Understanding the Interfacial Reactions and Band Alignment for Efficient and Stable Perovskite Solar Cells Built on Metal Substrates with Reduced Upscaling Losses

Abstract Conventional perovskite solar cells (PSC) built on transparent conductive oxide (TCO) glass face a fundamental challenge to retain fill factor (FF) for large‐area upscaling due to series resistance loss. Building a perovskite solar cell on metal has the potential to reduce this FF loss and is promising for flexible applications. However, their efficiency and stability lag far behind their TCO counterparts. Herein, findings on the complex chemical reactions and degradation‐promoting processes at different perovskite/metal (Cu, Au, Ag, and Mo) interfaces, which are closely linked with the inherent stability; and the interlayer engineering for perovskite/metal interface's band alignment, which plays an essential role in achieving high efficiency, are reported. Leveraging these findings, 21% power conversion efficiency (PCE) is achieved for 1 cm 2 perovskite solar cells using a p–i–n top‐illumination structure on a molybdenum substrate, the highest reported for a PSC built on metal. Notably, the FF and PCE losses due to area upscaling are remarkably reduced by one order of magnitude relative to the counterparts on conventional TCO glass, highlighting an alternative pathway for PSC upscaling and module design.