Article 6 – Tunable Ferroionic Properties in CeO2/BaTiO3 Heterostructures

Abstract:

Ferroionic materials combine ferroelectric properties and spontaneous polarization with ionic phenomena of fast charge recombination and electrodic functionalities. In this paper, we propose the concept of tunable polarization in CeO2−δ (ceria) thin (5 nm) films induced by built-in remnant polarization of a BaTiO3 (BTO) ferroelectric thin film interface, which is buried under the ceria layer. Upward and downward fixed polarizations at the BTO thin film (10 nm) are achieved by the lattice termination engineering of the SrO or TiO2 terminated Nb:SrTiO3 (NSTO or STN) substrate. We find that the ceria layer punctually replicates the polarization of the BTO interface via a dynamic reconfiguration of its intrinsic defects, i.e., oxygen vacancies and small polarons. Tunable oxidative or reducing properties (redox) also arise at the surface from the built-in polarization. Opposite polarities at the ceria termination tune the chemo-physical dynamics toward water molecule adsorbates. The inversion of the surface potential leads to a modulation of the water adsorption−desorption equilibrium and water ionization (splitting) redox overpotentials within ±400 mV at room temperature, depending on the ceria termination’s charges. Such tunability opens up the perspectives of using ferroionics for wireless electrochemically enhanced catalysis.

 

Title: Tunable Ferroionic Properties in CeO2/BaTiO3 Heterostructures

Authors: Milica Vasiljevic, Francesco Chiabrera, Denis Alikin, Federico Motti, Achilles Bergne, Javier Zamudio-García, Xueping Qin, Deepak Dagur, Shinhee Yun, David Marrero-López, Giovanni Vinai, Ivano Castelli, Andrei Kholkin, and Vincenzo Esposito

Reference: ACS Appl. Mater. Interfaces 2024, XXXX, XXX, XXX-XXX

DOI: https://doi.org/10.1021/acsami.4c09477

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