Halogenated Metal‐Organic Clusters for High‐Resolution Extreme Ultraviolet Lithography Resists †

Comprehensive Summary The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub‐20 nm features for next‐generation extreme ultraviolet (EUV) lithography. Metal‐oxo clusters, with sub‐5 nm molecular dimensions, structural tunability, and high EUV absorption via metal centers, have emerged as promising EUV photoresist candidates. Advancing next‐generation photoresist materials necessitates resolving the inherent trade‐offs between sensitivity, resolution, and line‐edge roughness. In this work, we report a series of halogenated metal‐organic clusters based EUVL photoresists, aiming to modulate the sensitivity, resolution, and line‐edge roughness. Here, we report the synthesis of halogenated metal‐organic clusters as EUVL photoresists, designed to modulate the resolution‐line edge roughness‐sensitivity trade‐off. Sub‐20 nm critical dimensions and line edge roughness below 2 nm were achieved with the clusters by EUVL. The results demonstrated that halogen elements influenced the sensitivity of the clusters. To unravel the EUV‐driven reaction pathways, we analyzed the chemical transformations in these clusters after exposure using X‐ray photoelectron spectroscopy and Fourier‐transform infrared spectroscopy. These findings pave the way for the rational design of high‐performance EUV photoresists.