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In multiferroic BiFeO3 thin films grown on highly mismatched LaAlO3 substrates, we reveal the coexistence of two differently distorted polymorphs that leads to striking features in the temperature dependence of the structural and multiferroic properties. Notably, the highly distorted phase quasiconcomitantly presents an abrupt structural change, transforms from a standard to a nonconventional ferroelectric, and transitions from antiferromagnetic to paramagnetic at 360 ± 20 K. These coupled ferroic transitions just above room temperature hold promises of giant piezoelectric, magnetoelectric, and piezomagnetic responses, with potential in many applications fields. [ABSTRACT FROM AUTHOR]

An escalating challenge in condensed-matter research is the characterization of emergent order-parameter nanostructures such as ferroelectric and ferromagnetic skyrmions. Their small length scales coupled with complex, three-dimensional polarization or spin structures makes them demanding to trace out fully. Resonant elastic x-ray scattering (REXS) has emerged as a technique to study chirality in spin textures such as skyrmions and domain walls. It has, however, been used to a considerably lesser extent to study analogous features in ferroelectrics. Here, we present a framework for modeling REXS from an arbitrary arrangement of charge quadrupole moments, which can be applied to nanostructures in materials such as ferroelectrics. With this, we demonstrate how extended reciprocal space scans using REXS with circularly polarized x rays can probe the three-dimensional structure and chirality of polar skyrmions. Measurements, bolstered by quantitative scattering calculations, show that polar skyrmions of mixed chirality coexist, and that REXS allows valuation of relative fractions of right- and left-handed skyrmions. Our quantitative analysis of the structure and chirality of polar skyrmions highlights the capability of REXS for establishing complex topological structures toward future application exploits.

Model materials are precious test cases for elementary theories and provide building blocks for the understanding of more complex cases. Here, we describe the lattice dynamics of the structural phase transition in francisite Cu_{3}Bi(SeO_{3})_{2}O_{2}Cl at 115 K and show that it provides a rare archetype of a transition driven by a soft antipolar phonon mode. In the high-symmetry phase at high temperatures, the soft mode is found at (0,0,0.5) at the Brillouin zone boundary and is measured by inelastic x-ray scattering and thermal diffuse scattering. In the low-symmetry phase, this soft-mode is folded back onto the center of the Brillouin zone as a result of the doubling of the unit cell, and appears as a fully symmetric mode that can be tracked by Raman spectroscopy. On both sides of the transition, the mode energy squared follows a linear behavior over a large temperature range. First-principles calculations reveal that, surprisingly, the flat phonon band calculated for the high-symmetry phase seems incompatible with the displacive character found experimentally. We discuss this unusual behavior in the context of an ideal Kittel model of an antiferroelectric transition.

We demonstrate theoretically how, by imposing epitaxial strain in a ferroelectric perovskite, it is possible to achieve a dynamical control of phonon propagation by means of external electric fields, which yields a giant electrophononic response, i.e., the dependence of the lattice thermal conductivity on external electric fields. Specifically, we study the strain-induced manipulation of the lattice structure and analyze its interplay with the electrophononic response. We show that tensile biaxial strain can drive the system to a regime where the electrical polarization can be effortlessly rotated and thus yield giant electrophononic responses that are at least one order of magnitude larger than in the unstrained system. These results derive directly from the almost divergent behavior of the electrical susceptibility at those critical strains that drive the polarization on the verge of a spontaneous rotation.

Ferroic materials naturally exhibit a rich number of functionalities, which often arise from thermally, chemically, or mechanically induced symmetry breakings or phase transitions. Based on density functional calculations, we demonstrate here that light can drive phase transitions as well in ferroelectric materials such as the perovskite oxides lead titanate and barium titanate. Phonon analysis and total energy calculations reveal that the polarization tends to vanish under illumination, to favor the emergence of nonpolar phases, potentially antiferroelectric, and exhibiting a tilt of the oxygen octahedra. Strategies to tailor photoinduced phases based on phonon instabilities in the electronic ground state are also discussed.

Controlling the direction of the magnetization by an electric field in multiferroics that are both ferroelectric and strongly ferromagnetic will open the door to the design of the next generation of spintronics and memory devices. Using first-principles simulations, we report that the discovery that the PbTiO_{3}/LaTiO_{3} (PTO/LTO) superlattice possesses such highly desired control, as evidenced by the electric-field-induced rotation of 90° and even a possible full reversal of its magnetization in some cases. Moreover, such systems also exhibit Jahn-Teller distortions, as well as orbital orderings, that are switchable by the electric field, therefore making PTO/LTO of importance for the tuning of electronic properties too. The origin for such striking electric-field controls of magnetization, Jahn-Teller deformations, and orbital orderings resides in the existence of three different types of energetic coupling: one coupling polarization with antiphase and in-phase oxygen octahedral tiltings, a second one coupling polarization with antiphase oxygen octahedra tilting and Jahn-Teller distortions, and finally a biquadratic coupling between antiphase oxygen octahedral tilting and magnetization.

