Protonation-Induced Colossal Lattice Expansion in La2/3Sr1/3MnO3

Abstract

Ion injection controlled by an electric field is a powerful method to manipulate the diverse physical and chemical properties of metal oxides. However, the dynamic control of ion concentrations and their correlations with lattices in perovskite systems have not been fully understood. In this study, we systematically demonstrate the electric-field-controlled protonation of La_2/3Sr_1/3MnO₃ (LSMO) films. The rapid and room-temperature protonation induces a colossal lattice expansion of 9.35% in tensile-strained LSMO, which is crucial for tailoring material properties and enabling a wide range of applications in advanced electronics, energy storage, and sensing technologies. This large expansion in the lattice is attributed to the higher degree of proton diffusion, resulting in a significant elongation in the Mn-O bond and octahedral tilting, which is supported by results from density functional theory calculations. Interestingly, such a colossal expansion is not observed in LSMO under compressive strain, indicating the close dependence of ion-electron-lattice coupling on strain states. These efficient modulations of the lattice and magnetoelectric functionalities of LSMO via proton diffusion offer a promising avenue for developing multifunctional iontronic devices.

Keywords: ionic liquid gating; lattice expansion; protonation; strain; transition-metal oxides.