Significantly Improved Morphology and Efficiency of Nonhalogenated Solvent‐Processed Solar Cells Derived from a Conjugated Donor–Acceptor Block Copolymer

A highly crystalline conjugated donor (D)-acceptor (A) block copolymer (PBDT2T-<i>b</i>-N2200) that has good solubility in nonhalogenated solvents is successfully synthesized. PBDT2T-<i>b</i>-N2200 shows a broad complementary absorption behavior owing to a wide-band gap donor (PBDT2T) present as a D-block and a narrow-band gap acceptor (N2200) present as an A-block. Polymer solar cells (PSCs) with conjugated block copolymer (CBCP) are fabricated using a toluene solution and PSC created with an annealed film showing the highest power conversion efficiency of 6.43%, which is 2.4 times higher than that made with an annealed blend film of PBDT2T and N2200. Compared to the blend film, the PBDT2T-<i>b</i>-N2200 film exhibits a highly improved surface and internal morphology, as well as a faster photoluminescence decay lifetime, indicating a more efficient photoinduced electron transfer. In addition, the PBDT2T-<i>b</i>-N2200 film shows high crystallinity through an effective self-assembly of each block during thermal annealing and a predominant face-on chain orientation favorable to a vertical-type PSC. Moreover, the CBCP-based PSCs exhibit an excellent shelf-life time of over 1020 h owing to their morphological stability. From these results, a D-A block copolymer system is one of the efficient strategies to improve miscibility and morphological stability in all polymer blend systems.