On the Interplay Between Oxygen Vacancies and Small Polarons in Manganese Iron Spinel Oxides.

Ternary spinel oxides are promising materials due to their potentially versatile properties resulting from the disorder inherent in their crystal structure. To fully unlock the potential of these materials, a deeper understanding of their electronic structures, both as pristine and defective crystals, is required. In the present work, we investigate the effects of oxygen vacancies on the electronic structure and charge transport properties of the ternary spinel oxide Mn x Fe3-x O4, modeled on epitaxial thin films of the material, using density functional theory + U (DFT + U). The formation energy of a single oxygen vacancy in the spinel cell is found to be large and unaffected by changes in stoichiometry, in agreement with experimental results. We find that the immediate vicinity of the vacancy has a marked impact on the formation energy. In particular, Mn cations are found to be preferred over Fe as sites for charge localization around the vacancy. Finally, we examine the charge transport in the defective cell using the formalism of Marcus theory and find that the activation barrier for electron small-polaron hopping between sites not adjacent to the vacancy is significantly increased, with a large driving force toward sites that reside on the same (001) plane as the vacancy. Hence, vacancies delay charge transport by increasing the activation barrier, attributed to a rearrangement of vacancy-released charge on the cations immediately neighboring the vacancy site. These results highlight the impact of oxygen vacancies on charge transport in spinel oxides.

Breakdown of the Small-Polaron Hopping Model in Higher-Order Spinels.

The small-polaron hopping model has been used for six decades to rationalize electronic charge transport in oxides. The model was developed for binary oxides, and, despite its significance, its accuracy has not been rigorously tested for higher-order oxides. Here, the small-polaron transport model is tested by using a spinel system with mixed cation oxidation states (Mnx Fe3- x O4 ). Using molecular-beam epitaxy (MBE), a series of single crystal Mnx Fe3- x O4 thin films with controlled stoichiometry, 0 ≤ x ≤ 2.3, and lattice strain are grown, and the cation site-occupation is determined through X-ray emission spectroscopy (XES). Density functional theory + U analysis shows that charge transport occurs only between like-cations (Fe/Fe or Mn/Mn). The site-occupation data and percolation models show that there are limited stoichiometric ranges for transport along Fe and Mn pathways. Furthermore, due to asymmetric hopping barriers and formation energies, the Mn O h 2 + polaron is energetically preferred to the Fe O h 2 + polaron, resulting in an asymmetric contribution of Mn/Mn pathways. All of these findings are not contained in the conventional small-polaron hopping model, highlighting its inadequacy. To correct the model, new parameters in the nearest-neighbor hopping equation are introduced to account for percolation, cross-hopping, and polaron-distribution, and it is found that a near-perfect correlation can be made between experiment and theory for the electronic conductivity.