n‑Type Semiconducting Naphthalene Diimide-Perylene Diimide Copolymers: Controlling Crystallinity, Blend Morphology, and Compatibility Toward High-Performance All-Polymer Solar Cells

Knowledge of the critical factors that determine compatibility, blend morphology, and performance of bulk heterojunction (BHJ) solar cells composed of an electron-accepting polymer and an electron-donating polymer remains limited. To test the idea that bulk crystallinity is such a critical factor, we have designed a series of new semiconducting naphthalene diimide (NDI)-selenophene/perylene diimide (PDI)-selenophene random copolymers, <i>x</i>PDI (10PDI, 30PDI, 50PDI), whose crystallinity varies with composition, and investigated them as electron acceptors in BHJ solar cells. Pairing of the reference crystalline (crystalline domain size <i>L</i>_c = 10.22 nm) NDI-selenophene copolymer (PNDIS-HD) with crystalline (<i>L</i>_c = 9.15 nm) benzodithiophene-thieno­[3,4-<i>b</i>]­thiophene copolymer (PBDTTT-CT) donor yields incompatible blends, whose BHJ solar cells have a power conversion efficiency (PCE) of 1.4%. However, pairing of the new 30PDI with optimal crystallinity (<i>L</i>_c = 5.11 nm) as acceptor with the same PBDTTT-CT donor yields compatible blends and all-polymer solar cells with enhanced performance (PCE = 6.3%, <i>J</i>_sc = 18.6 mA/cm², external quantum efficiency = 91%). These photovoltaic parameters observed in 30PDI:PBDTTT-CT devices are the best so far for all-polymer solar cells, while the short-circuit current (<i>J</i>_sc) and external quantum efficiency are even higher than reported values for [70]-fullerene:PBDTTT-CT solar cells. The morphology and bulk carrier mobilities of the polymer/polymer blends varied substantially with crystallinity of the acceptor polymer component and thus with the NDI/PDI copolymer composition. These results demonstrate that the crystallinity of a polymer component and thus compatibility, blend morphology, and efficiency of polymer/polymer blend solar cells can be controlled by molecular design