Molecular engineering of copolymers with donor-acceptor structure for bulk heterojunction photovoltaic cells toward high photovoltaic performance

A series of donor-acceptor (D-A) conjugated copolymers with benzo[1,2-b:4,5-b-]dithiophene (BDT) as donor and two different electron-accepting groups bithiophenevinyl-2-pyran-4-ylidenemalononitrile (TVM) and benzothiadiazole (BT) moieties as acceptors is designed and synthesized. The optical and electrochemical properties show that the band gaps of the copolymers are in the range of 1.70-1.84 eV, and the HOMO and LUMO energy levels can be tuned effectively by controlling the varied ratios between TVM and BT because of the change of the ICT interaction between donor and acceptor, the electron delocalization degree, and the electron cloud density distribution of the copolymers. Bulk heterojunction photovoltaic devices are fabricated by using the copolymers as donors and (6,6)-phenyl-C61-butyric acid methyl ester (PC61BM) or (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) as acceptors. The optimized photovoltaic performances show that the open-circuit voltage (Voc) was gradually increased from 0.7 to 0.94 V when decreasing the HOMO energy levels of copolymers, and the short-circuit current density (Jsc) is greatly improved by increasing the absorption spectrum in the visible region, increasing the hole mobility and optimizing the morphologies of blend films between copolymers and PCBM. The optimized photovoltaic performance with a Voc of 0.78 V, J sc of 5.47 mA/cm2, fill factor (FF) of 0.40, and power conversion efficiency (PCE) of 1.67% under simulated AM 1.5 solar irradiation of 100 mW/cm2 is obtained by the copolymer PM50 (PM50:PC 61BM, 1:3 w/w, in CB solution). This is due to its high hole mobility and interpenetrating network morphology of PM50:PC61BM blend film. The photovoltaic device based on PM50:PC71BM shows a Jsc of 8.32 mA/cm2 and a PCE of 2.89%