Wide Bandgap Polymer Donor with Acrylate Side Chains for Non‐Fullerene Acceptor‐Based Organic Solar Cells

Organic semiconductors inherently have a low dielectric constant and hence high exciton binding energy, which is largely responsible for the rather low power conversion efficiency of organic solar cells as well as the requirements to achieve delicate bulk‐heterojunction nanophase separation in the active layer. In this study, methyl acrylate as a weakly electron‐withdrawing side chain for the electron rich thiophene to prepare a new building block, methyl thiophene‐3‐acrylate (TA), with increased polarity is used. A wide bandgap polymer PBDT‐TA synthesized using TA and a benzodithiophene (BDT) monomer shows increased dielectric constant and reduced exciton binding energy compared to the analogous polymer PBDT‐TC, which is made of BDT and methyl thiophene‐3‐carboxylate (TC). An organic solar cell device based on PBDT‐TA:ITIC also achieves a higher power conversion efficiency of 10.47% than that of the PBDT‐TC:ITIC based solar cell (9.68%). This work demonstrates the effectiveness of using acrylate side chains to increase the dielectric constant, reduce the exciton binding energy, and enhance the solar cell efficiency of polymer semiconductors. Acrylate groups are used for the first time as weak electron‐withdrawing side chains for the construction of a wide‐bandgap polymer with increased dielectric constant and reduced exciton binding energy. As an electron donor, the polymer achieves enhanced efficiencies in non‐fullerene acceptor‐based organic solar cells.