Using Atom Dynamics to Map the Defect Structure Around an Impurity in Nano-Hematite

• Published in: The journal of physical chemistry letters Vol. 11; no. 24; pp. 10396 - 10400
• Main Authors: Ilton, Eugene S, Kovarik, Libor, Nakouzi, Elias, Mergelsberg, Sebastian T, McBriarty, Martin E, Bylaska, Eric J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17-12-2020
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.0c02798

The bulk behavior of materials is often controlled by minor impurities that create nonperiodic localized defect structures due to ionic size, symmetry, and charge balance mismatches. Here, we used transmission electron microscopy (TEM) of atom-resolved dynamics to directly map the topology of Fe vacancy clusters surrounding structurally incorporated U6+ in nanohematite (α-Fe2O3). Ab initio molecular dynamic simulations provided additional independent constraints on coupled U, Fe, and vacancy mobility in the solid. A clearer understanding of how such an apparently incompatible element can be accommodated by hematite emerged. The results were readily interpretable without the need for sophisticated data reconstruction methods, model structures, or ultrathin samples, and with the proliferation of aberration-corrected TEM facilities, the approach is accessible. Given sufficient z-contrast, the ability to observe impurity-vacancy structures by means of atom hopping can be used to directly probe the association of impurities and such defects in other materials, with promising applications across a broad range of disciplines.