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Polar metals exist as a rather unique class of materials as they combine two seemingly mutually exclusive properties (polar order and metallicity) in one system. So far only a few polar metals have been unambiguously identified; the magnetic ones are exceptionally rare. Here we investigate a 5% Fe-doped polar metal Ca3Ru2O7, via electrical transport, magnetization, microstrain, and optical second-harmonic generation measurements. We report the full magnetic phase diagrams (in the field-temperature space) for magnetic field Ha and Hb, which exhibit distinct field-dependent magnetizations behavior. In particular, for Ha we found a ferromagnetic incommensurate spin structure, which is absent in the pure Ca3Ru2O7. We propose a microscopic spin model to understand this behavior, highlighting the role of Fe doping in tipping the delicate balance of the underlying exchange-interaction energy in this system.

[EN] Polar instabilities are well known to be suppressed on scaling materials down to the nanoscale, when the electrostatic energy increase at surfaces exceeds lowering of the bulk polarization energy. Surprisingly, here we report an emergent low symmetry polar phase arising in nanoscale powders of CaTiO, the original mineral named perovskite discovered in 1839 and considered nominally nonpolar at any finite temperature in the bulk. Using nonlinear optics and spectroscopy, X-ray diffraction, and microscopy studies, we discover a well-defined polar to non-polar transition at a T = 350 K in these powders. The same polar phase is also seen as a surface layer in bulk CaTiO single crystals, forming striking domains with in-plane polarization orientations. Density functional theory reveals that oxygen octahedral distortions in the surface layer lead to the stabilization of the observed monoclinic polar phase. These results reveal new ways of overcoming the scaling limits to polarization in perovskites.

Using time- and spatially resolved hard x-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO3 are simultaneously captured on subnanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photoinduced electric field of up to 20×106 V/m is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling method is developed that reveals the microscopic origin of these dynamics, leading to gigahertz polarization and elastic waves traveling in the crystal with sonic speeds and spatially varying frequencies. The advances in spatiotemporal imaging and dynamical modeling tools open up opportunities for disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains.

The loss of centrosymmetry via oxygen octahedral rotations is demonstrated in the n = 2 Dion–Jacobson family of layered oxide perovskites, A′LaB2O7 (A′ = Rb, Cs; B = Nb, Ta). Ab initio density functional theory calculations predict that all four materials should adopt polar space groups, in contrast to the results of previous experimental studies that have assigned these materials to the centrosymmetric P4/mmm space group. Optical second harmonic generation experiments confirm the presence of a noncentrosymmetric phase at ambient temperature. Piezoresponse force microscopy experiments also show that this phase is piezoelectric. To elucidate the symmetry-breaking and assign the appropriate space groups, the crystal structure of CsLaNb2O7 is refined as a function of temperature from synchrotron X-ray diffraction data. Above 550 K, CsLaNb2O7 adopts the previously determined centrosymmetric P4/mmm space group. Between 550 and 350 K, the symmetry is lowered to the noncentrosymmetric space group Amm2. Below 350 K, additional symmetry lowering is observed as peak splitting, but the space group cannot be unambiguously identified.

An improper mechanism for breaking inversion symmetry is revealed and thus inducing piezoelectricity in the family of layered perovskites, LiRTiO4 (R = rare earths), which are previously reported as centrosymmetric. Noncentrosymmetry in this family of compounds arises from TiO6 octahedral rotation represented by a−boco/boa−co in the perovskite blocks between RO rock salt and LiO antifluorite layers. X-ray diffraction and optical second harmonic generation complemented by density functional theory predictions are crucial in determining the new structures. High transition temperature (Tac) of up to 1200 K from noncentrosymmetric to centrosymmetric phase is observed. Piezoelectric coefficients (d36) of up to −15 pC/N are predicted, and piezoelectric force microscopy experiments confirm a piezoelectric response. The demonstrated improper mechanism in this and other layered oxide families, with a wide range of available topologies and chemistries, could aid in the search for high temperature piezoelectrics.

Mn22+Fe2+W6+O6, a new polar magnetic phase, adopts the corundum-derived Ni3TeO6-type structure with large spontaneous polarization (P-S) of 67.8 mu C cm-2, complex antiferromagnetic order below approximate to 75 K, and field-induced first-order transition to a ferrimagnetic phase below approximate to 30 K. First-principles calculations predict a ferrimagnetic (udu) ground state, optimal switching path along the c-axis, and transition to a lower energy udu-udd magnetic double cell.

Oxynitrides have been explored extensively in the past decade because of their interesting properties, such as visible-light absorption, photocatalytic activity and high dielectric permittivity. Their synthesis typically requires high-temperature NH3 treatment (800-1,300 °C) of precursors, such as oxides, but the highly reducing conditions and the low mobility of N3- species in the lattice place significant constraints on the composition and structure-and hence the properties-of the resulting oxynitrides. Here we show a topochemical route that enables the preparation of an oxynitride at low temperatures (<500 °C), using a perovskite oxyhydride as a host. The lability of H- in BaTiO3-xHx (x ≤ 0.6) allows H-/N3- exchange to occur, and yields a room-temperature ferroelectric BaTiO3-xN2x/3. This anion exchange is accompanied by a metal-to-insulator crossover via mixed O-H-N intermediates. These findings suggest that this 'labile hydride' strategy can be used to explore various oxynitrides, and perhaps other mixed anionic compounds.

