Mechanism of Vapor-Phase Infiltration of Organometallic Hf in Poly(Methyl Methacrylate) for Hybrid Resist Applications

Inorganic–organic hybrid thin films synthesized by vapor-phase infiltration (VPI) of metal oxides into organic photoresists, such as poly(methyl methacrylate) (PMMA), have recently demonstrated their utility in extreme ultraviolet lithography, critical for angstrom-era semiconductor device miniaturization. Hafnium oxide infiltration has been reported recently for this purpose, but its detailed VPI mechanism has remained largely unexplored. In this study, we investigated the VPI characteristics and mechanisms of tetrakis(dimethylamido)hafnium (TDMAHf)─the hafnium precursor predominantly used for VPI in the field─into PMMA and examined its impact on electron-beam lithography (EBL) exposure behavior. VPI was performed at temperatures ranging from 85 to 150 °C, with chemical interactions characterized using infrared reflection-absorption spectroscopy, and resist patterning performance was evaluated through EBL dose-sensitivity assessments. The results indicate that TDMAHf forms a reversible adduct with PMMA at temperatures up to 120 °C, whereas at 150 °C, covalent bond formation occurs, most likely via dealkylation that leads to acetate formation. EBL studies reveal that resist sensitivity is influenced by both infiltration temperature and developer selection, with aqueous isopropyl alcohol development demonstrating enhanced sensitivity compared to organic solvent-based development. The optimized infiltration protocol at 120 °C ensures a uniform inorganic distribution without compromising resist dissolution. These findings not only help refine hybrid resist patterning performance but also offer insights potentially applicable to the VPI of other homoleptic metal-amide organometallic VPI precursors that include TDMA ligands.