Crossover from Linear to Quadratic Electro-optic Behavior in BaTiO_{3} and (Ba, Sr)TiO_{3} Solid Solution.

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.

Motion and teleportation of polar bubbles in low-dimensional ferroelectrics.

Electric bubbles are sub-10nm spherical vortices of electric dipoles that can spontaneously form in ultra-thin ferroelectrics. While the static properties of electric bubbles are well established, little to nothing is known about the dynamics of these particle-like structures. Here, we reveal pathways to realizing both the spontaneous and controlled dynamics of electric bubbles in ultra-thin Pb(Zr0.4Ti0.6)O3 films. In low screening conditions, we find that electric bubbles exhibit thermally-driven chaotic motion giving rise to a liquid-like state. In the high screening regime, we show that bubbles remain static but can be continuously displaced by a local electric field. Additionally, we predict and experimentally demonstrate the possibility of bubble teleportation - a process wherein a bubble is transferred to a new location via a single electric field pulse of a PFM tip. Finally, we attribute the discovered phenomena to the hierarchical structure of the energy landscape.

Tuning the Multiferroic Properties of BiFeO_{3} under Uniaxial Strain.

More than twenty years ago, multiferroic compounds combining in particular magnetism and ferroelectricity were rediscovered. Since then, BiFeO_{3} has emerged as the most outstanding multiferroic by combining at room temperature almost all the fundamental or applicative properties that may be desired: electroactive spin wave excitations called electromagnons, conductive domain walls, or a low band gap of interest for magnonic devices. All these properties have so far only been discontinuously strain engineered in thin films according to the lattice parameter imposed by the substrate. Here we explore the ferroelectricity and the dynamic magnetic response of BiFeO_{3} bulk under continuously tunable uniaxial strain. Using elasto-Raman spectroscopy, we show that the ferroelectric soft mode is strongly enhanced under tensile strain and driven by the volume preserving deformation at low strain. The magnonic response is entirely modified with low energy magnon modes being suppressed for tensile strain above pointing out a transition from a cycloid to an homogeneous magnetic state. Effective Hamiltonian calculations show that the ferroelectric and the antiferrodistortive modes compete in the tensile regime. In addition, the homogeneous antiferromagnetic state becomes more stable compared to the cycloidal state above a +2% tensile strain close to the experimental value. Finally, we reveal the ferroelectric and magnetic orders of BiFeO_{3} under uniaxial strain and how the tensile strain allows us to unlock and to modify in a differentiated way the polarization and the magnetic structure.

Realistic Spin Model for Multiferroic NiI_{2}.

A realistic first-principle-based spin Hamiltonian is constructed for the type-II multiferroic NiI_{2}, using a symmetry-adapted cluster expansion method. Besides single ion anisotropy and isotropic Heisenberg terms, this model further includes the Kitaev interaction and a biquadratic term, and can well reproduce striking features of the experimental helical ground state, that are, e.g., a proper screw state, canting of rotation plane, propagation direction, and period. Using this model to build a phase diagram, it is demonstrated that, (i) the in-plane propagation direction of ⟨11[over ¯]0⟩ is determined by the Kitaev interaction, instead of the long-believed exchange frustrations and (ii) the canting of rotation plane is also dominantly determined by Kitaev interaction, rather than interlayer couplings. Furthermore, additional Monte Carlo simulations reveal three equivalent domains and different topological defects. Since the ferroelectricity is induced by spins in type-II multiferroics, our work also implies that Kitaev interaction is closely related to the multiferroicity of NiI_{2}.

Magnetization Compensation Temperature and Frustration-Induced Topological Defects in Ferrimagnetic Antiperovskite Mn_{4}N.

First-principles-based simulations are conducted to investigate magnetic properties and topological spin textures in the antiperovskite Mn_{4}N ferrimagnet. A magnetization compensation temperature, resulting from a competition between different Mn sublattices, is found in this system, when under thermal equilibrium. Striking metastable topological states are also discovered, including nanometric hedgehog-antihedgehog pairs that originate from frustrated exchange interactions rather than the usual Dzyaloshinskii-Moriya interaction.

Ultrafast Neuromorphic Dynamics Using Hidden Phases in the Prototype of Relaxor Ferroelectrics.

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.

Topology and control of self-assembled domain patterns in low-dimensional ferroelectrics.

