It is a great challenge to simultaneously improve the two tangled parameters, open circuit voltage (Voc) and short circuit current density (Jsc) for organic solar cells (OSCs). Herein, such a challenge is addressed by a synergistic approach using fine‐tuning molecular backbone and morphology control simultaneously by a simple yet effective side chain modulation on the backbone of an acceptor–donor–acceptor (A–D–A)‐type acceptor. With this, two terthieno[3,2‐b]thiophene (3TT) based A–D–A‐type acceptors, 3TT‐OCIC with backbone modulation and 3TT‐CIC without such modification, are designed and synthesized. Compared with the controlled molecule 3TT‐CIC, 3TT‐OCIC shows power conversion efficiency (PCE) of 13.13% with improved Voc of 0.69 V and Jsc of 27.58 mA cm−2, corresponding to PCE of 12.15% with Voc of 0.65 V and Jsc of 27.04 mA cm−2 for 3TT‐CIC–based device. Furthermore, with effective near infrared absorption, 3TT‐OCIC is used as the rear subcell acceptor in a tandem device and gave an excellent PCE of 15.72%.

No abstract

An acceptor molecule with a cyclopentathiophene fused backbone, BCPT-4F, has been designed and synthesized. A power conversion efficiency of 14.23% was achieved for BCPT-4F based organic solar cells.

No abstract

No abstract