Tuning magnetic spirals beyond room temperature with chemical disorder.

In the past years, magnetism-driven ferroelectricity and gigantic magnetoelectric effects have been reported for a number of frustrated magnets featuring ordered spiral magnetic phases. Such materials are of high-current interest due to their potential for spintronics and low-power magnetoelectric devices. However, their low-magnetic ordering temperatures (typically <100 K) greatly restrict their fields of application. Here we demonstrate that the onset temperature of the spiral phase in the perovskite YBaCuFeO5 can be increased by more than 150 K through a controlled manipulation of the Fe/Cu chemical disorder. Moreover, we show that this novel mechanism can stabilize the magnetic spiral state of YBaCuFeO5 above the symbolic value of 25 °C at zero magnetic field. Our findings demonstrate that the properties of magnetic spirals, including its wavelength and stability range, can be engineered through the control of chemical disorder, offering a great potential for the design of materials with magnetoelectric properties beyond room temperature.

New synthesis route and magnetic structure of Tm2Mn2O7 pyrochlore.

In this work, we present a new chemical route to synthesize Tm2Mn2O7 pyrochlore, which a compound that is thermodynamically unstable at ambient pressure. Differently from the reported in the past high-pressure synthesis of the same compound applying oxides as starting materials, we have obtained a pure Tm2Mn2O7 phase by a converting TmMnO3 at 1100 °C and an oxygen pressure of 1300 bar. The studies of Tm2Mn2O7 performed by a high-resolution neutron powder diffraction have shown that a pure pyrochlore cubic phase Tm2Mn2O7 (space group Fd3¯m) have been obtained. Upon cooling below 25 K, there is a transition to a ferromagnetically (FM) ordered phase observed with an additional antiferromagnetic (AFM) canting, suggesting a lowering of the initial cubic crystal symmetry. The magnetic transition is accompanied by a small but very visible magnetostriction effect. Using symmetry analysis, we have found a solution for the AFM structure in the maximal Shubnikov subgroup I41/am'd'.

Lattice dynamics to trigger low temperature oxygen mobility in solid oxide ion conductors.

SrFeO(2.5) and SrCoO(2.5) are able to intercalate oxygen in a reversible topotactic redox reaction already at room temperature to form the cubic perovskites Sr(Fe,Co)O(3), while CaFeO(2.5) can only be oxidized under extreme conditions. To explain this significant difference in low temperature oxygen mobility, we investigated the homologous SrFeO(2.5) and CaFeO(2.5) by temperature dependent oxygen isotope exchange as well as by inelastic neutron scattering (INS) studies, combined with ab initio (DFT) molecular dynamical calculations. From (18)O/(16)O isotope exchange experiments we proved free oxygen mobility to be realized in SrFeO(x) already below 600 K. We have also evidence that low temperature oxygen mobility relies on the existence of specific, low energy lattice modes, which trigger and amplify oxygen mobility in solids. We interpret the INS data together with the DFT-based molecular dynamical simulation results on SrFeO(2.5) and CaFeO(2.5) in terms of an enhanced, phonon-assisted, low temperature oxygen diffusion for SrFeO(3-x) as a result of the strongly reduced Fe-O-Fe bond strength of the apical oxygen atoms in the FeO(6) octahedra along the stacking axis. This dynamically triggered phenomenon leads to an easy migration of the oxide ions into the open vacancy channels and vice versa. The decisive impact of lattice dynamics, giving rise to structural instabilities in oxygen deficient perovskites, especially with brownmillerite-type structure, is demonstrated, opening new concepts for the design and tailoring of low temperature oxygen ion conductors.