A Narrow-Bandgap n-Type Polymer Semiconductor Enabling Efficient All-Polymer Solar Cells

Currently, n-type acceptors in high-performance all-polymer solar cells (all-PSCs) are dominated by imide-functionalized polymers, which typically show medium bandgap. Herein, a novel narrow-bandgap polymer, poly(5,6-dicyano-2,1,3-benzothiadiazole-alt-indacenodithiophene) (DCNBT-IDT), based on dicyanobenzothiadiazole without an imide group is reported. The strong electron-withdrawing cyano functionality enables DCNBT-IDT with n-type character and, more importantly, alleviates the steric hindrance associated with typical imide groups. Compared to the benchmark poly(naphthalene diimide-alt-bithiophene) (N2200), DCNBT-IDT shows a narrower bandgap (1.43 eV) with a much higher absorption coefficient (6.15 × 10⁴ cm⁻¹). Such properties are elusive for polymer acceptors to date, eradicating the drawbacks inherited in N2200 and other high-performance polymer acceptors. When blended with a wide-bandgap polymer donor, the DCNBT-IDT-based all-PSCs achieve a remarkable power conversion efficiency of 8.32% with a small energy loss of 0.53 eV and a photoresponse of up to 870 nm. Such efficiency greatly outperforms those of N2200 (6.13%) and the naphthalene diimide (NDI)-based analog NDI-IDT (2.19%). This work breaks the long-standing bottlenecks limiting materials innovation of n-type polymers, which paves a new avenue for developing polymer acceptors with improved optoelectronic properties and heralds a brighter future of all-PSCs.