Understanding Pore Formation in ALD Alumina Overcoats.

Abstract

AlOX thin films deposited by atomic layer deposition (ALD) have previously been used to increase both stability and selectivity of supported palladium catalysts and are known to develop nanoscale porosity upon heating. Understanding the factors that affect ALD thin-film porosityenables future design of layered catalytic structures with tunable nanoscale features on industrially-relevant high-surface-area materials. In this study, porous and nonporous aluminum oxide supports with and without palladium nanoparticles were overcoated with thin films of 2-7 nm AlOX by ALD deposited at temperatures of 100, 200, and 300 °C. Hydroxyl loss and changes in surface chemistry were observed upon heating the films, and changes in surface area and pore volume of the annealed films were correlated to AlOX deposition temperature and the presence of Pd. Crystallization of the overcoat to γ-Al2O3 is shown to occur separately from hydroxyl loss and pore formation. A mechanistic understanding of pore formation in AlOX ALD films is obtained by reference to studies of the structural transformations accompanying the formation of transition aluminas from hydroxide precursors. Additionally, a direct and tunable correlation is established between pore development and the overall hydroxyl content of AlOX ALD coatings.