Chang-Yang Kuo

Electrically controllable spontaneous magnetism in nanoscale mixed phase multiferroics

Magnetoelectrics and multiferroics present exciting opportunities for electric-field control of magnetism. However, there are few room-temperature ferromagnetic-ferroelectrics. Among the various types of multiferroics the bismuth ferrite system has received much attention primarily because both the ferroelectric and the antiferromagnetic orders are quite robust at room temperature. Here we demonstrate the emergence of an enhanced spontaneous magnetization in a strain-driven rhombohedral and super-tetragonal mixed phase of BiFeO₃. Using X-ray magnetic circular dichroism-based photoemission electron microscopy coupled with macroscopic magnetic measurements, we find that the spontaneous magnetization of the rhombohedral phase is significantly enhanced above the canted antiferromagnetic moment in the bulk phase, as a consequence of a piezomagnetic coupling to the adjacent tetragonal-like phase and the epitaxial constraint. Reversible electric-field control and manipulation of this magnetic moment at room temperature is also shown.

k=0 Magnetic Structure and Absence of Ferroelectricity in SmFeO3

SmFeO3 has attracted considerable attention very recently due to its reported multiferroic properties above room temperature. We have performed powder and single crystal neutron diffraction as well as complementary polarization dependent soft X-ray absorption spectroscopy measurements on floating-zone grown SmFeO3 single crystals in order to determine its magnetic structure. We found a k=0 G-type collinear antiferromagnetic structure that is not compatible with inverse Dzyaloshinskii-Moriya interaction driven ferroelectricity. While the structural data reveal a clear sign for magneto-elastic coupling at the Néel-temperature of ∼675  K, the dielectric measurements remain silent as far as ferroelectricity is concerned.

Spectroscopic evidence for exceptionally high orbital moment induced by local distortions in α-CoV2O6

N. Hollmann, S. Agrestini, Z. Hu, Z. He, M. Schmidt, C.-Y. Kuo, M. Rotter, A. A. Nugroho, V. Sessi, A. Tanaka, N. B. Brookes, and L. H. Tjeng Max-Planck-Institut für Chemische Physik fester Stoffe, Nöthnitzer Str. 40, 01187 Dresden, Germany State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia European Synchrotron Radiation Facility, Bôıte Postale 220, F-38043 Grenoble Cédex, France Department of Quantum Matter, ADSM, Hiroshima University, Higashi-Hiroshima 739-8530, Japan (Dated: May 11, 2014)

Coupled valence and spin state transition in (Pr0.7Sm0.3)0.7Ca0.3CoO3

The coupled valence and spin state transition (VSST) taking place in (Pr0.7Sm0.3)0.7Ca0.3CoO3 was investigated by soft x-ray absorption spectroscopy (XAS) experiments carried out at the Pr-M4,5, Co-L2,3, and O-1s edges. This VSST is found to be composed of a sharp Pr/Co valence and Co spin state transition centered at T*=89.3 K, followed by a smoother Co spin-state evolution at higher temperatures. At T < T*, we found that the praseodymium displays a mixed valence Pr3+/Pr4+ with about 0.13 Pr4+/f.u., while all the Co3+ is in the low-spin (LS) state. At T around T*, the sharp valence transition converts all the Pr4+ to Pr3+ with a corresponding Co3+ to Co4+ compensation. This is accompanied by an equally sharp spin state transition of the Co3+ from the low to an incoherent mixture of low and high spin (HS) states. An involvement of the intermediate spin (IS) state can be discarded for the Co3+. While above T* and at high temperatures the system shares rather similar properties as Sr-doped LaCoO3, at low temperatures it behaves much more like EuCoO3 with its highly stable LS configuration for the Co3+. Apparently, the mechanism responsible for the formation of Pr4+ at low temperatures also helps to stabilize the Co3+ in the LS configuration despite the presence of Co4+ ions. We also found out that that the Co4+ is in an IS state over the entire temperature range investigated in this study (10-290 K). The presence of Co3+ HS and Co4+ IS at elevated temperatures facilitates the conductivity of the material.

Synthesis and Characterization of Ba[CoSO]: Magnetic Complexity in the Presence of Chalcogen Ordering

Barium thio-oxocobaltate(II), Ba[CoS2/2 O2/2 ], was synthesized by the reaction of equimolar amounts of BaO, Co, and S in closed silica ampoules. The title compound (Cmcm, a=3.98808(3), b=12.75518(9), c=6.10697(4) Å) is isostructural to Ba[ZnSO]. The use of soft X-ray absorption spectroscopy confirmed that cobalt is in the oxidation state +2 and tetrahedrally coordinated. Its coordination consists of two sulfur and two oxygen atoms in an ordered fashion. High-temperature magnetic susceptibility data indicate strong low-dimensional spin-spin interactions, which are suggested to be closely related to the layer-type crystal structure and perhaps the ordered distribution of sulfur and oxygen. Antiferromagnetic ordering below TN =222 K is observed as an anomaly in the specific heat, coinciding with a significant lowering of the magnetic susceptibility. Density functional theory calculations within a generalized-gradient approximation (GGA)+U approach identify an antiferromagnetic ground state within the square-like two-dimensional layers of Co, and antiferromagnetic correlations for nearest and next nearest neighbors along bonds mediated by oxygen or sulfur. However, this magnetic state is subject to frustration by relatively strong interlayer couplings.

