• Two pre-crystallization processes, gas quenching and vacuum quenching, lead to different crystallization dynamics within perovskite thin films, affecting additive distribution.
• A tailor-designed additive, 1,3-bis(4-methoxyphenyl)thiourea, improves the buried interface, achieving a certified efficiency of 23.75% for blade-coated perovskite solar cells.
• The perovskite solar module (aperture area: 60.84 cm2) demonstrates an efficiency of 20.18% with excellent operational stability (T90 > 1000 h under maximum power point tracking).
• The work provides insights into crystallization dynamics and additive engineering for scalable fabrication of efficient and stable perovskite photovoltaics.