Quinoxaline-Based Wide Band Gap Polymers for Efficient Nonfullerene Organic Solar Cells with Large Open-Circuit Voltages

We present here a series of wide-band-gap (E_g: >1.8 eV) polymer donors by incorporating thiophene-flanked phenylene as an electron-donating unit and quinoxaline as an electron-Accepting co-unit to attain large open-circuit voltages (V_ocs) and short-circuit currents (J_scs) in nonfullerene organic solar cells (OSCs). Fluorination was utilized to fine-Tailor the energetics of polymer frontier molecular orbitals (FMOs) by replacing a variable number of H atoms on the phenylene moiety with F. It was found that fluorination can effectively modulate the polymer backbone planarity through intramolecular noncovalent S···F and/or H···F interactions. Polymers (P2-P4) show an improved molecular packing with a favorable face-on orientation compared to their nonfluorinated analogue (P1), which is critical to charge carrier transport and collection. When mixed with IDIC, a nonfullerene acceptor, P3 with two F atoms, achieves a remarkable V_oc of 1.00 V and a large J_sc of 15.99 mA/cm², simultaneously, yielding a power-conversion efficiency (PCE) of 9.7%. Notably, the 1.00 V V_oc is among the largest values in the IDIC-based OSCs, leading to a small energy loss (E_loss: 0.62 eV) while maintaining a large PCE. The P3:IDIC blend shows an efficient exciton dissociation through hole transfer even under a small energy offset of 0.16 eV. Further fluorination leads to the polymer P4 with increased chain-Twisting and mismatched FMO levels with IDIC, showing the lowest PCE of 2.93%. The results demonstrate that quinoxaline-based copolymers are promising donors for efficient OSCs and the fluorination needs to be fine-Adjusted to optimize the interchain packing and physicochemical properties of polymers. Additionally, the structure-property correlations from this work provide useful insights for developing wide-band-gap polymers with low-lying highest occupied molecular orbitals to minimize E_loss and maximize V_oc in nonfullerene OSCs for efficient power conversion.