Revealing Structure-Driven Performance of Molecular-Atomic Layer Deposited Resists for Extreme Ultraviolet Lithography through In Situ Analysis

Advancing resist chemistry remains a central challenge for extreme ultraviolet (EUV) lithography to sustain device scaling beyond the sub-1 nm technology node. Molecular-atomic layer deposited (MALD) inorganic–organic hybrid resists offer a promising route owing to their precisely controlled molecular architectures. However, the molecular design principles that drive their lithographic performance remain poorly understood, with prior studies primarily emphasizing inorganic constituents. Here, we systematically decouple the roles of metal centers and organic linkers in MALD-based hybrid EUV resists using a library of inorganic–organic thin films composed of three metal species and chemically distinct aromatic and aliphatic linkers. We reveal that organic linker chemistry, rather than the metal component, is the dominant factor governing resist sensitivity. Aliphatic-linker resists exhibit up to approximately 130-fold higher EUV sensitivity than their aromatic counterparts. Real-time monitoring via in situ Fourier transform infrared spectroscopy (FTIR) reveals distinct radiation-induced reaction pathways: aromatic systems primarily undergo inter-ring cross-linking, whereas aliphatic systems rapidly form dense metal–S and metal–O cross-linked networks. This work highlights organic-linker selection as a critical molecular design rule for MALD hybrid dry resists and provides mechanistic guidance for next-generation EUV lithography.