Fluid-Crystallization Synergy for >26% Efficiency Fully Ambient-Printed SAM-Based Perovskite Photovoltaics

While lab-scale spin-coating in inert environments has delivered record efficiencies for perovskite solar cells (PSCs) employing self-assembled monolayers (SAMs), their fabrication via fully ambient-air printing-a prerequisite for low-cost industrialization-remains unreported. Here, we report the first PSCs exceeding 26% efficiency based on fully ambient-air printed SAMs and perovskite films and elucidate the governing role of SAM physicochemical properties through fluid-crystallization synergy. SAMs with higher surface energy (γ) flatten the perovskite ink meniscus, attenuating the temperature gradient and Marangoni stress along the gas-liquid interface, thereby enabling more uniform perovskite deposition and smoother films. Simultaneously, γ systematically modulates perovskite crystallization by delaying nucleation onset and shifting the growth mode from continuous to instantaneous on higher-γ SAMs. The fluid-crystallization synergy yields a record power conversion efficiency (PCE) of 26.31% (certified 25.85%), a benchmark for all reported ambient-air printed devices, including non-SAM-based counterparts. The approach further enables scalable fabrication, achieving a champion PCE of 22.3% in 13.04 cm² mini-modules with over 90% performance retention after 1200 h operation under the ISOS-L-1 protocol. This work establishes a quantitative link between SAM physicochemical properties and perovskite fluid dynamics and crystallization thermodynamics in ambient-air printing, providing guidance for perovskite photovoltaics toward scalable ambient manufacturing.