A Polymer Donor Based on Difluoro-Quinoxaline with a Naphthalimide Substituent Unit Exhibits a Low-Lying HOMO Level for Efficient Non-Fullerene Polymer Solar Cells.

The design and synthesis of polymer donors with a low-lying highest occupied molecular orbital (HOMO) level are crucial for increasing open-circuit voltages (VOC) and achieving high-performance non-fullerene polymer solar cells. Here, we developed two copolymers using non-fluorinated or fluorinated thienyl-conjugated benzodithiophenes as electron donor units, and difluoro-quinoxaline with a naphthalimide substituent (DNB) as the electron acceptor unit. These copolymers, namely PDNB and PDNB-2F, exhibited deep HOMO levels owing to the strong electron-withdrawing ability of the naphthalimide substituent. Density-functional theory calculations demonstrated that the skeletons of the two copolymers featured good coplanarity. Owing to the fluorination, PDNB-2F displayed an increased absorption coefficient and deeper HOMO level than PDNB. Moreover, the blended film based on PDNB-2F:Y6 demonstrated enhanced carrier mobility, decreased bimolecular recombination as well as favorable phase-separation regions. Consequently, the PDNB-2F:Y6-based device yielded a superior power conversion efficiency (PCE) of 12.18%, whereas the device based on PDNB:Y6 showed a comparatively lower PCE of 8.83%. These results indicate that difluoro-quinoxaline with a naphthalimide substituent is a prospective electron-deficient building block to develop donor polymers with low-lying HOMO levels to achieve efficient non-fullerene polymer solar cells.