Whilst often discussed as non-trivial phases of low-dimensional ferroelectrics, modulated polar phases such as the dipolar maze and the nano-bubble state have been appraised as essentially distinct. Here we emphasize their topological nature and show that these self-patterned polar states, but also additional mesophases such as the disconnected labyrinthine phase and the mixed bimeron-skyrmion phase, can be fathomed in their plurality through the unifying canvas of phase separation kinetics. Under compressive strain, varying the control parameter, i.e., the external electric field, conditions the nonequilibrium self-assembly of domains, and bridges nucleation and spinodal decomposition via the sequential onset of topological transitions. The evolutive topology of these polar textures is driven by the (re)combination of the elementary topological defects, merons and antimerons, into a plethora of composite topological defects such as the fourfold junctions, the bimeron and the target skyrmion. Moreover, we demonstrate that these manipulable defects are stable at room temperature and feature enhanced functionalities, appealing for devising future topological-based nanoelectronics.

Magnetic-Domain-Wall-Induced Electrical Polarization in Rare-Earth Iron Garnet Systems: A First-Principles Study.

First-principles methods are employed to understand the existence of magnetic-domain-wall-induced electric polarization observed in rare-earth iron garnets. In contrast with previous beliefs, it is found that the occurrence of such polarization neither requires the local magnetic moments of the rare-earth ions nor noncollinear magnetism. It can rather be understood as originating from a magnetoelectric effect arising from ferromagnetic interactions between octahedral and tetrahedral Fe ions at the domain walls, and the mechanism behind is found to be a symmetric exchange-striction mechanism.

Electric-Field Switching of Magnetic Topological Charge in Type-I Multiferroics.

Applying electric field to control magnetic properties is a very efficient way for spintronics devices. However, the control of magnetic characteristics by electric fields is not straightforward, due to the time-reversal symmetry of magnetism versus spatial inversion symmetry of electricity. Such fundamental difficulty makes it challenging to modify the topology of magnetic skyrmionic states with electric field. Here, we propose a novel mechanism that realizes the electric-field (E) switching of magnetic topological charge (Q) in a controllable and reversible fashion, through the mediation of electric polarization (P) and Dzyaloshinskii-Moriya interaction (D). Such a mechanism is coined here EPDQ. Its validity is demonstrated in a multiferroic VOI_{2} monolayer, which is predicted to host magnetic bimerons. The change in magnetic anisotropy is found to play a crucial role in realizing the EPDQ process and its microscopic origin is discussed. Our study thus provides a new approach toward the highly desired electric-field control of magnetism.

Linear Versus Nonlinear Electro-Optic Effects in Materials.

Two schemes are proposed to compute the nonlinear electro-optic (EO) tensor for the first time. In the first scheme, we compute the linear EO tensor of the structure under a finite electric field, while we compute the refractive index of the structure under a finite electric field in the second scheme. Such schemes are applied to Pb(Zr,Ti)O_{3} and BaTiO_{3} ferroelectric oxides. It is found to reproduce a recently observed feature, namely, why Pb(Zr_{0.52}Ti_{0.48})O_{3} adopts a mostly linear EO response while BaTiO_{3} exhibits a strongly nonlinear conversion between electric and optical properties. Furthermore, the atomistic insight provided by the proposed ab initio scheme reveals the origin of such qualitatively different responses, in terms of the field-induced behavior of the frequencies of some phonon modes and of some force constants.

Possible Kitaev Quantum Spin Liquid State in 2D Materials with S=3/2.

Quantum spin liquids (QSLs) form an extremely unusual magnetic state in which the spins are highly correlated and fluctuate coherently down to the lowest temperatures, but without symmetry breaking and without the formation of any static long-range-ordered magnetism. Such intriguing phenomena are not only of great fundamental relevance in themselves, but also hold promise for quantum computing and quantum information. Among different types of QSLs, the exactly solvable Kitaev model is attracting much attention, with most proposed candidate materials, e.g., RuCl_{3} and Na_{2}IrO_{3}, having an effective S=1/2 spin value. Here, via extensive first-principles-based simulations, we report the investigation of the Kitaev physics and possible Kitaev QSL state in epitaxially strained Cr-based monolayers, such as CrSiTe_{3}, that rather possess a S=3/2 spin value. Our study thus extends the playground of Kitaev physics and QSLs to 3d transition metal compounds.

Inverse transition of labyrinthine domain patterns in ferroelectric thin films.

