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We derive a numerical method based on coupled density functional theory and effective Hamiltonian schemes to calculate the linear and quadratic electro-optic response of ferroelectrics at finite temperature and in different frequency ranges. By applying the developed method to BaTiO_{3}, we successfully resolve apparent discrepancies in the experimental literature that reported a linear or quadratic electro-optic response when visible or terahertz radiation was employed to measure the optical index, respectively. We further demonstrate that (and explain why), in the case of the Ba_{1-x}Sr_{x}TiO_{3} disordered solid solutions, structural phase transitions not only lead to larger linear electro-optic constants, as previously demonstrated in the literature, but also significantly enhance the quadratic electro-optic constants.
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The Dzyaloshinskii-Moriya interaction (DMI) between two magnetic moments mi and mj is of the form [Formula: see text]. It originates from spin-orbit coupling, and is at the heart of fascinating phenomena involving non-collinear magnetism, such as magnetic topological defects (for example, skyrmions) as well as spin-orbit torques and magnetically driven ferroelectricity, that are of significant fundamental and technological interest. In sharp contrast, its electric counterpart, which is an electric DMI characterized by its [Formula: see text] strength and describing an interaction between two polar displacements ui and uj, has rarely been considered, despite the striking possibility that it could also generate new features associated with non-collinear patterns of electric dipoles. Here we report first-principles simulations combined with group theoretical symmetry analysis which not only demonstrate that electric DMI does exist and has a one-to-one correspondence with its magnetic analogue, but also reveals a physical source for it. These findings can be used to explain and/or design phenomena of possible technological importance in ferroelectrics and multiferroics.
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Materials possessing multiple states are promising to emulate synaptic and neuronic behaviors. Their operation frequency, typically in or below the GHz range, however, limits the speed of neuromorphic computing. Ultrafast THz electric field excitation has been employed to induce nonequilibrium states of matter, called hidden phases in oxides. One may wonder if there are systems for which THz pulses can generate neuronic and synaptic behavior, via the creation of hidden phases. Using atomistic simulations, we discover that relaxor ferroelectrics can emulate all the key neuronic and memristive synaptic features. Their occurrence originates from the activation of many hidden phases of polarization order, resulting from the response of nanoregions to THz pulses. Such phases further possess different dielectric constants, which is also promising for memcapacitor devices.
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An atomistic effective Hamiltonian scheme is employed within molecular dynamics simulations to investigate how the electrical polarization and magnetization of the multiferroic BiFeO_{3} respond to time-dependent ac magnetic fields of various frequencies, as well as to reveal the frequency dependency of the dynamical (quadratic) magnetoelectric coefficient. We found the occurrence of vibrations having phonon frequencies in both the time dependency of the electrical polarization and magnetization (for any applied ac frequency), therefore making such vibrations of electromagnonic nature, when the homogeneous strain of the system is frozen (case 1). Moreover, the quadratic magnetoelectric coupling constant is monotonic and almost dispersionless in the sub-THz range in this case 1. In contrast, when the homogeneous strain can fully relax (case 2), two additional low-frequency and strain-mediated oscillations emerge in the time-dependent behavior of the polarization and magnetization, which result in resonances in the quadratic magnetoelectric coefficient. Such additional oscillations consist of a mixing between acoustic phonons, optical phonons, and magnons, and reflect the existence of a new quasiparticle that can be coined an "electroacoustic magnon." This latter finding can prompt experimentalists to shape their samples to take advantage of, and tune, the magnetostrictive-induced mechanical resonance frequency, in order to achieve large dynamical magnetoelectric couplings.
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In the early 2000s, low dimensional ferroelectric systems were predicted to have topologically nontrivial polar structures, such as vortices or skyrmions, depending on mechanical or electrical boundary conditions. A few variants of these structures have been experimentally observed in thin film model systems, where they are engineered by balancing electrostatic charge and elastic distortion energies. However, the measurement and classification of topological textures for general ferroelectric nanostructures have remained elusive, as it requires mapping the local polarization at the atomic scale in three dimensions. Here we unveil topological polar structures in ferroelectric BaTiO3 nanoparticles via atomic electron tomography, which enables us to reconstruct the full three-dimensional arrangement of cation atoms at an individual atom level. Our three-dimensional polarization maps reveal clear topological orderings, along with evidence of size-dependent topological transitions from a single vortex structure to multiple vortices, consistent with theoretical predictions. The discovery of the predicted topological polar ordering in nanoscale ferroelectrics, independent of epitaxial strain, widens the research perspective and offers potential for practical applications utilizing contact-free switchable toroidal moments.
