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

Abstract

ABSTRACT 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 cm 2 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.