Ferromagnetism and antiferromagnetism coexistence in SrRu1−xMnxO3: Density functional calculation

We have calculated the electronic structure of SrRu_1−xMn_xO₃ using the full potential linearized augmented plane wave method by LSDA and LSDA+U. The antiparallel alignment between the Mn and Ru ions are consistent with the competition between ferromagnetism and antiferromagnetism in the low Mn-doped polycrystalline samples. This is in contrast to the appearance of quantum critical point and FM and AFM transitions in the single crystal measurement. Our results show that the discrepancy between different experimental phase diagrams is related to the conditions of sample preparation and also the difference between the degree of magnetic interactions between the Mn and Ru moments. The DOS and the calculated Mn magnetic moment is similar to the magnetic moment of a purely ionic compound with d³ configuration. The AFM state has band gap of 1.2 eV at the Fermi energy predicting an insulating behavior.     

Phase formation, crystal structures and magnetic properties of perovskite-type phases in the system La2Co1+z(MgxTi1−x)1−zO6

Perovskite-type cobaltates in the system La₂Co_1+z(Mg_xTi_1−x)_1−zO₆ were studied for z=0≤x≤0.6 and 0≤x<0.9, using X-ray and neutron powder diffraction, electron diffraction (ED), magnetic susceptibility measurements and X-ray absorption near-edge structure (XANES) spectroscopy. The samples were synthesised using the citrate route in air at 1350 °C. The space group symmetry of the structure changes from P2₁/n via Pbnm to R3¯c with both increasing Mg content and increasing Co content. The La₂Co(Mg_xTi_1−x)O₆ (z=0) compounds show anti-ferromagnetic couplings of the magnetic moments for the Co below 15 K for x=0, 0.1 and 0.2. XANES spectra show for the compositions 0≤x≤0.5 a linear decrease in the L₃/(L₃+L₂) Co-L_2,3 edge branching ratio with x, in agreement with a decrease of the average Co ion spin-state, from a high-spin to a lower-spin-state, with decreasing nominal Co²⁺ ion content.     

Structural Characterization of the Complex Perovskites Ba1−xLaxTi1−xCrxO3

The series Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤1) was synthesized at 1400°C for about 60 h. Their structure was carefully analyzed by the use of powder X-ray diffraction and Rietveld analysis software GSAS (General Structure Analysis System). Four solid solutions are found in this series: tetragonal solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0≤x≤0.029), cubic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.0365≤x≤0.600), rhombohedral solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.700≤x≤0.873), and orthorhombic solid solution Ba_1−xLa_xTi_1−xCr_xO₃ (0.956≤x≤1). There are corresponding two-phase regions between the adjacent two solid solutions. The detailed lattice parameters are presented. The relationship between the lattice parameters and the composition of the solid solutions is developed.     

Structural, magnetic, and electrochemical studies on lithium insertion materials LiNi1−xCoxO2 with 0≤x≤0.25

The structural, magnetic, and electrochemical properties of the LiNi_1−xCo_xO₂ samples with x= 0, 0.05, 0.1, and 0.25 have been investigated by powder X-ray diffraction analyses, magnetic susceptibility (χ) measurements, and electrochemical charge and discharge test in non-aqueous lithium cell. According to the structural analyses using a Rietveld method, the occupancy of the Ni ions in the Li layer was estimated to be below 0.01 for all the samples and was eventually independent of x. The temperature (T) dependence of χ⁻¹ obtained with the magnetic field H=10 kOe indicated that all the samples are a Curie-Weiss paramagnet down to . At low T, all the samples entered into a spin-glass-like phase below T_f. The magnitude of T_f was found to decrease almost linearly with x, as in the case for the x dependences of the lattice parameters of a_h- and c_h-axes, Weiss temperature, and effective magnetic moment. It is, therefore, found that the change of the magnetic properties with x is simply explained by a dilution effect due to the increase of the quantity of Co³⁺ ions. On the other hand, the electrochemical measurements demonstrated that the irreversible capacity at the initial cycle is drastically decreased by the small amount of Co ions. Furthermore, the discharge capacity (Q_dis) for the x=0.05 and 0.1 samples are larger than that for the x=0 sample; namely, Q_dis=180 mAh g⁻¹ for x=0, Q_dis=217 mAh g⁻¹ for x=0.05, and Q_dis=206 mAh g⁻¹ for x=0.1. Comparing with the past results, the amount of Ni ions in the Li layer is found to play a significant role for determining the magnetic and electrochemical properties of LiNi_1−xCo_xO₂.     

LaxSr1−xRuO3: A new perovskite series

The compound LaRuO₃ was prepared for the first time. It appears to be metallic and antiferromagnetic. Solid solutions with ferromagnetic SrRuO₃ of the type La_xSr_1−xRuO₃ exist for all values of x. All compounds have the orthorhombic GdFeO₃-type perovskite structure. The ferromagnetism observed for SrRuO₃ (x = 0) diminishes rapidly with increasing La content, and antiferromagnetism or parasitic ferromagnetism sets in at approximately 35% La. All compounds show Curie-Weiss behavior at fairly low temperatures. The properties of LaRhO₃ are also discussed.     

