Improved Efficiency of Polymer Solar Cells by Modifying the Side Chain of Wide-Band Gap Conjugated Polymers Containing Pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione Moiety

Two novel wide-band gap donor–acceptor-type conjugated copolymers, PTzBI-S and PTzBI-Ph, are designed and synthesized, based on alkylthio-thienyl- or alkylphenyl-substituted benzodithiophene (BDT) derivatives as the electron-donating unit and pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione as the electron-withdrawing unit. The as-generated copolymers show the comparable optical and electrochemical properties. The alkylthio-thienyl-substituted BDT unit facilities a benign decrease of the highest occupied molecular orbital (HOMO) levels. This consequently enhances open-circuit voltages (VOC) over 0.9 V in relevant solar cells with the fullerene acceptor ([6, 6]-phenyl-C71-butyric acid methyl ester, PC71BM) or the nonfullerene acceptor (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene, ITIC). The combination studies of Fourier transform photocurrent spectroscopy and electroluminescence further rationalize the VOC difference between solar cells with fullerene and nonfullerene acceptors. An impressively high power conversion efficiency of 10.19% is obtained for the device based on PTzBI-Ph:ITIC, outperforming the 8.84% achieved by the PC71BM-based device. Our results demonstrate that the modification of substituents of BDT units can effectively decrease the HOMO level and consequently improve VOC, ultimately allowing the attainment of high-efficiency polymer solar cells.