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Despite its potential, the problems of area\u2010selectivity losing beyond a certain thickness remain critical in ASD applications. This study reports a novel approach to sustain the area\u2010selectivity of Ir films as the thickness increases. Ir films are deposited on Al<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub> as the growth area and SiO<jats:sub>2<\/jats:sub> as the non\u2010growth area using atomic\u2010layer\u2010deposition with tricarbonyl\u2010(1,2,3\u2010<jats:italic>\u03b7<\/jats:italic>)\u20101,2,3\u2010tri(<jats:italic>tert<\/jats:italic>\u2010butyl)\u2010cyclopropenyl\u2010iridium and O<jats:sub>3<\/jats:sub>. O<jats:sub>3<\/jats:sub> exhibits a dual effect, facilitating both deposition and etching. In the steady\u2010state growth regime, O<jats:sub>3<\/jats:sub> solely contributes to deposition, whereas in the initial growth stages, longer exposure to O<jats:sub>3<\/jats:sub> etches the initially formed isolated Ir nuclei through the formation of volatile IrO<jats:sub>3<\/jats:sub>. Importantly, longer O<jats:sub>3<\/jats:sub> exposure is required for the initial etching on the growth area(Al<jats:sub>2<\/jats:sub>O<jats:sub>3<\/jats:sub>) compared to the non\u2010growth area(SiO<jats:sub>2<\/jats:sub>). By controlling the O<jats:sub>3<\/jats:sub> injection time, the area selectivity is sustained even above a thickness of 25\u00a0nm by suppressing nucleation on the non\u2010growth area. These findings shed light on the fundamental mechanisms of ASD using O<jats:sub>3<\/jats:sub> and offer a promising avenue for advancing thin\u2010film technologies. Furthermore, this approach holds promise for extending ASD to other metals susceptible to forming volatile species.<\/jats:p>","DOI":"10.1002\/smll.202402543","type":"journal-article","created":{"date-parts":[[2024,7,30]],"date-time":"2024-07-30T10:51:05Z","timestamp":1722336665000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Sustained Area\u2010Selectivity in Atomic Layer Deposition of Ir Films: Utilization of Dual Effects of O<sub>3<\/sub> in Deposition and Etching"],"prefix":"10.1002","volume":"20","author":[{"given":"Han","family":"Kim","sequence":"first","affiliation":[{"name":"KU\u2010KIST Graduate School of Converging Science and Technology Korea University  Seoul 02841 South Korea"},{"name":"Electronic Materials Research Center Korea Institute of Science and Technology  Seoul 02792 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Taeseok","family":"Kim","sequence":"additional","affiliation":[{"name":"KU\u2010KIST Graduate School of Converging Science and Technology Korea University  Seoul 02841 South Korea"},{"name":"Electronic Materials Research Center Korea Institute of Science and Technology  Seoul 02792 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hong Keun","family":"Chung","sequence":"additional","affiliation":[{"name":"Electronic Materials Research Center Korea Institute of Science and Technology  Seoul 02792 South Korea"},{"name":"Department of Materials Science and Chemical Engineering Hanyang University  Ansan 15588 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jihoon","family":"Jeon","sequence":"additional","affiliation":[{"name":"KU\u2010KIST Graduate School of Converging Science and Technology Korea University  Seoul 02841 South Korea"},{"name":"Electronic Materials Research Center Korea Institute of Science and Technology  Seoul 02792 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sung\u2010Chul","family":"Kim","sequence":"additional","affiliation":[{"name":"Advanced Analysis and Data Center Korea Institute of Science and Technology  Seoul 02792 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sung Ok","family":"Won","sequence":"additional","affiliation":[{"name":"Advanced Analysis and Data Center Korea Institute of Science and Technology  Seoul 02792 South Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryosuke","family":"Harada","sequence":"additional","affiliation":[{"name":"Chemical Materials Development Department TANAKA Kikinzoku Kogyo K.K.  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