Electrical and magnetic properties of the complete solid solution series between SrRuO3 and LaRhO3: Filling t2g versus tilting

A complete solid solution series between the t2g^4 perovskite ferromagnet SrRuO3 and the diamagnetic t2g^6 perovskite LaRhO3 has been prepared. The evolution with composition x in (SrRuO3)(1-x)(LaRhO3)(x) of the crystal structure and electrical and magnetic properties has been studied and is reported here. As x increases, the octahedral tilt angle gradually increases, along with the pseudocubic lattice parameter and unit cell volume. Electrical resistivity measurements reveal a compositionally driven metal to insulator transition between x = 0.1 and 0.2. Ferromagnetic ordering gives over to glassy magnetism for x > 0.3 and no magnetic ordering is found above 2 K for x > 0.5. M_sat and Theta_CW decrease with increasing x and remain constant after x = 0.5. The magnetism appears poised between localized and itinerant behavior, and becomes more localized with increasing x as evidenced by the evolution of the Rhodes-Wohlfarth ratio. mu_eff per Ru is equal to the quenched spin-only S value across the entire solid solution. Comparisons with Sr(1-x)Ca(x)RuO3 reinforce the important role of structural distortions in determining magnetic ground state. It is suggested that electrical transport and magnetic properties are not strongly coupled in this system

Does the 8−N8-N bonding rule break down in As2_2Se3_3 glass?

The local coordination numbers of As$_2$Se$_3$ glass were determined by a combination of anomalous x-ray scattering experiments, reverse Monte Carlo calculations, and {\it ab initio} molecular dynamics simulations. The well-known `8-$N$ bonding rule' proposed by Mott breaks down around the As atoms, exceeding the rule by 7--26%. An experimental prediction based on mean-field theory agrees with the present experimental and theoretical results. The fourfold coordinated As atoms likely form As-As wrong bond chains rather than ethan-like configurations, which is identified as the origin for the breakdown of the `8-$N$ bonding rule'.Comment: 6 pages, 6figures, 1table, submitted to Europhysics Letter

Total scattering descriptions of local and cooperative distortions in the oxide spinel (Mg,Cu)Cr2O4 with dilute Jahn-Teller ions

The normal spinel oxide MgCr2O4 is cubic at room temperature while the normal spinel CuCr2O4 is tetragonal as a consequence of the Jahn-Teller nature of Cu2+ on the tetrahedral sites. Despite different end-member structures, complete solid solutions of Mg_{1-x}Cu_xCr2O4 can be prepared that display a first-order structural transition with composition x = 0.43 at room temperature. Reverse Monte Carlo analysis of total neutron scattering on data acquired between 300 K and 15 K on samples with x = 0.10, 0.20, and 0.43 provides unbiased local and average structure descriptions of the samples, including an understanding of the transition from local Jahn-Teller distortions in the cubic phase to cooperative distortions that result in a tetragonal structure. Distributions of continuous symmetry measures help to understand and distinguish distorted and undistorted coordination around the tetrahedral site in the solid solutions. Magnetic exchange bias is observed in field-cooled hysteresis loops of samples with dilute Cu2+ concentration and in samples with tetragonal--cubic phase coexistence around 300 K.Comment: 10 pages, 14 figure

Exchange biasing of single-domain Ni nanoparticles spontaneously grown in an antiferromagnetic MnO matrix

Exchange biased composites of ferromagnetic single-domain Ni nanoparticles embedded within large grains of MnO have been prepared by reduction of Ni$_x$Mn$_{1-x}$O$_4$ phases in flowing hydrogen. The Ni precipitates are 15-30 nm in extent, and the majority are completely encased within the MnO matrix. The manner in which the Ni nanoparticles are spontaneously formed imparts a high ferromagnetic- antiferromagnetic interface/volume ratio, which results in substantial exchange bias effects. Exchange bias fields of up to 100 Oe are observed, in cases where the starting Ni content $x$ in the precursor Ni$_x$Mn$_{1-x}$O$_4$ phase is small. For particles of approximately the same size, the exchange bias leads to significant hardening of the magnetization, with the coercive field scaling nearly linearly with the exchange bias field.Comment: 6 pages PDFLaTeX with 9 figure

