Benzodithiophene-Dithienylbenzothiadiazole Copolymers for Efficient Polymer Solar Cells: Side-Chain Effect on Photovoltaic Performance

A new series of low band gap D-A alternating polymers based on 4,S-bis((2-ethylhexyl)oxy)benzo[2,1-b:3,4b']dithiophene (BDT) and 5-fluoro-4,7-bis(4-alkylthien-2-yl)benzo[c][1,2,5]thiadiazole bearing different size of lateral alkyl substituents, namely, PfBB-n, n = 8, 10, 12, 14, and 16, was designed and synthesized for high-performance bulk heterojunction (BHJ) polymer solar cells (PSCs). PfBB-n-bearing linear alkyl side chains exhibited strong and controllable aggregation in both solution and solid states, which gives rise to a significant bathochromic shift of the absorption cut-off down to similar to 780 nm in thin film. In addition, the strong and wide absorption (350-800 nm) of PfBB-n polymers can compensate for the relatively weak absorption of PC71BM, particularly in the 300-400 range nm to enhance light harvesting of such an active blend. BHJ solar cells based on PfBB-n:PC71BM blends as an active layer showed power conversion efficiency (PCE) in the range 7.8-9.7%. Because of the strong stacking interchain interactions, PfBB-12-based PSC exhibited aggregation-induced spectral broadening, superior structural order, higher exciton dissociation, higher and more balanced charge carrier mobilities, as well as reduced recombination losses. As a result, PfBB-12-based device afforded the best PCE of 9.7%, with the highest short-circuit current density (J(sc)) of 16.6 mA cm(-2) and open-circuit voltage (V-oc) of 0.92 V among devices fabricated. These results demonstrate that the alkyl side chain of the polymer significantly affects the absorption, morphology, and electronic properties of the active blend of PfBB-n/PC71BM, which would provide an alternative useful tool to fine-tune the device performance. Our results also highlight that the electron-rich benzo[2,1-b:3,4-b']dithiophene building block, BDT, is highly useful for the construction of low band gap D-A polymer for highly efficient PSCs.