Surface Dynamics of Selective Hydration of Rutile TiO₂: A Kinetic Monte Carlo Approach

The utility of atomic layer deposition (ALD) continues to expand beyond conformal thin-film fabrication to include area- or site-selective ALD. We previously identified a strategy for site-selective ALD (SS-ALD) via the evaluation of thermodynamically preferred hydration of rutile TiO₂ surfaces, as deduced from electronic structure calculations. Here, we report a novel kinetic Monte Carlo (KMC) model that allows for the investigation of surface dynamics and kinetics that improves our understanding of and intuition for the selective hydration strategy. Here we demonstrate the validity of the strategy with respect to step-edge defects for the lowest energy (110) facet as well as report results for the other common facets which agree with experimental STM observations. The results here indicate that the selective hydration strategy is feasible both thermodynamically (evaluated in our previous publication) and kinetically (from the KMC model). Because diffusion has a slower rate than others, we find that any proximity effects between terrace and defect sites are unlikely to affect the selective hydration strategy for rutile TiO₂. The KMC model further provides relevant timescales for achieving selectivity experimentally and establishes the kinetic viability of the selective hydration approach to SS-ALD.. Authors: Kamphaus, Ethan P. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000158212223); Jones, Jessica Catharine [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000174754620); Xu, Jiayi [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000317636251); Guest, Jeffrey R. [Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)] (ORCID:0000000297568801); Liu, Cong [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000221455034). DOE Contract: AC02-06CH11357. Subjects: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Adsorption; Atomic layer deposition; Hydration; Oxides; Thermodynamics