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Despite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high-energy-density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead-free NaNbO3 membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric-to-ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single-phase below 40 nm, as well as a mixed-phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First-principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size-driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead-free oxides with the membrane platform.
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First-principles-based Monte Carlo approaches are developed to investigate finite-temperature properties of stress-free nanodots made of the ferroelectric Pb(Zr,Ti)O3 system and of the multiferroic BiFeO3 compound. These zero-dimensional materials both exhibit various, novel chiral patterns for the tilting of the oxygen octahedra. Such exotic patterns originate from the coupling between the tiltings of the oxygen octahedra and the electric dipole vortices, and require original order parameters to quantify them.
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Highly-strained coherent interfaces, between rhombohedral-like (R) and tetragonal-like (T) phases in BiFeO3 thin films, often show enhanced electrical conductivity in comparison to non-interfacial regions. In principle, changing the population and distribution of these interfaces should therefore allow different resistance states to be created. However, doing this controllably has been challenging to date. Here, we show that local thin film phase microstructures (and hence R-T interface densities) can be changed in a thermodynamically predictable way (predictions made using atomistic simulations) by applying different combinations of mechanical stress and electric field. We use both pressure and electric field to reversibly generate metastable changes in microstructure that result in very large changes of resistance of up to 108%, comparable to those seen in Tunnelling Electro-Resistance (TER) devices.
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Correction for 'Giant resistive switching in mixed phase BiFeO3via phase population control' by David Edwards et al., Nanoscale, 2018, 10, 17629-17637.
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This corrects the article DOI: 10.1038/ncomms15944.
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In light of directives around the world to eliminate toxic materials in various technologies, finding lead-free materials with high piezoelectric responses constitutes an important current scientific goal. As such, the recent discovery of a large electromechanical conversion near room temperature in (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 compounds has directed attention to understanding its origin. Here, we report the development of a large-scale atomistic scheme providing a microscopic insight into this technologically promising material. We find that its high piezoelectricity originates from the existence of large fluctuations of polarization in the orthorhombic state arising from the combination of a flat free-energy landscape, a fragmented local structure, and the narrow temperature window around room temperature at which this orthorhombic phase is the equilibrium state. In addition to deepening the current knowledge on piezoelectricity, these findings have the potential to guide the design of other lead-free materials with large electromechanical responses.
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Special quasirandom structures (SQS) are presently generated for disordered (A'1-x [Formula: see text] x )BX3 and A(B'1-x [Formula: see text] x )X3 perovskite solid solutions, with x = 1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x = 1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained.
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A review of the recent development and application of a first-principles-derived effective Hamiltonian technique to the study of lead-free Ba(Zr,Ti)O3 (BZT) relaxor ferroelectrics is provided. In addition to the computation and analysis of macroscopic properties (such as different types of dielectric responses and electric polarization) and their connections to previous published works, particular emphasis is given to microscopic insights arising from this atomistic technique. These include (i) the numerically-found determination of the physical origin of the relaxor behavior in BZT; and (ii) the prediction of polar nanoregions and the evolution of their morphology as a response to temperature, electric fields and epitaxial misfit strain. Other striking phenomena that were predicted in BZT compounds, such as Fano resonance and field-driven percolation, are also documented and discussed. Finally, a brief perspective of possible remaining computational studies to be conducted in relaxor ferroelectrics, in order to further understand them, is attempted.
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In the present study, we diluted either A- or B- sublattice of perovskite multiferroic PbFe(0.5)Nb(0.5)O(3) (PFN) and studied the changes of the magnetic and ferroelectric phase transition temperatures and dielectric properties caused by such dilution. Dielectric studies of PFN single crystals show that, in contrast to the commonly adopted view, the ferroelectric phase transition in PFN is non-diffused and the relaxor-like behavior usually observed in ceramic samples has an extrinsic nature. A-site substitutions (Ba, Ca) lead to the smearing of the permittivity-temperature maximum, lowering its maximum temperature, T(m) and inducing relaxor behavior. B-site diluting of PFN by Ti increases T(m) and only slightly affects the permittivity maximum diffuseness. Both A-site and B-site substitutions in PFN lead to lowering of its Neel temperature, T(N). However, above a certain compositional threshold, fast lowering of T(N) stops and a new magnetic state with comparatively high (~50K) transition temperature becomes stable in a rather wide compositional range.