Tailoring the Nature of Interface States in Efficient and Stable Bilayer Organic Solar Cells by a Transfer‐Printing Technique

Abstract Bulk heterojunction organic solar cells (BHJ‐OSCs) are designed to overcome inefficient charge generation and limited exciton diffusion of organic semiconductors. However, there are some disadvantages involving inherent voltage losses, microstructure control, and operational instability. Bilayer solar cells (BL‐OSCs) without mixed regions are free from these problems and offer a platform to explore the photophysical processes at the donor–acceptor interface. Here, a breakthrough for n‐i‐p BL‐OSCs in charge generation efficiency is reported. A gradual adjustment of the molecular interface orientation of the polymer donor (PM6) is accompanied by the evolution of charge‐transfer states and Forster energy transfer. Besides, less recombination losses and superior morphological stability of BL‐OSCs are achieved at a PCE comparable to that of BHJ‐OSCs with similar layer thickness. This investigation confirms the feasibility of manufacturing BL‐OSCs by a transfer printing method and provides a versatile architecture to study fundamental interface phenomena in OSCs independent from microstructure disorder.