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Hydrogenation or protonation offers a feasible pathway for exploring exotic physical functionality and phenomena within correlated oxide system through introducing an ion degree of freedom. This breakthrough endows with great potential for boosting multidisciplinary device applications in artificial intelligence, correlated electronics and energy conversions. Unlike conventional substitutional chemical doping, hydrogenation enables the controllable and reversible control over the charge-lattice-spin-orbital coupling and magnetoelectric states in correlated system, free of the solid-solution limits. Our findings identify proton evolution as a powerful tuning knob to cooperatively regulate the magnetoelectric transport properties in correlated oxide heterostructures, specifically in metastable VO2 (B)/La0.7Sr0.3MnO3 (LSMO) systems grown via laser molecular beam epitaxy (LMBE). Upon hydrogenation, correlated VO2 (B)/LSMO heterostructure undergoes a reversible magnetoelectric phase transition from a ferromagnetic half-metallic state to a weakly ferromagnetic insulating state, accompanied by a pronounced out-of-plane lattice expansion due to the incorporation of protons and the formation of O-H bonds, as confirmed by X-ray diffraction (XRD). Proton evolution extensively suppresses both the electrical conductivity and ferromagnetic order in pristine VO2 (B)/LSMO system, with a remarkable recovery through dehydrogenation via annealing in an oxygen-rich atmosphere, underscoring the high reversibility of hydrogen-induced magnetoelectric transitions. Spectroscopic analyses related to X-ray photoelectron spectroscopy (XPS) and synchrotron-based soft X-ray absorption spectroscopy (sXAS) provide further insights into the physical origin underlying the hydrogen-mediated magnetoelectric transitions. Hydrogen-related band filling in d-orbital of correlated oxides accounts for the electron localization in VO2 (B)/LSMO heterostructure through hydrogenation, while the suppression in the Mn3+-Mn4+ double exchange instead leads to the magnetic transitions. The present work not only expands the hydrogen-related phase diagram for correlated oxide system but also establishes a versatile pathway for designing exotic magnetoelectric functionalities via ionic evolution, with great potential for developing protonic devices.
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Keywords:
- Magnetic Modulation /
- Magnetoelectric Phase Transition /
- Correlated Oxides /
- Ionic Evolution
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