Rotations of oxygen octahedra are ubiquitous, but they cannot break inversion symmetry in simple perovskites. However, in a layered oxide structure, this is possible, as we demonstrate here in A-site ordered Ruddlesden-Popper NaRTiO4 (R denotes rare-earth metal), previously believed to be centric. By revisiting this series via synchrotron x-ray diffraction, optical second-harmonic generation, piezoresponse force microscopy, and first-principles phonon calculations, we find that the low-temperature phase belongs to the acentric space group P4̄21m, which is piezoelectric and nonpolar. The mechanism underlying this large new family of acentric layered oxides is prevalent, and could lead to many more families of acentric oxides.

Lattice volume expansion or amorphization renders EuTiO[3] ferromagnetic, although the stable phase of crystalline EuTiO[3] is an antiferromagnet. The lattice volume expansion is induced into the crystalline EuTiO[3] thin film by utilizing the lattice mismatch between the thin film and a substrate. The magnetization at low temperatures monotonically increases with an increase in lattice volume for the crystalline EuTiO3 thin film, coincident with the results of calculations based on the hybrid Hartree–Fock density functional approach. The ferromagnetic interaction between Eu[2+] ions is enhanced by the amorphization as well; the amorphous EuTiO[3] thin film becomes a ferromagnet, and the Curie temperature is higher for amorphous Eu[2]TiO[4] than for its crystalline counterpart. The phenomenon, that is, the volume expansion- and amophization-induced ferromagnetism, is explained in terms of the competition between ferromagnetic and antiferromagnetic interactions among Eu[2+] ions.

Measurements of fundamental magnetic properties including not only dc and ac susceptibilities but also magnetic aging effects have been performed for aluminoborate glasses with high concentrations of iron and rare-earth R^3+ ions (R=Sm, Gd, and Tb) in order to give an insight into the magnetic structures and interactions in amorphous oxides containing both 3d transition metal and 4f rare-earth ions, which manifest magnetic interactions that differ from each other. We demonstrate that the antiferromagnetic interactions between iron and rare-earth ions as well as those between iron ions play a significant role for their magnetic properties, while those between rare-earth ions are of little importance. Most of the rare-earth ions remain paramagnetic even below the spin-freezing temperatures under the strong molecular field caused by the spin-glass freezing of the iron ions, as in the case of rare-earth garnet ferrites.

A superexchange mechanism between Eu^2+ 4f spins via the 3d states of nonmagnetic Ti^4+ ions is proposed through first-principles calculations based on a hybrid Hartree-Fock density functional approach to explain G-type antiferromagnetism in EuTiO3. This mechanism is supported by systematic calculations for related Eu2+-based perovskite oxides. In EuTiO3, the competition between the antiferromagnetic superexchange and an indirect ferromagnetic exchange via the Eu 5d states leads to a delicate balance between antiferromagnetic and ferromagnetic phases. The superexchange mechanism involving the Ti 3d states hints at the microscopic origin of the strong spin-lattice coupling in EuTiO3.

Measurements of fundamental magnetic properties including not only dc and ac susceptibilities but also magnetic aging effects have been performed for aluminoborate glasses with high concentrations of iron and rare-earth R^3+ ions (R=Sm, Gd, and Tb) in order to give an insight into the magnetic structures and interactions in amorphous oxides containing both 3d transition metal and 4f rare-earth ions, which manifest magnetic interactions that differ from each other. We demonstrate that the antiferromagnetic interactions between iron and rare-earth ions as well as those between iron ions play a significant role for their magnetic properties, while those between rare-earth ions are of little importance. Most of the rare-earth ions remain paramagnetic even below the spin-freezing temperatures under the strong molecular field caused by the spin-glass freezing of the iron ions, as in the case of rare-earth garnet ferrites.

In most amorphous insulating magnets, the magnetic structure is dominated by the random distribution of magnetic moments as well as the predominant antiferromagnetic interaction among them, inevitably leading to a transition from high-temperature paramagnetic to low-temperature spin glass phase. In this paper, we report our discovery of ferromagnetic amorphous oxides with reentrant spin glass behavior. Unlike most oxide glasses, there is a strong tendency for the magnetic interaction of Eu2+ ions to be ferromagnetic in oxide glasses, as obviously indicated by the positive values of Weiss temperature. Comprehensive investigations of low-temperature magnetic properties for the present Eu2+-containing glasses have revealed a typical behavior of reentrant ferromagnets. We discuss the possible mechanisms behind the ferromagnetic interactions, as well as the origin of reentrant spin glass nature, based on the specific electronic structure of Eu2+ compounds.