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Ionic Liquid-Mediated Route to Atomic Layer Deposition of Tin(II) Oxide via a C-C Bond Cleavage Ligand Modification Mechanism.

Atomic layer deposition (ALD) is a technologically important method to grow thin films with high conformality and excellent thickness control from vapor phase precursors. The development of new thermal ALD processes can be limited by precursor reactivity and stability: reaction temperature and precursor design are among the few variables available to achieve higher reactivity in gas-phase reactions, unlike in solution synthesis, where the use of solvent and/or a catalyst can promote a desired reaction. To bridge this synthesis gap between vapor-phase and solution-phase, we demonstrate the use of an ultrathin coating layer of a vapor phase-compatible solvent─an ionic liquid (IL)─on our growth substrate to perform ALD of SnO. Successful SnO deposition is achieved using tin acetylacetonate and water, a process that otherwise would require a stronger counter-reactant such as ozone. The presence of the layer of IL allows a solvent-mediated reaction mechanism to take place on the growth substrate surface. We report a growth per cycle of 0.67 Å/cycle at a deposition temperature of 100 °C in an IL comprising 1-ethyl-3-methylimidazolium hydrogen sulfate. Characterization of the ALD films confirms the SnO film composition, and 1H and 13C NMR are used to probe the solvent-mediated ALD reaction, suggesting a solvent-mediated addition-elimination-type mechanism which breaks a C-C bond in acetylacetonate to form acetone and acetate. Density functional theory calculations show that the IL solvent is beneficial to the proposed solvent-mediated mechanism by lowering the C-C bond cleavage energetics of acetylacetonate compared to the vapor phase. A general class of ligand modification reactions for thermal ALD is thus introduced in this work.