A fused-ring electron acceptor (FREA) NDIC is designed and synthesized. Inspired by IDIC, NDIC was constructed by replacing the benzene with a naphthalene ring in its core unit. IDIC exhibits an optical bandgap of 1.60 eV and a lower lowest unoccupied molecular orbital (LUMO) energy level of -3.92 eV. In comparison, NDIC displays an optical band gap of 1.72 eV and a higher lying LUMO energy level of -3.88 eV. Due to the higher energy level, inverted devices based on NDIC exhibit a higher open circuit voltage (V oc) of 0.90 V, which is much higher than that of IDIC (0.77 V). After a series of optimizations, a power conversion efficiency (PCE) of 9.43% was obtained with a PBDB-T:NDIC blend active layer, in comparison, a PCE of 9.19% was achieved based on IDIC. Our results demonstrate that a tiny variation in the molecular structure could dramatically affect the optical and electrochemical properties, and thus the photovoltaic performance.
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