Interfacial Hybrid Engineering Strategy for Highly Efficient and Stable Large‐Area Perovskite Solar Modules

Abstract Self‐assembled molecules (SAMs) are considered promising materials for hole transport layers (HTL) in inverted perovskite solar cells (p‐i‐n PSCs). However, incomplete coverage, poor uniformity, and insufficient stability of SAM films still hinder the large‐scale industrial application of SAM‐based HTLs in PSCs. Here, an interfacial hybrid engineering (IHE) strategy is proposed that incorporates a molecular suppressor, 4,4,4‐tris(phosphoryl) triphenylmethane (PA), to regulate SAM assembly and optimize interfacial properties. PA effectively mitigates molecular aggregation of 2‐(9H‐carbazol‐9‐yl) ethylphosphonic acid (2PACz) through steric hindrance and chemical interactions, which ensures the homogeneous distribution, well‐ordered assembly, and scale‐up preparation of SAM molecules. Thereby, the perovskite/HTL interface exhibits improved energy level alignment, charge extraction efficiency, and defect passivation. The champion PCE of the PA‐based small‐area devices is 26.55%. Large‐area modules incorporating PA exhibit record‐breaking efficiencies of 22.81% (22.8 cm 2 ) and 20.16% (750.5 cm 2 ), representing the highest performance reported for single SAM‐HTL layers in scalable PSCs. Additionally, PA‐modified devices demonstrate remarkable operational stability under ISOS‐D and ISOS‐L testing conditions. This IHE strategy provides an effective and scalable solution for achieving uniform SAM deposition in large‐area PSCs while simultaneously enhancing device efficiency and long‐term durability, paving the way for the commercialization of SAM‐based perovskite photovoltaics.