A Surface‐Reconstructed Bilayer Heterojunction Enables Efficient and Stable Inverted Perovskite Solar Cells

Abstract The efficiency of perovskite photovoltaics remains distant from their theoretical limits, primarily due to high photovoltage losses. Here a strategy is reported to minimize voltage losses by reconstructing the perovskite surface into a bilayer heterojunction (BLH) structure. Unlike conventional low‐dimensional capping layers, typically constrained to a few nanometers to prevent low fill factors, this methodology facilitates a more comprehensive reaction with surface defects, allowing a more substantial capping layer (≈50 nanometers) without compromising charge transport integrity. Time‐resolved microwave conductivity analysis indicates a significant reduction in trap density at the top region of the perovskite film, showing an order of magnitude lower than that of the pristine sample. Incorporating this BLH in inverted cells results in a remarkably low photovoltage deficit of 325 mV, leading to a power conversion efficiency (PCE) of 26.1% (25.72% certified). The encapsulated device maintains 94% of its original efficiency after 1200 h of maximum power point tracking under one sun illumination at 65 °C.