Protonation-Induced Colossal Chemical Expansion and Property Tuning in NdNiO<sub>3</sub> Revealed by Proton Concentration Gradient Thin Films.

Chen, Haowen; Dong, Mingdong; Hu, Yang; Lin, Ting; Zhang, Qinghua; Guo, Er-Jia; Gu, Lin; Wu, Jie et al. · Nano Lett · 2022

basic_science · Level V

Where this comes from

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 NdNiO<sub>3</sub> (NNO) as a model system to understand the protonation process from pristine NNO to protonated H<sub><i>x</i></sub>NdNiO<sub>3</sub> (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 NiO<sub>6</sub> 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.