Sustained Area‐Selectivity in Atomic Layer Deposition of Ir Films: Utilization of Dual Effects of O₃ in Deposition and Etching

Area‐selective deposition (ASD) based on self‐aligned technology has emerged as a promising solution for resolving misalignment issues during ultrafine patterning processes. Despite its potential, the problems of area‐selectivity losing beyond a certain thickness remain critical in ASD applications. This study reports a novel approach to sustain the area‐selectivity of Ir films as the thickness increases. Ir films are deposited on Al 2 O 3 as the growth area and SiO 2 as the non‐growth area using atomic‐layer‐deposition with tricarbonyl‐(1,2,3‐ η )‐1,2,3‐tri( tert ‐butyl)‐cyclopropenyl‐iridium and O 3 . O 3 exhibits a dual effect, facilitating both deposition and etching. In the steady‐state growth regime, O 3 solely contributes to deposition, whereas in the initial growth stages, longer exposure to O 3 etches the initially formed isolated Ir nuclei through the formation of volatile IrO 3 . Importantly, longer O 3 exposure is required for the initial etching on the growth area(Al 2 O 3 ) compared to the non‐growth area(SiO 2 ). By controlling the O 3 injection time, the area selectivity is sustained even above a thickness of 25 nm by suppressing nucleation on the non‐growth area. These findings shed light on the fundamental mechanisms of ASD using O 3 and offer a promising avenue for advancing thin‐film technologies. Furthermore, this approach holds promise for extending ASD to other metals susceptible to forming volatile species.