Highly Efficient and Stable ITO‐Free Organic Solar Cells Based on Squaraine N‐Doped Quaternary Bulk Heterojunction

Simultaneously achieving high efficiency and robust device stability remains a significant challenge for organic solar cells (OSCs). Solving this challenge is highly dependent on the film morphology of the bulk heterojunction (BHJ) photoactive blends; however, there is a lack of rational control strategy. Herein, it is shown that the molecular crystallinity and nanomorphology of nonfullerene-based BHJ can be effectively controlled by a squaraine-based doping strategy, leading to an increase in device efficiency from 17.26% to 18.5% when doping 2 wt% squaraine into the PBDB-TF:BTP-eC9:PC₇₁ BM ternary BHJ. The efficiency is further improved to 19.11% (certified 19.06%) using an indium-tin-oxide-free column-patterned microcavity (CPM) architecture. Combined with interfacial modification, CPM quaternary OSC excitingly shows an extrapolated lifetime of ≈23 years based on accelerated aging test, with the mechanism behind enhanced stability well studied. Furthermore, a flexible OSC module with a high and stable efficiency of 15.2% and an overall area of 5 cm² is successfully fabricated, exhibiting a high average output power for wearable electronics. This work demonstrates that OSCs with new design of BHJ and device architecture are highly promising to be practical relevance with excellent performance and stability.