The Pseudo-Bilayer Bulk Heterojunction Active Layer of Polymer Solar Cells in Green Solvent with 18.48% Efficiency

Planar heterojunction (PHJ) is employed to obtain proper vertical phase separation for highly efficient polymer solar cells (PSCs). However, it heavily relies on the choice of orthogonal solvent in the production process. Here, we fabricated a pseudo-bilayer bulk heterojunction (PBHJ) PSC with cross-distribution in the vertical direction by preparing two layers of PM6 and BTP-eC9 blends in an <i>o</i>-XY solution with different dilution ratios to study the morphological evolution of PBHJ film. We found that the PBHJ film exhibits more uniform and suitable continuous interpenetrating network morphology and proper phase separation in the vertical direction for the formation of p-i-n structure. This provides an effective channel for exciton dissociation and charge transport, which is confirmed by both exciton generation simulations and charge dynamics measurements. The PBHJ devices can effectively inhibit trap recombination and accelerate charge separation and transfer. Based on good active layer morphology and balanced charge mobility, all-green solvent-processed PSCs with champion power conversion efficiencies (PCEs) of 18.48% and 16.83% are obtained in PM6:BTP-eC9 and PTQ10:BTP-eC9 systems, respectively. This work reveals the potential mechanism of morphological evolution induced by the PBHJ structure and provides an alternative approach for developing solution processing PSCs.