Phase relations in K_xFe_{2-y}Se_2 and the structure of superconducting K_xFe_2Se_2 via high-resolution synchrotron diffraction

Superconductivity in iron selenides has experienced a rapid growth, but not without major inconsistencies in the reported properties. For alkali-intercalated iron selenides, even the structure of the superconducting phase is a subject of debate, in part because the onset of superconductivity is affected much more delicately by stoichiometry and preparation than in cuprate or pnictide superconductors. If high-quality, pure, superconducting intercalated iron selenides are ever to be made, the intertwined physics and chemistry must be explained by systematic studies of how these materials form and by and identifying the many coexisting phases. To that end, we prepared pure K_2Fe_4Se_5 powder and superconductors in the K_xFe_{2-y}Se_2 system, and examined differences in their structures by high-resolution synchrotron and single-crystal x-ray diffraction. We found four distinct phases: semiconducting K_2Fe_4Se_5, a metallic superconducting phase K_xFe_2Se_2 with x ranging from 0.38 to 0.58, an insulator KFe_{1.6}Se_2 with no vacancy ordering, and an oxidized phase K_{0.51(5)}Fe_{0.70(2)}Se that forms the PbClF structure upon exposure to moisture. We find that the vacancy-ordered phase K_2Fe_4Se_5 does not become superconducting by doping, but the distinct iron-rich minority phase K_xFe_2Se_2 precipitates from single crystals upon cooling from above the vacancy ordering temperature. This coexistence of metallic and semiconducting phases explains a broad maximum in resistivity around 100 K. Further studies to understand the solubility of excess Fe in the K_xFe_{2-y}Se_2 structure will shed light on the maximum fraction of superconducting K_xFe_2Se_2 that can be obtained by solid state synthesis.Comment: 12 pages, 16 figures, supplemental materia

Tuning magnetic frustration on the diamond lattice of the A-site magnetic spinels CoAl2−x_{2-x}Gax_xO4_4: Lattice expansion and site disorder

The spinels CoB$_2$O$_4$ with magnetic Co$^{2+}$ ions on the diamond lattice A site can be frustrated because of competing near-neighbor ($J_1$) and next-near neighbor ($J_2$) interactions. Here we describe attempts to tune the relative strengths of these interactions by substitution on the non-magnetic B-site. The system we employ is CoAl$_{2-x}$Ga$_x$O$_4$, where Al is systematically replaced by the larger Ga, ostensibly on the B site. As expected, Ga substitution expands the lattice, resulting in Co atoms on the A-site being pushed further from one other and thereby weakening magnetic interactions. In addition, Ga distributes between the B and the A site in a concentration dependent manner displacing an increasing amount of Co from the A site with increasing $x$. This increased inversion, which is confirmed by neutron diffraction studies carried out at room temperature, affects magnetic ordering very significantly, and changes the nature of the ground state. Modeling of the magnetic coupling illustrates the complexity that arises from the cation site disorder.Comment: 9 pages, 10 figure

Magnetodielectric coupling in Mn3O4

We have investigated the dielectric anomalies associated with spin ordering transitions in the tetragonal spinel Mn$_3$O$_4$, using thermodynamic, magnetic, and dielectric measurements. We find that two of the three magnetic ordering transitions in Mn$_3$O$_4$ lead to decreases in the temperature dependent dielectric constant at zero applied field. Applying a magnetic field to the polycrystalline sample leaves these two dielectric anomalies practically unchanged, but leads to an increase in the dielectric constant at the intermediate spin-ordering transition. We discuss possible origins for this magnetodielectric behavior in terms of spin-phonon coupling. Band structure calculations suggest that in its ferrimagnetic state, Mn$_3$O$_4$ corresponds to a semiconductor with no orbital degeneracy due to strong Jahn-Teller distortion.Comment: 6 pages, 7 figure