Bulk LiOsO_{3} was experimentally identified as a "ferroelectric" metal where polar distortions coexist with metallicity [Shi et al., Nat. Mater. 12, 1024 (2013)NMAACR1476-112210.1038/nmat3754]. It is generally believed that polar displacements in a ferroelectric metal cannot be switched by an external electric field. Here, via comprehensive density functional theory calculations, we demonstrate that a two-unit cell-thick LiOsO_{3} thin film exhibits a ferroelectric ground state having an out-of-plane electric dipole moment that can be switched by an external electric field. Moreover, its dipole moment-versus-electric field hysteresis loop is asymmetric because only surface Li ions' displacements are reversed by the external electric field whereas the field-induced force on inner Li atoms is nearly fully screened by itinerant electrons. As a relevant by-product of our study, we also extend the concept of "Born effective charge" to finite metallic systems, and show its usefulness to rationalize the observed effects.

The structure of ABO_{3} perovskites is dominated by two types of unstable modes, namely, the oxygen octahedral rotation (AFD) and ferroelectric (FE) mode. It is generally believed that such AFD and FE modes tend to compete and suppress each other. Here we use first-principles methods to show that a dual nature of the FE-AFD coupling, which turns from competitive to cooperative as the AFD mode strengthens, occurs in numerous perovskite oxides. We provide a unified model of such a dual interaction by introducing novel high-order coupling terms and explain the atomistic origin of the resulting new form of ferroelectricity in terms of universal steric mechanisms. We also predict that such a novel form of ferroelectricity leads to atypical behaviors, such as an enhancement of all the three Cartesian components of the electric polarization under hydrostatic pressure and compressive epitaxial strain.

We present a first-principles study of model domain walls (DWs) in prototypic ferroelectric PbTiO(3). At high temperature the DW structure is somewhat trivial, with atoms occupying high-symmetry positions. However, upon cooling the DW undergoes a symmetry-breaking transition characterized by a giant dielectric anomaly and the onset of a large and switchable polarization. Our results thus corroborate previous arguments for the occurrence of ferroic orders at structural DWs, providing a detailed atomistic picture of a temperature-driven DW-confined transformation. Beyond its relevance to the field of ferroelectrics, our results highlight the interest of these DWs in the broader areas of low-dimensional physics and phase transitions in strongly fluctuating systems.

Our first-principles results show that geometric frustration can be induced in thin films of multiferroic BiFeO(3). We find that competing magnetic interactions occur in the so-called supertetragonal phase of this material, which can be grown on strongly compressive substrates. We show that the frustration level can be tuned by appropriately choosing the substrate; in fact, the phase diagram of the films presents a critical line at which the three-dimensional spin order gets annihilated. We argue that these effects are not exclusive to BiFeO(3) and predict that they also occur in BiCoO(3).

In multiferroic BiFeO(3) thin films grown on highly mismatched LaAlO(3) substrates, we reveal the coexistence of two differently distorted polymorphs that leads to striking features in the temperature dependence of the structural and multiferroic properties. Notably, the highly distorted phase quasiconcomitantly presents an abrupt structural change, transforms from a standard to a nonconventional ferroelectric, and transitions from antiferromagnetic to paramagnetic at 360±20 K. These coupled ferroic transitions just above room temperature hold promises of giant piezoelectric, magnetoelectric, and piezomagnetic responses, with potential in many applications fields., (© 2011 American Physical Society)

We have used first-principles-based simulations and Raman scattering techniques to reveal a novel dynamical phenomenon in Pb(Zr,Ti)O(3) solid solutions: a Fermi resonance (FR) emerging from the nonlinear coupling between ferroelectric (FE) motions and tiltings of oxygen octahedra. This FR manifests itself as the doubling of a nominally single FE mode in a purely FE phase, when the resonant frequency of the FE mode is close to the first overtone of the tiltings. We show that the FR is the result of a nonlinear coupling that is proportional to the spontaneous polarization of the material and derive an analytical model that captures the essence of the effect., (© 2011 American Physical Society)

We present an ab initio study of the BFCO solid solution formed by multiferroics BiFeO(3) (BFO) and BiFeO(3) (BCO). We find that BFCO presents a strongly discontinuous morphotropic transition between BFO-like and BCO-like ferroelectric phases. Further, for all compositions such phases remain (meta)stable and retain well-differentiated properties. Our results thus suggest that an electric field can be used to switch between these structures and show that such a switching involves large phase-change effects of various types, including piezoelectric, electric, and magnetoelectric ones., (© 2011 American Physical Society)