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The power conversion efficiencies (PCEs) of state-of-the-art polymer solar cells (PSCs) have been promoted to over 9%. However, halogenated solvents like chlorobenzene (CB), o-dichlorobenzene (DCB), 1,8-diiodooctane (DIO) or their mixtures are still predominately used in the fabrications of these high performance PSCs. With the rapid progress in PCEs, to remove the halogenated solvents from the fabrication processes of PSCs becomes an urgent task for the practical utilization of PSC technology. In this contribution, a halogen-free solvent system consisting of o-xylene (XY) and N-methylpyrrolidone (NMP) was successfully applied in fabrications of the PSCs based on a variety of highly efficient polymers including PBDT-TS1 and other eight types of photovoltaic polymers. Notably, utilizing XY/2% NMP mixture as processing solvent, PBDT-TS1/PC71BM-based PSC realized a PCE of 9.47%, which is the highest value in halogen-free solvent processed PSCs till now. The photovoltaic properties and nanoscale morphology clearly indicated that the halogen-free solvent system featuring XY/NMP mixture can replace the role of the widely utilized halogenated solvents in fabricating environmental-friendly PSCs with high efficiency.

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