Multiferroic bismuth ferrite-based materials for multifunctional applications: Ceramic bulks, thin films and nanostructures

Multiferroics are compounds that show ferroelectricity and magnetism. BiFeO3, by far the most studied, has outstanding ferroelectric properties, a cycloidal magnetic order in the bulk, and many unexpected virtues such as conductive domain walls or a low bandgap of interest for photovoltaics. Although this flurry of properties makes BiFeO3 a paradigmatic multifunctional material, most are related to its ferroelectric character, and its other ferroic property--antiferromagnetism--has not been investigated extensively, especially in thin films. Here we bring insight into the rich spin physics of BiFeO3 in a detailed study of the static and dynamic magnetic response of strain-engineered films. Using Mossbauer and Raman spectroscopies combined with Landau-Ginzburg theory and effective Hamiltonian calculations, we show that the bulk-like cycloidal spin modulation that exists at low compressive strain is driven towards pseudo-collinear antiferromagnetism at high strain, both tensile and compressive. For moderate tensile strain we also predict and observe indications of a new cycloid. Accordingly, we find that the magnonic response is entirely modified, with low-energy magnon modes being suppressed as strain increases. Finally, we reveal that strain progressively drives the average spin angle from in-plane to out-of-plane, a property we use to tune the exchange bias and giant-magnetoresistive response of spin valves.

Crafting the magnonic and spintronic response of BiFeO3 films by epitaxial strain

The celebrated renaissance of the multiferroics family over the past ten years has also been that of its most paradigmatic member, bismuth ferrite (BiFeO3). Known since the 1960s to be a high temperature antiferromagnet and since the 1970s to be ferroelectric, BiFeO3 only had its bulk ferroic properties clarified in the mid-2000s. It is however the fabrication of BiFeO3 thin films and their integration into epitaxial oxide heterostructures that have fully revealed its extraordinarily broad palette of functionalities. Here we review the first decade of research on BiFeO3 films, restricting ourselves to epitaxial structures. We discuss how thickness and epitaxial strain influence not only the unit cell parameters, but also the crystal structure, illustrated for instance by the discovery of the so-called T-like phase of BiFeO3. We then present its ferroelectric and piezoelectric properties and their evolution near morphotropic phase boundaries. Magnetic properties and their modification by thickness and strain effects, as well as optical parameters, are covered. Finally, we highlight various types of devices based on BiFeO3 in electronics, spintronics, and optics, and provide perspectives for the development of further multifunctional devices for information technology and energy harvesting.

https://iopscience.iop.org/article/10.1088/0953-8984/26/47/473201/pdf

BiFeO3 epitaxial thin films and devices: past, present and future

Piezoelectric materials are used in numerous applications requiring a coupling between electrical fields and mechanical strain. Despite the technological importance of this class of materials, for only a small fraction of all inorganic compounds which display compatible crystallographic symmetry, has piezoelectricity been characterized experimentally or computationally. In this work we employ first-principles calculations based on density functional perturbation theory to compute the piezoelectric tensors for nearly a thousand compounds, thereby increasing the available data for this property by more than an order of magnitude. The results are compared to select experimental data to establish the accuracy of the calculated properties. The details of the calculations are also presented, along with a description of the format of the database developed to make these computational results publicly available. In addition, the ways in which the database can be accessed and applied in materials development efforts are described.

/pdf/a-database-to-enable-discovery-and-design-of-piezoelectric-36v4ckzqhq.pdf

A database to enable discovery and design of piezoelectric materials

Non-coplanar swirling field textures, or skyrmions, are now widely recognized as objects of both fundamental interest and technological relevance. So far, skyrmions were amply investigated in magnets, where due to the presence of chiral interactions, these topological objects were found to be intrinsically stabilized. Ferroelectrics on the other hand, lacking such chiral interactions, were somewhat left aside in this quest. Here we demonstrate, via the use of a first-principles-based framework, that skyrmionic configuration of polarization can be extrinsically stabilized in ferroelectric nanocomposites. The interplay between the considered confined geometry and the dipolar interaction underlying the ferroelectric phase instability induces skyrmionic configurations. The topological structure of the obtained electrical skyrmion can be mapped onto the topology of domain-wall junctions. Furthermore, the stabilized electrical skyrmion can be as small as a few nanometers, thus revealing prospective skyrmion-based applications of ferroelectric nanocomposites.

/pdf/discovery-of-stable-skyrmionic-state-in-ferroelectric-28x0fc7xvp.pdf

Discovery of stable skyrmionic state in ferroelectric nanocomposites

Epitaxial strain has recently emerged as a powerful means to engineer the properties of ferroelectric thin films, for instance to enhance the ferroelectric Curie temperature (T(C)) in BaTiO(3). However, in multiferroic BiFeO(3) thin films an unanticipated strain-driven decrease of T(C) was reported and ascribed to the peculiar competition between polar and antiferrodistortive instabilities. Here, we report a systematic characterization of the room-temperature ferroelectric and piezoelectric properties for strain levels ranging between -2.5% and +1%. We find that polarization and the piezoelectric coefficient increase by about 20% and 250%, respectively, in this strain range. These trends are well reproduced by first-principles-based techniques.

https://iopscience.iop.org/article/10.1088/0953-8984/24/16/162202/pdf

T. Bouvet

Papers

Strain dependence of polarization and piezoelectric response in epitaxial BiFeO3 thin films