Protonation-Induced Colossal Chemical Expansion and Property Tuning in NdNiO3 Revealed by Proton Concentration Gradient Thin Films.

Abstract

Protonation can be used to tune diverse physical and chemical properties of functional oxides. Although protonation of nickelate perovskites has been reported, details on the crystal structure of the protonated phase and a quantitative understanding of the effect of protons on physical properties are still lacking. Therefore, in this work, we select NdNiO3 (NNO) as a model system to understand the protonation process from pristine NNO to protonated HxNdNiO3 (H-NNO). We used a reliable electrochemical method with well-defined reference electrode to trigger the protonation-induced phase transition. We found that the protonated H-NNO phase showed a colossal ∼13% lattice expansion caused by a large tilt of NiO6 octahedra and displacement of Nd cations. Importantly, we further designed a novel device configuration to induce a gradient of proton concentration into a single NNO thin film to establish a quantitative correlation between the proton concentration and the lattice constant and transport property of H-NNO.