Pioneering Carboxylated Zirconium Oxo Cluster Resist for Precision Nanoscale Patterning

Abstract As the demand for nanoscale semiconductors grows, Advanced resist materials for next‐generation lithography becomes increasingly critical. Expanding the range of available resists, particularly those incorporating metals, is essential to advancing lithographic technologies. Metal‐based photoresists have attracted attention due to their inherently high etch resistance, yet many suffer from poor pattern robustness, limited solution stability, and the need for photoacid generators (PAGs). Here, a zirconium (Zr)‐based oxo cluster bonded with benzoic acid (Zr‐OCB) photoresist that overcomes these limitations through a molecular design strategy is presented. This molecularly designed resist strengthens patterned features through dimerization and oligomerization under exposure, while benzoate ligands provide stability via strong coordination with the Zr cluster. This study demonstrates a new class of structurally defined, PAG‐free metal‐based hybrid resists with superior pattern fidelity and formulation stability. This allowed for the formation of high‐resolution patterns with a feature size of sub‐40 nm, a sensitivity of 1905 µC cm ^{− 2} , a low line edge roughness of 3.1 nm, and excellent solution stability for up to 6 months, highlighting its potential for industrial applications. This work presents a promising Zr‐based hybrid resist, offering enhanced stability and simplified processing, making it a valuable candidate for next‐generation lithography.