Fluorine Modification Strategy for Switching Lithographic Polarity of Sb₂−Oxo Clusters: Conversion of Negative‐Tone to Positive‐Tone Patterns†

Comprehensive Summary Extreme ultraviolet (EUV) lithography is a key technology for sub‐7 nm nodes semiconductor manufacturing but faces challenges due to low energy conversion efficiency and weak sensitivity of photoresists. Antimony (Sb)‐based materials have attracted increasing attention for their high EUV absorption cross‐section. Herein, through a fluorine modification strategy, we functionalized a Sb 2 ‐oxo cluster with tailored carboxylic acid ligands to achieve dual‐tone photoresist control. Crucially, fluorinated ligands induced positive‐ tone patterning with enhanced sensitivity, while the non‐fluorinated ligand decorated Sb 2 ‐oxo cluster maintained conventional negative‐tone behavior. Combined X‐ray photoelectron spectroscopy (XPS) analysis, UV‐vis absorption spectroscopy analysis, and theoretical calculations highlight the potential of fluorine to alter the inherent cross‐linking mechanisms. This work not only enriches the examples of metal oxo cluster based positive photoresists but also provides an effective approach to manipulating photoresist polarity at the molecular level.