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To meet the industrial requirements of organic photovoltaic (OPV) cells, it is imperative to accelerate the development of cost‐effective materials. Thiophene‐benzene‐thiophene central unit‐based acceptors possess the advantage of low synthetic cost, while their power conversion efficiency (PCE) is relatively low. Here, by incorporating a para‐substituted benzene unit and 1st‐position branched alkoxy chains with large steric hindrance, a completely non‐fused non‐fullerene acceptor, TBT‐26, was designed and synthesized. The narrow band gap of 1.38 eV ensures the effective utilization of sunlight. The favorable phase separation morphology of TBT‐26‐based blend film facilitates the efficient exciton dissociation and charge transport in corresponding OPV cell. Therefore, the TBT‐26‐based small‐area cell achieves an impressive PCE of 17.0 %, which is the highest value of completely non‐fused OPV cells. Additionally, we successfully demonstrated the scalability of this design by fabricating a 28.8 cm2 module with a high PCE of 14.3 %. Overall, our work provides a practical molecular design strategy for developing high‐performance and low‐cost acceptors, paving the way for industrial applications of OPV technology. [ABSTRACT FROM AUTHOR]

Organic photovoltaic (OPV) cells, with highly tunable light‐response ranges, offer significant potential for use in driving low‐power consumption off‐grid electronics in multi‐scenarios. However, development of photoactive layer materials that can meet simultaneously the requirements of diverse irradiation conditions is a still challenging task. Herein, a low‐cost fully non‐fused acceptor (denoted as GS60) featuring well‐matched absorption spectra with solar, scattered light and artificial light radiation was designed and synthesized. Systematic characterizations revealed that GS60 possessed outstanding photoelectron properties and ideal morphology, which resulted in reduced voltage loss and suppressed charge recombination. By blending with a non‐fused ring polymer PTVT−T, the as‐obtained GS60 based OPV cells achieved a good power conversion efficiency (PCE) of 14.1 %, a high value for the cells based on non‐fused ring bulk heterojunction. Besides, manufactured large‐area OPV modules based on PTVT−T:GS60 yielded PCEs of 11.2 %, 11.8 %, 12.1 %, 23.1 %, and 20.3 % under irradiation of AM 1.5G, natural light of cloudy weather, natural light in shadow, laser and indoor, respectively. The PTVT−T:GS60 devices exhibited considerable potential in terms of improving photostability and reducing material cost. Overall, this work provides novel insight into the molecular design of low‐cost non‐fused ring acceptors, and extended potential of medium band gap acceptors based OPV cells used in various application scenarios. [ABSTRACT FROM AUTHOR]