Dibenzopyran-Based Wide Band Gap Conjugated Copolymers: Structural Design and Application for Polymer Solar Cells

With the efficient synthesis of the crucial dibenzopyran building block, a series of PDBPTBT polymers containing different alkyl side chains and/or fluorine substitution were designed and synthesized via the microwave-assisted Suzuki polycondensation. Quantum chemistry calculations based on density functional theory indicated that different substitutions have significant impacts on the planarity and rigidity of the polymer backbones. Interestingly, the alkyloxy chains of PDBPTBT-4 tend to stay in the same plane with the benzothiadiazole unit, but the others appear to be out of plane. With the S···O and F···H/F···S supramolecular interactions, the conformations of the four polymers will be locked in different ways as predicted by the quantum chemistry calculation. Such structural variation resulted in varied solid stacking and photophysical properties as well as the final photovoltaic performances. Conventional devices based on these four polymers were fabricated, and PDBPTBT-5 displayed the best PCE of 5.32%. After optimization of the additive types, ratios, and the interlayers at the cathode, a high PCE of 7.06% (V_oc = 0.96 V, J_sc = 11.09 mA/cm², and FF = 0.67) is obtained for PDBPTBT-5 with 2.0% DIO as the additive and PFN-OX as the electron-transporting layer. These results indicated DBP-based conjugated polymers are promising wide band gap polymer donors for high-efficiency polymer solar cells.