Zn-Ti oxo cluster photoresists for EUV Lithography: Cluster structure and lithographic performance

[Display omitted] •Mixed metal clusters display enhanced solubility and film-forming properties than Ti clusters.•The presence of unstable ligands improves the lithographic sensitivity of clusters.•17 nm minimum linewidth was successfully achieved under EBL.•Successful patterning of mixed metal clusters by EUV. Low reflectivity of multilayer mirror–induced low efficiency of existing extreme ultraviolet lithography (EUVL) has triggered the search for photoresists with heightened sensitivity. For this purpose, considerable research has focused on elements with high extreme ultraviolet (EUV) absorption, leading to considerable advancements. Solubility alteration, often resulting from ligand variations after exposure, is influenced by the cluster structure, markedly impacting lithography sensitivity. Herein, three Ti-based metal clusters, Ti6O4(OEt)8(OMc)8 (T-2), Zn2Ti4O4(OiPr)2(OMc)10 (TZ-1), and Zn4Ti2O2(OAc)2(OBu)2(OMc)10 (TZ-2), are designed and synthesized to elucidate the effects of the structure on lithography. These mixed metal–oxo clusters derived from Ti6O4(OR)8(OOCR)8 and stabilized by identical ligands exhibit structural diversity. The increase in the number of zinc atoms results in marked alterations in the oxo core, thereby triggering alterations in ligand coordination modes. These variations confer metal clusters with different solubility and lithographic properties. Analysis of the photochemical reaction mechanism and theoretical calculations reveal a reactive tridentate ligand coordination mode that considerably improves lithography sensitivity. Therefore, changing the ligand coordination mode by designing a mixed metal–oxo core holds promise for discovering new photoresists for EUV lithography.