Asymmetric Fluorinated Spiro Hole-Transport Materials Enabled by a Rapid Core-Forming Strategy for Blade-Coated...

Developing hole-transporting materials (HTMs) that simultaneously enable high efficiency, stability, and scalable processing remains a key challenge for perovskite solar cells (PSCs). Here, we report the facile synthesis of asymmetric fluorinated spiro-type HTMs that integrate molecular design with scalable fabrication. The controlled incorporation and positioning of fluorine within a common asymmetric molecular framework tune the energy levels, solid-state organization, and interfacial interactions of the HTMs. Coupling these materials with a fully blade-coating-based fabrication process and vacuum-assisted crystallization enables controlled film formation, yielding uniform, compact films with reduced defect density. As a result, PSCs based on the optimized HTM achieve a PCE of 24.49%, maintaining 23.28% for large-area (1.00 cm²) devices with excellent operational stability. This work establishes a synergistic molecular-processing engineering strategy toward high-performance and manufacturable PSCs.