The Physical Properties of Materials Group

The layered perovskite YBaCuFeO₅ is a rare example of a cycloidal spiral magnet whose ordering temperature Tspiral can be tuned far beyond room temperature by adjusting the degree of Cu²⁺/ Fe³⁺ chemical disorder in the structure. This unusual property qualifies this material as one of the most promising spin-driven multiferroic candidates. However, very little is known about the response of the spiral to magnetic fields, crucial for magnetoelectric cross-control applications. Using bulk magnetization and neutron powder diffraction measurements under magnetic fields up to 9 T, we report here a temperature-magnetic field phase diagram of this material. Besides revealing a strong stability of the spiral state, our data uncover the presence of weak ferromagnetism coexisting with the spiral modulation. Since ferromagnets can be easily manipulated with magnetic fields, this observation opens new perspectives for the control of the spiral orientation, directly linked to the polarization direction, as well as for a possible future use of this material in technological applications.

The rare earth nickelates RNiO₃ are metallic at high temperatures and insulating and magnetically ordered at low temperatures. The low temperature phase has been predicted to be type II multiferroic, i.e., ferroelectric and magnetic order are coupled and occur simultaneously. Confirmation of those ideas has been inhibited by the absence of experimental data on single crystals. Here we report on Raman spectroscopic data of RNiO₃ single crystals (R = Y, Er, Ho, Dy, Sm, Nd) for temperatures between 10 and 1000 K. Entering the magnetically ordered phase we observe the appearance of a large number of additional vibrational modes, implying a breaking of inversion symmetry expected for multiferroic order.

The electronic properties of transition-metal oxides with highly correlated electrons are of central importance in modern condensed-matter physics and chemistry, both for their fundamental scientific interest and for their potential for advanced electronic applications. However, the design of materials with tailored properties has been restricted by the limited understanding of their structure–property relationships, which are particularly complex in the proximity of the regime where localized electrons become gradually mobile. RENiO₃ perovskites, characterized by the presence of spontaneous metal to insulator transitions, are some of the most widely used model materials for the investigation of this region in theoretical studies. However, crucial experimental information needed to validate theoretical predictions is still lacking due to their challenging high-pressure synthesis, which has prevented to date the growth of sizable bulk single crystals with RE ≠ La, Pr, and Nd. Here we report the first successful growth of single crystals with RE = Nd, Sm, Gd, Dy, Y, Ho, Er, and Lu in sizes up to ∼75 μm, grown from molten salts in a temperature gradient under 2000 bar of oxygen gas pressure. The crystals display regular prismatic shapes with flat facets, and their crystal structures and metal–insulator and antiferromagnetic order transition temperatures are in excellent agreement with previously reported values obtained from polycrystalline samples. The availability of such crystals opens access to measurements that have hitherto been impossible to conduct. This should contribute to a better understanding of the fascinating properties of materials with highly correlated electrons and guide future efforts to engineer transition-metal oxides with tailored functional properties.

The possibility of tuning the magnetic properties of materials with voltage (converse magnetoelectricity) or generating electric voltage with magnetic fields (direct magnetoelectricity) has opened new avenues in a large variety of technological fields, ranging from information technologies to healthcare devices and including a great number of multifunctional integrated systems, such as mechanical antennas, magnetometers, and radio frequency (RF) tunable inductors, which have been realized due to the strong strain-mediated magnetoelectric (ME) coupling found in ME composites. The development of single-phase multiferroic materials (which exhibit simultaneous ferroelectric and ferromagnetic or antiferromagnetic orders), multiferroic heterostructures, as well as progress in other ME mechanisms, such as electrostatic surface charging or magneto-ionics (voltage-driven ion migration), have a large potential to boost energy efficiency in spintronics and magnetic actuators. This article focuses on existing ME materials and devices and reviews the state of the art in their performance.

The role of the perovskite lattice oxygen in the oxygen evolution reaction (OER) is systematically studied in the PrBaCo₂O_5+δ family. The reduced number of physical/chemical variables combined with in-depth characterizations such as neutron dif-fraction, O K-edge X-ray absorption spectroscopy (XAS), electron energy loss spectroscopy (EELS), magnetization and scanning transmission electron microscopy (STEM) studies, helps investigating the complex correlation between OER activity and a single perovskite property, such as the oxygen content. Larger amount of oxygen vacancies appears to facilitate the OER, possibly contributing to the mechanism involving the oxidation of lattice oxygen, i.e., the lattice oxygen evolution reaction (LOER). Furthermore, not only the number of vacancies but also their local arrangement in the perovskite lattice influences the OER activity, with a clear drop for the more stable, ordered stoichiometry.