First-principles study of hydrogen configurations at the core of a high-angle grain boundary in cubic yttria-stabilized zirconia.

Hydrogen is a common impurity in oxides and has been studied extensively by first-principles electronic structure methods. From the calculated charge-transition levels and their position with respect to the conduction-band edge, definitive conclusions can be drawn concerning the electrical activity of hydrogen either as an isolated defect or as part of a defect complex with intrinsic defects of the host lattice. For those oxides such as yttria-stabilized zirconia, which in many cases are used in polycrystalline or nanocrystalline forms, the interaction of hydrogen with grain boundaries needs to be better understood. Using both density-functional theory in the generalized-gradient approximation and a hybrid-functional approach, the present study reports on the types of isolated hydrogen configuration that can be stabilized at the core of the Σ5(310) tilt grain boundary, an interface whose atomistic structure has been determined in good detail by Z-contrast transmission electron microscopy. Initially, the present calculations elucidated the major relaxation modes that lead to low-energy structures for this boundary. Hydrogen exhibited dual behavior by binding to oxygen ions in bond-type OH(-) configurations in its positively charged state, H(+), whereas the negative H(-) species occupied preferably interstitial positions in the available empty space of the grain-boundary core regions. The neutral paramagnetic state, H(0), detected recently in muonium-based spectroscopic studies, was found to be stable in two different configurations: a deep-donor bond-type and a higher-energy quasiatomic interstitial. These configurations are characterized in terms of the trapping character of their excess electron, the spatial localization of the spin density and the resulting hyperfine parameters.