Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions.

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La0.7 Sr0.3 MnO3-δ epitaxial thin films, both at the surface and throughout the bulk. Using polarized neutron reflectometry, a quantitative depth profile of the oxygen content gradient is achieved, which, alongside atomic-resolution scanning transmission electron microscopy, uniquely reveals the formation of a novel structural phase near the surface. Surface-sensitive X-ray spectroscopies further confirm a significant change of the electronic structure accompanying the transition. The anisotropic features of this novel phase enable a distinct oxygen diffusion pathway in contrast to conventional observation of oxygen motion at moderate temperatures. The results provide insights furthering the design of solid oxygen ion conductors within the framework of topotactic phase transitions.

Ordering of Oxygen Vacancies and Related Ferroelectric Properties in HfO_{2-δ}.

Using density functional theory combined with an evolutionary algorithm, we investigate ferroelectricity in substoichiometric HfO_{2-δ} with fixed composition δ=0.25. We find that oxygen vacancies tend to cluster in the form of two-dimensional extended defects, revealing several patterns of local relative arrangements within an energy range of 100 meV per Hf atom. Two lowest-energy patterns result in polar monoclinic structures with different transformation properties. The lowest one elastically transforms to the ferroelectric orthorhombic structure via a shear deformation, overcoming an energy barrier, which is more than twice lower than in the stoichiometric hafnia. The second-lowest structure transforms at smaller volumes to a nonpolar tetragonal one. We discuss the experimentally observed wake-up effect, fatigue, and imprint in HfO_{2}-based ferroelectrics in terms of different local ordering of oxygen-vacancy extended defects, which favor specific crystallographic phases.

Ab initio phase diagrams of Hf-O, Zr-O and Y-O: a comparative study.

We present phase diagrams of binary oxides, Hf-O, Zr-O and Y-O, obtained by ab initio evolutionary simulations, in order to explore possible metastable crystalline suboxide structures which could be quenched during the electroforming processes within the conductive filaments in stoichiometric HfO2, ZrO2 and Y2O3 host materials, in resistive switching devices. We find that, in the range MO-MO2 (where M = Hf, Zr, Y), the most energetically favourable atomic configurations have properties which facilitate the ionic conduction of oxygen. Namely, the calculations reveal that oxygen vacancies tend to order in arrays of one-dimensional channels, along which the migration barrier of anions is much lower than for the stoichiometric hosts. We explore for Hf-O and Zr-O a new set of structural patterns, different from those of the host materials, for which a change of oxygen stoichiometry does not change the underlying structural frame. However, a sufficient change of oxygen stoichiometry drives metallic conductivity in oxygen-deficient compounds, whereas their oxygen-rich counterparts are insulating. In contrast to Hf-O and Zr-O, in the Y-O system we find an atomic structure with metallic conductivity, which has the same structural frame as the stoichiometric Y2O3 host. We believe that this property enables the forming-free resistive switching in Y2O3.

Melting of Pb Charge Glass and Simultaneous Pb-Cr Charge Transfer in PbCrO3 as the Origin of Volume Collapse.

A metal to insulator transition in integer or half integer charge systems can be regarded as crystallization of charges. The insulating state tends to have a glassy nature when randomness or geometrical frustration exists. We report that the charge glass state is realized in a perovskite compound PbCrO3, which has been known for almost 50 years, without any obvious inhomogeneity or triangular arrangement in the charge system. PbCrO3 has a valence state of Pb(2+)(0.5)Pb(4+)(0.5)Cr(3+)O3 with Pb(2+)-Pb(4+) correlation length of three lattice-spacings at ambient condition. A pressure induced melting of charge glass and simultaneous Pb-Cr charge transfer causes an insulator to metal transition and ∼10% volume collapse.

Ferroelectricity, nonlinear dynamics, and relaxation effects in monoclinic Sn2P2S6.

An ab initio-based model of the temperature-induced ferroelectric phase transition in Sn2P2S6 (SPS) as a prototype of an unconventional ferroelectric is developed. The order parameter in SPS is found as the valley line on a total-energy surface of the zone-center fully symmetrical Ag and polar Bu distortions. Significant nonlinear coupling between order parameter and strain is observed. Monte Carlo simulations describe the additional low-temperature rearrangement in polar structure, which appears in domain boundaries, and describe the relaxation phenomena near the ferroelectric phase transition.