Magnetic properties of FexV3−xS4 (0 ≤ x ≤ 2)

The magnetic susceptibility data of Fe_xV_3?xS₄ (0 ≤ x ≤ 2) are reported in the temperature range between 4.2 and 1300 K. The behavior of the susceptibility at high temperatures changes significantly at the composition boundary x = 1.0. The magnitude of the effective magnetic moment remains unchanged at 3.2 μ_B in the composition range x < 1.0. It decreases with increasing iron content in the range > 1.0, and rapidly decreases for x close to 2.0. The c lattice parameter varies in a manner analogous to the change in magnetic moment. These phenomena suggest that metallic bonding forms between metal layers and that it becomes stronger with increasing in x. The susceptibility measurements at low temperatures show that Fe_xV_3?xS₄ is basically antiferromagnetic, although some of the Fe_xV_3?xS₄ compounds become weakly ferromagnetic after cooling in a magnetic field. The origin of the weak ferromagnetism is briefly discussed.     

Correlation between structure and magnetic properties of Cd-substituted La0.7(Ca0.3−xCdx)MnO3 CMR manganites

Structural, electrical and magnetic properties of Cd-doped La_0.7(Ca_0.3−xCd_x)MnO₃ (0?x?0.3) manganites are presented. All compositions were indexed in the orthorhombic (Pnma) space group, except the Cd_0.3 sample, indexed as a combination of trigonal and orthorhombic (Pnma) space groups. Substitution of Ca by Cd has a strong influence on the magnetic and magnetoresistive properties of these compounds, continuously decreasing both the magnetic moment and the Curie temperature (from 3.5 μ_B and 270 K for the x=0 composition to 1.59 μ_B and 90 K for the fully doped x=0.3 one). Samples corresponding to x=0 and 0.1 show a semiconductor-metal transition at temperatures close to the Curie ones. The measured magnetoresistance change is about 49% at 270 K and 95% at 165 K for those samples, respectively. However, the x=0.2 and 0.3 compositions show insulating behaviour in the whole temperature range studied, with values of the magnetoresistance about 85% at 105 K and 74% at 90 K, respectively. The observed weakening of the double-exchange mechanism as the Cd doping level in these samples increases is discussed in terms of structural properties, cationic disorder and Mn³⁺/Mn⁴⁺content ratio.     

Neutron diffraction studies of RSn1+xGe1−x (R=Tb-Er) compounds

The magnetic structures of RSn_1+xGe_1−x (R=Tb, Dy, Ho and Er, x≈0.1) compounds have been determined by neutron diffraction studies on polycrystalline samples. The data recorded in a paramagnetic state confirmed the orthorhombic crystal structure described by the space group Cmcm. These compounds are antiferromagnets at low temperatures. The magnetic ordering in TbSn_1.12Ge_0.88 is sine-modulated described by the propagation vector k=(0.4257(2), 0, 0.5880(3)). Tb magnetic moment equals 9.0(1) μ_B at 1.62 K. It lies in the b-c plane and form an angle θ=17.4(2)° with the c-axis. This structure is stable up to the Nèel temperature equal to 31 K. The magnetic structures of RSn_1+xGe_1−x, where R are Dy, Ho and Er at low temperatures are described by the propagation vector k=(1/2, 1/2, 0) with the sequence (++−+) of magnetic moments in the crystal unit cell. In DySn_1.09Ge_0.91 and HoSn_1.1Ge_0.9 magnetic moments equal 7.25(15) and 8.60(6) μ_B at 1.55 K, respectively. The moments are parallel to the c-axis. For Ho-compound this ordering is stable up to T_N=10.7 K. For ErSn_1.08Ge_0.92, the Er magnetic moment equals 7.76(7) μ_B at T=1.5 K and it is parallel to the b-axis. At T_t=3.5 K it tunes into the modulated structure described by the k=(0.496(1), 0.446(4), 0). With the increase of temperature there is a slow decrease of k_x component and a quick decrease of k_y component. The Er magnetic moment is parallel to the b-axis up to 3.9 K while at 4 K and above it lies in the b-c plane and form an angle 48(3)° with the c-axis. In compounds with R=Tb, Ho and Er the magnetostriction effect at the Nèel temperature is observed.     

