Selenite‐Directed Organotin–Oxo Macrocycles for Nanolithography

The systematic design of organotin-oxo macrocycles with enhanced extreme ultraviolet (EUV) photon-harvesting capability and sub-50 nm lithographic resolution remains a pivotal challenge in advancing nanofabrication technologies. Herein, we present a novel series of polynuclear ⁿbutyltin-oxygen macrocycles-Sn₈, Sn₁₂-α, Sn₁₂-β, and Sn₁₂Fe₁₈-constructed through selenite ligand-driven supramolecular assembly. Among these, Sn₁₂-α demonstrated exceptional electron beam lithography (EBL) performance, achieving a critical dimension resolution of 50 nm at a low dose of 50 µC·cm^-2, attributed to its elevated Sn/Se content, compact molecular architecture (diameter, 1.5 nm), and excellent film-forming ability (surface roughness, 0.59 nm). By replacing conventional carboxylate ligands with inorganic selenite, this study addresses longstanding limitations in structural versatility and EUV absorption efficiency inherent to traditional organotin-oxo systems. These findings establish a paradigm for engineering metal-oxide photoresists through ligand-driven cluster dimensionality control, offering a scalable pathway to high-sensitivity, high-resolution patterning for next-generation semiconductor manufacturing.