Dilute ferrimagnetic semiconductors in Fe-substituted spinel ZnGa2_2O4_4

Solid solutions of nominal composition [ZnGa$_2$O$_4$]$_{1-x}$[Fe$_3$O$_4$]$_x$, of the semiconducting spinel ZnGa$_2$O$_4$ with the ferrimagnetic spinel Fe$_3$O$_4$ have been prepared with $x$ = 0.05, 0.10, and 0.15. All samples show evidence for long-range magnetic ordering with ferromagnetic hysteresis at low temperatures. Magnetization as a function of field for the $x$ = 0.15 sample is S-shaped at temperatures as high as 200 K. M\"ossbauer spectroscopy on the $x$ = 0.15 sample confirms the presence of Fe$^{3+}$, and spontaneous magnetization at 4.2 K. The magnetic behavior is obtained without greatly affecting the semiconducting properties of the host; diffuse reflectance optical spectroscopy indicates that Fe substitution up to $x$ = 0.15 does not affect the position of the band edge absorption. These promising results motivate the possibility of dilute ferrimagnetic semiconductors which do not require carrier mediation of the magnetic moment.Comment: 9 pages and 6 figure

Electronic structure, magnetism, and disorder in the Heusler compound Co2_2TiSn

Polycrystalline samples of the half-metallic ferromagnet Heusler compound Co$_2$TiSn have been prepared and studied using bulk techniques (X-ray diffraction and magnetization) as well as local probes ($^{119}$Sn M\"ossbauer spectroscopy and $^{59}$Co nuclear magnetic resonance spectroscopy) in order to determine how disorder affects half-metallic behavior and also, to establish the joint use of M\"ossbauer and NMR spectroscopies as a quantitative probe of local ion ordering in these compounds. Additionally, density functional electronic structure calculations on ordered and partially disordered Co$_2$TiSn compounds have been carried out at a number of different levels of theory in order to simultaneously understand how the particular choice of DFT scheme as well as disorder affect the computed magnetization. Our studies suggest that a sample which seems well-ordered by X-ray diffraction and magnetization measurements can possess up to 10% of antisite (Co/Ti) disordering. Computations similarly suggest that even 12.5% antisite Co/Ti disorder does not destroy the half-metallic character of this material. However, the use of an appropriate level of non-local DFT is crucial.Comment: 11 pages and 5 figure

Structural and magnetic characterization of the complete delafossite solid solution (CuAlO2){1-x}(CuCrO2){x}

We have prepared the complete delafossite solid solution series between diamagnetic CuAlO2 and the t2g^3 frustrated antiferromagnet CuCrO2. The evolution with composition x in CuAl(1-x)Cr(x)O2 of the crystal structure and magnetic properties has been studied and is reported here. The room-temperature unit cell parameters follow the Vegard law and increase with x as expected. The effective moment is equal to the Cr^3+ spin-only S = 3/2 value throughout the entire solid solution. Theta is negative, indicating that the dominant interactions are antiferromagnetic, and its magnitude increases with Cr substitution. For dilute Cr compositions, J_BB was estimated by mean-field theory to be 2.0 meV. Despite the sizable Theta, long-range antiferromagnetic order does not develop until very large x, and is preceeded by glassy behavior. Data presented here, and that on dilute Al-substitution from Okuda et al., suggest that the reduction in magnetic frustration due to the presence of non-magnetic Al does not have as dominant an effect on magnetism as chemical disorder and dilution of the magnetic exchange. For all samples, the 5 K isothermal magnetization does not saturate in fields up to 5 T and minimal hysteresis is observed. The presence of antiferromagnetic interactions is clearly evident in the sub-Brillouin behavior with a reduced magnetization per Cr atom. An inspection of the scaled Curie plot reveals that significant short-range antiferromagnetic interactions occur in CuCrO2 above its Neel temperature, consistent with its magnetic frustration. Uncompensated short-range interactions are present in the Al-substituted samples and are likely a result of chemical disorder