Strain-Induced Uphill Hydrogen Distribution in Perovskite Oxide Films

Incorporating hydrogen into transition-metal oxides (TMOs) provides a facile and powerful way to manipulate the performances of TMOs, and thus numerous efforts have been invested in developing hydrogenation methods and exploring the property modulation via hydrogen doping. However, the distribution of hydrogen ions, which is a key factor in determining the physicochemical properties on a microscopic scale, has not been clearly illustrated. Here, focusing on prototypical perovskite oxide (NdNiO₃ and La_0.67Sr_0.33MnO₃) epitaxial films, we find that hydrogen distribution exhibits an anomalous "uphill" feature (against the concentration gradient) under tensile strain, namely, the proton concentration enhances upon getting farther from the hydrogen source. Distinctly, under a compressive strain state, hydrogen shows a normal distribution without uphill features. The epitaxial strain significantly influences the chemical lattice coupling and the energy profile as a function of the hydrogen doping position, thus dominating the hydrogen distribution. Furthermore, the strain-(H⁺) distribution relationship is maintained in different hydrogenation methods (metal-alkali treatment) which is first applied to perovskite oxides. The discovery of strain-dependent hydrogen distribution in oxides provides insights into tailoring the magnetoelectric and energy-conversion functionalities of TMOs via strain engineering.