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Comprehensive Summary The industrialization of organic solar cells (OSCs) faces challenges due to complex synthesis routes and high costs of organic photovoltaic materials. To address this, we designed and synthesized a series of polythiophene‐based donor materials, PTVT‐T‐ x Cl (20%Cl, 50%Cl and 100%Cl), by introducing different degrees of chlorine substitution within their conjugated skeletons. The incorporation of chlorine atoms does not change the planar conformation of the conjugated main chain of the control polymer, PTVT‐T, but effectively reduces their HOMO energy levels (≤ –5.3 eV) and alters the crystallinity of the polymers. In addition, when preparing OSC by blending with non‐fused electron acceptor A4T‐16, the non‐radiative energy loss of the three photovoltaic devices gradually decreased with the increase of chlorine content (0.343, 0.278 and 0.189 eV, respectively). Notably, PTVT‐T‐20%Cl exhibited a more moderate nanoscale phase separation with the acceptor, leading to efficient exciton dissociation, lower bimolecular recombination, and thus a favorable current in the OSCs. Consequently, the photovoltaic device based on PTVT‐T‐20%Cl:A4T‐16 achieved a remarkable photovoltaic efficiency of 11.8%. In addition, the PTVT‐T‐xCl series polymers show much lower material‐only‐cost (MOC) values than the other reported photoactive material systems. This work provides the way for the development of low‐cost photovoltaic materials and the industrial application of OSC, overcoming previous limitations posed by high energy losses in polythiophene‐based donors.
Li et al. (Sat,) studied this question.