devices. These findings demonstrate that selenophene substitution for thiophene in donor–acceptor copolymers is an effective strategy that enhances the intrinsic polymer properties as well as the performance of all-polymer solar cells incorporating them.