摘要： Two new D-A type photovoltaic polymers, namely PITPh-DfQx and PITPhf-DfQx, based on asymmetric indenothiophene (IT) donor units with alkoxyphenyl or fluoroalkoxyphenyl substitutes were designed and synthesized. Effects of the fluorine substitution in the asymmetric IT donor units on the electronic structure, ordering structure, photovoltaic properties, and charge generation and recombination dynamics were investigated. It is found that side-chain fluorination in the asymmetric donor units of the D-A polymers endowed the relative polymers with a deeper HOMO level, higher and more balanced charge mobilites, increased charge dissociation efficiency and reduced bimolecular recombination. As a result, the bulk heterojunction solar cell based on the blend film of PITPhf-DfQx and PC71BM demonstrated an efficiency of 6.10%, whereas the cell efficiency based on PITPh-DfQx was only 3.00%. In addition, a triblock copolymer, poly(styrene-block-butadiene-block-styrene) (SBS), was employed for the first time as a polymer additive into the active layers based on PITPh-DfQx/PC71BM and PITPhf-DfQx/PC71BM devices to promote donor crystallization and tune the extent of phase separation between the donor and acceptor. The presence of SBS obviously improved the molecule packing and induced the crystallization of the two polymers, giving rise to a better phase separation due to enhanced aggregation effect of photovoltaic polymers. Therefore, with a small addition of SBS, the optimal PCE was further increased from 6.10% to 6.60% for PITPhf-DfQx based device and from 3.00% to 5.50% for PITPh-DfQx based device. The positive effects of SBS additive on the performance of photovoltaic polymer/fullerene BHJ solar cells provide a new strategy for developing high performance polymer solar cells.