Antiferromagnetic correlations in the metallic strongly correlated transition metal oxide LaNiO3

The material class of rare earth nickelates with high Ni3+ oxidation state is generating continued interest due to the occurrence of a metal-insulator transition with charge order and the appearance of non-collinear magnetic phases within this insulating regime. The recent theoretical prediction for superconductivity in LaNiO3 thin films has also triggered intensive research efforts. LaNiO3 seems to be the only rare earth nickelate that stays metallic and paramagnetic down to lowest temperatures. So far, centimeter-sized impurity-free single crystal growth has not been reported for the rare earth nickelates material class since elevated oxygen pressures are required for their synthesis. Here, we report on the successful growth of centimeter-sized LaNiO3 single crystals by the floating zone technique at oxygen pressures of up to 150 bar. Our crystals are essentially free from Ni2+ impurities and exhibit metallic properties together with an unexpected but clear antiferromagnetic transition.The phase transitions of rare earth nickelates have attracted intensive study as they arise from the complex interplay of charge, spin and lattice degrees of freedom. Here Guo et al. present evidence that LaNiO3 has an unanticipated magnetically ordered metallic phase.

Three Oxidation States of Manganese in the Barium Hexaferrite BaFe12–xMnxO19

The coexistence of three valence states of Mn ions, namely, +2, +3, and +4, in substituted magnetoplumbite-type BaFe12-xMnxO19 was observed by soft X-ray absorption spectroscopy at the Mn-L2,3 edge. We infer that the occurrence of multiple valence states of Mn situated in the pristine purely iron(III) compound BaFe12O19 is made possible by the fact that the charge disproportionation of Mn3+ into Mn2+ and Mn4+ requires less energy than that of Fe3+ into Fe2+ and Fe4+, related to the smaller effective Coulomb interaction of Mn3+ (d4) compared to Fe3+ (d5). The different chemical environments determine the location of the differently charged ions: with Mn3+ occupying positions with (distorted) octahedral local symmetry, Mn4+ ions prefer octahedrally coordinated sites in order to optimize their covalent bonding. Larger and more ionic bonded Mn2+ ions with a spherical charge distribution accumulate at tetrahedrally coordinated sites. Simulations of the experimental Mn-L2,3 XAS spectra of two different samples with x = 1.5 and x = 1.7 led to Mn2+:Mn3+:Mn4+ atomic ratios of 0.16:0.51:0.33 and 0.19:0.57:0.24.

Electronic and spin states of SrRuO3 thin films: An x-ray magnetic circular dichroism study

We report a study of the local magnetism in thin films of SrRuO3 grown on (111) and (001) oriented SrTiO3 substrates using x-ray magnetic circular dichroism spectroscopy (XMCD) at the Ru-L2,3 edges. The application of the sum rules to the XMCD data gives an almost quenched orbital moment and a spin moment close to the value expected for the low spin state S = 1 . Full-multiplet cluster calculations indicate that the low spin state is quite stable and suggest that the occurrence of a transition to the high spin state S = 2 in strained thin films of SrRuO3 is unlikely as it would be too expensive in energy.

Ba3V2S4O3: A Mott Insulating Frustrated Quasi‐One‐Dimensional S=1 Magnet

Through a solid-state reaction, a practically phase pure powder of Ba3 V2 S4 O3 was obtained. The crystal structure was confirmed by X-ray single-crystal and synchrotron X-ray powder diffraction (P63 , a=10.1620(2), c=5.93212(1) Å). X-ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge-disproportionated V(III) S6 and V(V) SO3 coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long-range order from evolving.

Incommensurate spin correlations in highly oxidized cobaltates La2-xSrxCoO4.

We observe quasi-static incommensurate magnetic peaks in neutron scattering experiments on layered cobalt oxides La2−xSrxCoO4 with high Co oxidation states that have been reported to be paramagnetic. This enables us to measure the magnetic excitations in this highly hole-doped incommensurate regime and compare our results with those found in the low-doped incommensurate regime that exhibit hourglass magnetic spectra. The hourglass shape of magnetic excitations completely disappears given a high Sr doping. Moreover, broad low-energy excitations are found, which are not centered at the incommensurate magnetic peak positions but around the quarter-integer values that are typically exhibited by excitations in the checkerboard charge ordered phase. Our findings suggest that the strong inter-site exchange interactions in the undoped islands are critical for the emergence of hourglass spectra in the incommensurate magnetic phases of La2−xSrxCoO4.