Abstract

AbstractTwo new wide‐bandgap D–A–π copolymer donor materials, PBDT‐2TC and PBDT‐S‐2TC, based on benzodithiophene and asymmetric bithiophene with one carboxylate (2TC) substituent are synthesized by a facile approach for fullerene‐free organic solar cells (OSCs). The combination of one carboxylate‐substituted thiophene with one thiophene bridge in the backbone substantially reduces the steric hindrance, thereby favoring a planar geometry for efficient charge transport and molecular packing. A reasonable highest‐occupied‐molecular‐orbital energy level in relation to that of the acceptor and balanced hole and electron transport are observed for both polymers. This asymmetric structure unit is flexible and versatile, allowing the absorption, energy levels, and morphology of the blend films to be tailored. Fullerene‐free OSCs based on PBDT‐S‐2TC:ITIC achieve a high power conversion efficiency of 10.12%. More impressively, a successful nonhalogen solvent‐processed solar cell with 9.55% efficiency is also achieved, which is one of the highest values for a fullerene‐free OSC processed using an ecofriendly solvent.

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