To pursue high power conversion efficiency (PCE) of polymer solar cells (PSCs), more and more new active layer materials, especially polymeric photovoltaic materials, have been developed in the past several years, and benzo[1,2-b:4,5-b′]dithiophene (BDT) plays a very important role in these polymer materials. The applications of these new polymer materials boost the PCE of polymer solar cells greatly, and recent results indicate that 7–8% PCEs have been achieved by using BDT-based polymers. In this review, we summarize the recent works related to BDT-based polymers for the applications in PSCs and try to reveal the correlations of molecular structures of BDT-based polymers with their band gaps and molecular energy levels.
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