Effect of Co-Reactants on Interfacial Oxidation in Atomic Layer Deposition of Oxides on Metal Surfaces

Swarup, Jay V.; Chuang, Heng-Ray; You, Amy L.; Engstrom, James R.

doi:10.1021/acsami.3c19033

Effect of Co-Reactants on Interfacial Oxidation in Atomic Layer Deposition of Oxides on Metal Surfaces

Journal Article · Wed Mar 20 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.3c19033· OSTI ID:2346145

Swarup, Jay V. ^[1]; Chuang, Heng-Ray ^[2]; ^[2]; ^[2]

Cornell University, Ithaca, NY (United States); Cornell University, Ithaca, NY
Cornell University, Ithaca, NY (United States)

We have examined the ALD of Al₂O₃ using TMA as the precursor and t-BuOH and H₂O as the co-reactants, focusing on the effects of the latter on both the ALD process and the possible modification of the underlying substrate. We have employed a quartz-crystal microbalance (QCM) to monitor ALD in situ and in real-time, and the deposited thin films have been characterized using X-ray photoelectron spectroscopy, spectroscopic ellipsometry, and X-ray reflectivity. Growth of thin films of Al₂O₃ using TMA and either t-BuOH or H₂O as the co-reactant at T = 285 °C produces thin films of similar physical properties (density, stoichiometry, minimal carbon incorporation), and the growth rate per cycle is similar for the two co-reactants at this temperature. At a lower temperature of T = 120 °C, the behavior is starkly different, where growth occurs with H₂O but not with t-BuOH. At either process temperature, we find no evidence for significant coverages of a long-lived tert-butoxy species from the reaction of t-BuOH. Deposition of thin films of Al₂O₃ on metal surfaces of Cu and Co has been examined for evidence of interfacial oxidation. While growth with either co-reactant does not lead to the oxidation of the underlying Cu substrate, use of H₂O leads to the oxidation of Co, while use of t-BuOH as the co-reactant does not. Thermodynamic factors may affect early stages of growth as Al species will likely scavenge all free O species. In contrast, at later times diffusion of species through the deposited Al²O₃ thin film could result in oxidation at the Al₂O₃|metal interface, a process that is strongly hindered in the case of t-BuOH due to its size. Furthermore, this observation highlights the importance of the choice of the co-reactant concerning ALD of oxides on metal surfaces.

View Accepted Manuscript (DOE)

Research Organization:: Cornell University, Ithaca, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0022059

OSTI ID:: 2346145

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 13 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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