Naphthalene diimide-based random terpolymer acceptors for constructing all-polymer solar cells with enhanced fill factors.

All-polymer solar cells (all-PSCs) with mechanical and thermal stability have potential for applications in flexible devices. Polymer acceptors based on naphthalene diimide (NDI) have been widely studied because of their strong electron affinity, high electron mobility, and high mechanical reliability. However, controlling the film morphology of the polymer-polymer blends of NDI-based all-PSCs is difficult. Consequently, all-PSCs based on NDI building blocks exhibit a low fill factor (FF) and a lower power-conversion efficiency (PCE) than state-of-the-art polymer solar cells. In this work, we added a small amount of dicyanodistyrylbenzene (DCB) unit to the NDI-based polymer acceptor N2200 through random copolymerization and synthesized a series of NDI-based terpolymer acceptors PNDI, where is the molar concentration of DCB units relative to NDI units. PNDI5 and PNDI10, corresponding to 5% and 10% molar concentrations of DCB, respectively, showed lower crystallization and good miscibility with PBDB-T, a widely used electron-donating copolymer, than the terpolymer based on DCB-free N2200. Moreover, compared to the PBDB-T:N2200 device, the PNDI5-based device exhibited a much higher PCE (8.01%), and an enhanced FF of 0.75 in all-PSCs. These results indicate that ternary random copolymerization is a convenient and effective strategy for optimizing the film morphology of NDI-based polymers, and that the resulting terpolymer acceptor is a promising n-type acceptor for constructing high-performance all-PSCs.