Formation of solid thorium monoxide at near-ambient conditions as observed by neutron reflectometry and interpreted by screened hybrid functional calculations

摘要

Oxidation of a similar to 1000 angstrom sputter-deposited thorium thin film at 150 degrees C in 100 ppm of flowing oxygen in argon produces the long-sought solid form of thorium monoxide. Changes in the scattering length density (SLD) distribution in the film over the 700-min experiment measured by in-situ, dynamic neutron reflectometry (NR) shows the densities, compositions and thickness of the various thorium oxides layers formed. Screened, hybrid density-functional theory calculations of potential thorium oxides aid interpretation, providing atomic-level picture and energetics for understanding oxygen migration. NR provided evidence of the formation of substoichiometric thorium oxide, ThOy (y < 1) at the interface between the unreacted thorium metal and its dioxide overcoat which grows inward, consuming the thorium at a rate of 2.1 angstrom/min while y increases until reaching 1:1 oxygen-to-thorium. Its presence indicates that kinetically-favored solid-phase ThO can be preferentially generated as a majority phase under the thermodynamically-favored ThO2 top layer at conditions close to ambient. (C) 2017 Elsevier B.V. All rights reserved.