No abstract

Ferroelectrics carry a switchable spontaneous electric polarization. This polarization is usually coupled to strain, making ferroelectrics good piezoelectrics. When coupled to magnetism, they become so-called multiferroic systems, a field that has been widely investigated since 2003. While ferroelectrics are birefringent and non-linear optically transparent materials, the coupling of polarization with optical properties has received, since 2009, renewed attention, triggered notably by low-bandgap ferroelectrics suitable for sunlight spectrum absorption and original photovoltaic effects. Consequently, power conversion efficiencies up to 8.1% were recently achieved and values of 19.5% were predicted, making photoferroelectrics promising photovoltaic alternatives. This article aims at providing an up-to-date review on this emerging and rapidly progressing field by highlighting several important issues and parameters, such as the role of domain walls, ways to tune the bandgap, consequences arising from the polarization switchability, and the role of defects and contact electrodes, as well as the downscaling effects. Beyond photovoltaicity, other polarization-related processes are also described, like light-induced deformation (photostriction) or light-assisted chemical reaction (photostriction). It is hoped that this overview will encourage further avenues to be explored and challenged and, as a byproduct, will inspire other research communities in material science, e.g., so-called hybrid halide perovskites.

We investigate the cubic to tetragonal phase transition in the pressure-temperature phase diagram of strontium titanate SrTiO3 (STO) by means of Raman spectroscopy and X-ray diffraction on single crystal samples. X-ray diffraction experiments are performed at room temperature, 381 K and 467 K up to 53 GPa, 30 GPa and 26 GPa respectively. The observation of the superstructure reflections in the X-ray patterns provides evidence that the crystal undergoes at all investigated temperatures a pressure-induced transition from cubic to the tetragonal I4/mcm phase, identical to the low-temperature phase. No other phase transition is observed at room temperature up to 53 GPa. Together with previously published data, our results allow us to propose a new linear phase boundary in the pressure-temperature phase diagram. The data are analyzed in the framework of the Landau theory of phase transitions. With a revised value of the coupling coefficient between the order parameter and the volume spontaneous strain, the model built from pressure-independent coefficients reproduces satisfactorily the boundary in the phase diagram, but fails at reflecting the more pronounced second-order character of the pressure-induced phase transition as compared to the temperature-induced transition. We propose a new Landau potential suitable for the description of the pressure-induced phase transition. Finally, we show that particular attention has to be paid to hydrostatic conditions in the study of the high-pressure phase transition in STO.

Ferroelectric and ferroelastic domain walls are two-dimensional (2D) topological defects with thicknesses approaching the unit cell level. When this spatial confinement is combined with observations of emergent functional properties, such as polarity in non-polar systems or electrical conductivity in otherwise insulating materials, it becomes clear that domain walls represent a new and exciting state of matter. In this review, we discuss the exotic polarisation profiles that can arise at domain walls with multiple order parameters and the different mechanisms that lead to domain wall polarity in non-polar ferroelastic materials. The emergence of energetically degenerate variants of the domain walls themselves suggests the existence of interesting quasi-1D topological defects within such walls. We also provide an overview of the general notions which have been postulated as fundamental mechanisms responsible for domain wall conduction in ferroelectrics. We then discuss the prospect of combining domain walls with transition regions observed at phase boundaries, homo-and heterointerfaces, and other quasi-2D objects, enabling emergent properties beyond those available in today's topological systems. Key points• In ferroelectrics, the emergence of a second polarisation component leads to analogues of Bloch and Néel walls. The stabilization of these walls opens the possibility for quasi-1D topological defects separating wall regions of opposite polarities.• Polar domain walls in ferroelastics rely on two mechanisms: a polarity imposed by the natural symmetry of strain-compatible domain walls, which can often be described by flexoelectric gradient coupling, and the emergence of a potentially switchable polarity when their natural symmetry is broken.• Several mechanisms are responsible for domain wall conduction in ferroelectrics: extrinsic intra-bandgap defect states, intrinsic suppression of the conduction band and intrinsic shift of the band structure induced by local electric fields.• Transition regions occurring at phase boundaries, homo-and heterointerfaces, and other quasi-2D objects probably exist at a smaller length scale, in the vicinity of domain walls, and could lead to exceptional properties and coupling phenomena.

We investigate the high-pressure phase transitions in BiFeO3 by single crystal and powder x-ray diffraction, as well as single crystal Raman spectroscopy. Six phase transitions are reported in the 0-60 GPa range. At low pressures, up to 15 GPa, 4 transitions are evidenced at 4, 5, 7 and 11 GPa. In this range, the crystals display large unit cells and complex domain structures, which suggests a competition between complex tilt systems and possibly off-center cation displacements. The non polar P nma phase remains stable over a large pressure range between 11 and 38 GPa, where the distortion (tilt angles) changes only little with pressure. The two high-pressure phase transitions at 38 and 48 GPa are marked by the occurence of larger unit cells and an increase of the distorsion away from the cubic parent perovskite cell. We find no evidence for a cubic phase at high pressure, nor indications that the structure tends to become cubic. The previously reported insulator-to-metal transition at 50 GPa appears to be symmetry breaking.

We report a Raman scattering study of six rare earth orthoferrites RFeO3, with R = La, Sm, Eu, Gd, Tb, Dy. The use of extensive polarized Raman scattering of SmFeO3 and first-principles calculations enable the assignment of the observed phonon modes to vibrational symmetries and atomic displacements. The assignment of the spectra and their comparison throughout the whole series allows correlating the phonon modes with the orthorhombic structural distortions of RFeO3 perovskites. In particular, the positions of two specific Ag modes scale linearly with the two FeO6 octahedra tilt angles, allowing the distortion throughout the series. At variance with literature, we find that the two octahedra tilt angles scale differently with the vibration frequencies of their respective Ag modes. This behavior as well as the general relations between the tilt angles, the frequencies of the associated modes and the ionic radii are rationalized in a simple Landau model. The reported Raman spectra and associated phonon-mode assignment provide reference data for structural investigations of the whole series of orthoferrites.

Raman scattering is used to observe pronounced electronic excitations around 230 meV--well above the two-phonon range--in the Mott insulators LaTiO3 and YTiO3. Based on the temperature, polarization, and photon energy dependence, the modes are identified as orbital excitations. The observed profiles bear a striking resemblance to magnetic Raman modes in the insulating parent compounds of the superconducting cuprates, indicating an unanticipated universality of the electronic excitations in transition metal oxides.

At variance with structural ferroic phase transitions which give rise to macroscopic tensors coupled to macroscopic fields, criteria defining antiferroelectric (AFE) phase transitions are still under discussion due to the absence of specific symmetry properties characterizing their existence. They are recognized by the proximity of a ferroelectric (FE) phase induced under applied electric field, with a double hysteresis loop relating the induced polarization to the electric field and a typical anomaly of the dielectric permittivity. Here, we show that there exist indeed symmetry criteria defining AFE transitions. They relate the local symmetry of the polar crystallographic sites emerging at an AFE phase transition with the macroscopic symmetry of the AFE phase. The dielectric properties of AFE transitions are deduced from a Landau theoretical model in which ferroelectric and ferrielectric phases are shown to stabilize as the result of specific symmetry-allowed couplings of the AFE order- parameter with the field-induced polarization.Comment: 7 pages, 5 figures, 1 tabl