Design of Cyanovinylene-Containing Polymer Acceptors with Large Dipole Moment Change for Efficient Charge Generation in High-Performance All-Polymer Solar Cells

Designing polymers that facilitate exciton dissociation and charge transport is critical for the production of highly efficient all-polymer solar cells (all-PSCs). Here, the development of a new class of high-performance naphthalenediimide (NDI)-based polymers with large dipole moment change (Δµ_ge) and delocalized lowest unoccupied molecular orbital (LUMO) as electron acceptors for all-PSCs is reported. A series of NDI-based copolymers incorporating electron-withdrawing cyanovinylene groups into the backbone (PNDITCVT-R) is designed and synthesized with 2-hexyldecyl (R = HD) and 2-octyldodecyl (R = OD) side chains. Density functional theory calculations reveal an enhancement in Δµ_ge and delocalization of the LUMO upon the incorporation of cyanovinylene groups. All-PSCs fabricated from these new NDI-based polymer acceptors exhibit outstanding power conversion efficiencies (7.4%) and high fill factors (65%), which is attributed to efficient exciton dissociation, well-balanced charge transport, and suppressed monomolecular recombination. Morphological studies by grazing X-ray scattering and resonant soft X-ray scattering measurements show the blend films containing polymer donor and PNDITCVT-R acceptors to exhibit favorable face-on orientation and well-mixed morphology with small domain spacing (30–40 nm).