Polymer Based on Asymmetrically Halogenated Benzotriazole Enables High Performance Organic Solar Cells Prepared in Nonhalogenated Solvent.

Halogenation on the A unit of the D-π-A-type polymer donor has been proven as an effective strategy to improve the performance of organic solar cells (OSCs). Compared with fluorination, chlorination usually increases the open-circuit voltage because of the downward shift of energy levels, but decreases the charge transport ability due to the large steric hindrance of the chlorine atom. We reported herein a method to balance the energy loss and charge transport through asymmetric halogenation on the benzotriazole (BTA) unit of the polymer. The designed PE3-FCl based on the BTA unit containing fluorine and chlorine atoms rendered the highest power conversion efficiency (PCE) of 17.83% when eC9-2Cl-γ and -xylene were used as the electron acceptor and solvent, respectively. The performance is obviously higher than that of the polymer PE3 containing a difluorinated BTA unit (16.65%) and polymer PE3-2Cl with dichlorinated BTA (14.65%) due to the manipulated morphology by preaggregation, improved and more balanced charge carrier transport, and reduced recombination loss. Notably, this PCE is a breakthrough for the BTA-based polymers processed by nonhalogenated solvent. This work gives deep insight into the asymmetric halogenation of polymer donors for high-performance green solvent-processed OSCs.