Phase separation is a cooperative process, the kinetics of which underpin the orderly morphogenesis of domain patterns on mesoscopic scales1,2. Systems of highly degenerate frozen states may exhibit the rare and counterintuitive inverse-symmetry-breaking phenomenon3. Proposed a century ago4, inverse transitions have been found experimentally in disparate materials, ranging from polymeric and colloidal compounds to high-transition-temperature superconductors, proteins, ultrathin magnetic films, liquid crystals and metallic alloys5,6, with the notable exception of ferroelectric oxides, despite extensive theoretical and experimental work on the latter. Here we show that following a subcritical quench, the non-equilibrium self-assembly of ferroelectric domains in ultrathin films of Pb(Zr0.4Ti0.6)O3 results in a maze, or labyrinthine pattern, featuring meandering stripe domains. Furthermore, upon increasing the temperature, this highly degenerate labyrinthine phase undergoes an inverse transition whereby it transforms into the less-symmetric parallel-stripe domain structure, before the onset of paraelectricity at higher temperatures. We find that this phase sequence can be ascribed to an enhanced entropic contribution of domain walls, and that domain straightening and coarsening is predominantly driven by the relaxation and diffusion of topological defects. Computational modelling and experimental observation of the inverse dipolar transition in BiFeO3 suggest the universality of the phenomenon in ferroelectric oxides. The multitude of self-patterned states and the various topological defects that they embody may be used beyond current domain and domain-wall-based7 technologies by enabling fundamentally new design principles and topologically enhanced functionalities within ferroelectric films.

Designing Multifunctionality via Assembling Dissimilar Materials: Epitaxial AlN/ScN Superlattices.

First-principles calculations are performed to investigate the effect of epitaxial strain on energetic, structural, electrical, electronic, and optical properties of 1×1 AlN/ScN superlattices. This system is predicted to adopt four different strain regions exhibiting different properties, including optimization of various physical responses such as piezoelectricity, electro-optic and elasto-optic coefficients, and elasticity. Varying the strain between these four different regions also allows the creation of an electrical polarization in a nominally paraelectric material, as a result of a softening of the lowest optical mode, and even the control of its magnitude up to a giant value. Furthermore, it results in an electronic band gap that cannot only change its nature (direct vs indirect), but also cover a wide range of the electromagnetic spectrum from the blue, through the violet and near ultraviolet, to the middle ultraviolet. These findings thus point out the potential of assembling two different materials inside the same heterostructure to design multifunctionality and striking phenomena.

Electric-Field Control of Magnetization, Jahn-Teller Distortion, and Orbital Ordering in Ferroelectric Ferromagnets.

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.

Novel Dynamical Magnetoelectric Effects in Multiferroic BiFeO_{3}.

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.

Cooperative Couplings between Octahedral Rotations and Ferroelectricity in Perovskites and Related Materials.

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.

Photostriction and elasto-optic response in multiferroics and ferroelectrics from first principles.

The present work reviews a series of recent first-principles studies devoted to the description of the interaction of light and strain in ferroelectric and multiferroic materials. Specifically, the modelling schemes used in these works to describe the so-called photostriction and elasto-optic effects are presented, in addition to the results and analysis provided by these ab initio calculations. In particular, the large importance of the piezoelectric effect in the polar direction in the photostriction of ferroelectric materials is stressed. Similarly, the occurrence of low-symmetry phases in lead titanate thin films under tensile strain is demonstrated to result in large elasto-optic constants. In addition, first-principle calculations allow to gain microscopic knowledge of subtle effects, for instance in the case of photostriction, where the deformation potential effect in directions perpendicular to the polar axis is shown to be almost as significant as the piezoelectric effect. As a result, the numerical methods presented here could propel the design of efficient opto-mechanical devices.

Corrigendum: Microscopic origins of the large piezoelectricity of leadfree (Ba,Ca)(Zr,Ti)O3.

This corrects the article DOI: 10.1038/ncomms15944.

Emergent Berezinskii-Kosterlitz-Thouless Phase in Low-Dimensional Ferroelectrics.

Using first-principles-based simulations merging an effective Hamiltonian scheme with scaling, symmetry, and topological arguments, we find that an overlooked Berezinskii-Kosterlitz-Thouless (BKT) phase sustained by quasicontinuous symmetry emerges between the ferroelectric phase and the paraelectric one of BaTiO_{3} ultrathin film, being under tensile strain. Not only do these results provide an extension of BKT physics to the field of ferroelectrics, but they also unveil their nontrivial critical behavior in low dimensions.