Organic solar cells (OSCs) have gained increasing attention. Among the various directions in OSCs, all-polymer solar cells (all-PSCs) have emerged as a highly promising and currently active research area due to their excellent film formation properties, mechanical properties, and thermal stabilities. However, most of the high-efficiency all-PSCs are processed from chloroform with an active layer thickness of ~100 nm. In order to meet the requirements for industrialization, a thicker active layer processed from low-vapor pressure solvents (preferentially a hydrocarbon solvent) is strongly desired. Herein, we employ toluene (a hydrocarbon solvent with a much higher boiling point than chloroform) and a method known as sequential processing (SqP) to mitigate the rapid decline in efficiency with increasing film thickness. We show that SqP enables a more favorable vertical phase segregation that leads to less trap-assisted recombination and enhanced charge extraction and lifetime than blend-cast devices at higher film thicknesses.
