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.