The effect of substitution on the thermo-physical properties of LaMnxV1−xO4−δ

LaMn_xV_1−xO_4−δ(0≤x≤1) samples were characterized using thermogravimetry, thermo-dilatometry, high-temperature X-ray diffraction (HTXRD) and temperature-programmed reduction techniques, with an objective to explore the role of substitution on their thermo-physical properties, which may have a direct bearing on their catalytic behavior. Even though the substituted compositions (x<0.8) were of a single phase, their reduction occurred in two steps, a lower temperature step corresponding to Mn⁴⁺→Mn³⁺/Mn²⁺ and another higher temperature one related to V⁵⁺→V³⁺. The dilatometric measurements gave similar values of linear thermal expansion coefficient (α₁) at temperatures up to 600 °C, both for LaVO₄ and substituted samples. A different behavior was, however, observed at higher temperatures, whereas thermal contraction was observed in case of LaVO₄ for measurements at temperatures above 700 °C, the value of α₁ remained almost constant in case of the substituted samples. Furthermore, the HTXRD data revealed expansion in cell volume for all temperatures up to 950 °C, irrespective of the substitution. These results therefore point to a higher degree of sintering in LaVO₄ as compared to Mn-doped samples on heating at temperatures above 700 °C. It is inferred that the resistance to sintering and the lowering of the reduction temperature are both responsible to the higher catalytic activity of the substituted samples and their compositional stability during the repeated cycles of reduction-reoxidation, as reported earlier [Appl. Catal. A 205 (2001) 295].     

Structure distortion and magnetism in double perovskites Ca2−xLaxFeReO6 (0≤x≤0.8)

The crystal structure and magnetism of Ca_2−xLa_xFeReO₆ (0≤x≤0.8) double perovskites have been investigated. The samples with low doping (x≤0.4) are found to crystallize with the monoclinic P2₁/n superstructure, while those in the high doping ones (x≥0.6) have orthorhombic Pbnm superstructure. With the increase of an La doping, the anti-site defects increases, giving rise to highly disordered samples at the Fe and Re positions. At the low doping region (x≤0.4), the compounds undergo a simultaneous structural and magnetic transition accompanying a slight increase of the Curie temperature. The increase of Curie temperature is discussed in terms of the structural change with doping.     

Crystal structure of Bi1−xTbxFeO3 from high-resolution neutron diffraction

Samples of Bi_1−xTb_xFeO₃, with x=0.05, 0.10, 0.15, 0.20 and 0.25, have been synthesised by solid state reaction. The crystal structures of the perovskite phases, characterised via Rietveld analysis of high resolution powder neutron diffraction data, reveal a structural transition from the R3c symmetry of the parent phase BiFeO₃ to orthorhombic Pnma symmetry, which is complete for x=0.20. The x=0.10 and 0.15 samples are bi-phasic. The transition from a rhombohedral to orthorhombic unit cell is suggested to be driven by the dilution of the stereochemistry of the Bi³⁺ lone pair at the A-site. The G-type antiferromagnetic spin structure, the size of the ordered magnetic moment (∼3.8 μ_B) and the T_N (∼375 °C) are relatively insensitive to increasing Tb concentrations at the A-site.     

Temperature and composition dependent structural investigation of the defect perovskite series Sr1−xTi1−2xNb2xO3, 0≤x≤0.2

The crystal structure of the defect perovskite series Sr_1−xTi_1−2xNb_2xO₃ has been investigated over a range of temperatures using high-resolution synchrotron X-ray diffraction, neutron diffraction and electron diffraction. Three distinct regions were observed: 0<x≤0.125 was a solid solution of Sr_1−xTi_1−2xNb_2xO₃ with minor SrTiO₃ intergrowth, 0.125<x≤0.2 was a pure Sr_1−xTi_1−2xNb_2xO₃ solid solution adopting the cubic perovskite type structure (Pm3¯m) and for x>0.2 Sr_0.8Ti_0.6Nb_0.4O₃ and Sr₃TiNb₄O₁₅ formed a two phase region. The cubic structure for Sr_0.8Ti_0.6Nb_0.4O₃ was stable over the temperature range 90-1248 K and the thermal expansion co-efficient was determined to be 8.72(9)×10⁻⁶ K⁻¹. Electron diffraction studies revealed diffuse scattering due to local scale Ti/Nb displacements and slightly enhanced octahedral rotations that did not lead to long range order. The octahedral rotations were observed to ‘lock-in’ at temperatures below ∼75 K resulting in a tetragonal structure (I4/mcm) with anti-phase octahedral tilting about the c-axis.     

Perovskite-type SrTi1−xNbx(O,N)3 compounds: Synthesis, crystal structure and optical properties

The synthesis, crystal structure, thermal stability and absorbance spectra of perovskite-type oxynitrides with the general formula SrTi_1−xNb_x(O,N)₃ (x=0.05, 0.10, 0.20, 0.50, 0.80, 0.90, 0.95) have been investigated. Oxide samples were prepared by a polymerized complex synthesis route and post-treated under ammonia at 850 °C for 24 h to substitute nitrogen for oxygen. Synchrotron X-ray powder diffraction (XRD) evidenced that the mixed oxide phases were all transformed into oxynitrides with perovskite-type structure during a thermal ammonolysis. SrTi_1−xNb_x(O,N)₃ with compositions x≤0.80 crystallized in a cubic and samples with x≥0.90 in a tetragonal structure. The Rietveld refinement indicated a continuous enlargement of the lattice parameters towards higher niobium content of the samples. Thermogravimetric analysis (TGA) and hotgas extraction revealed the dependence of the nitrogen incorporation upon the degree of niobium substitution. It showed that more nitrogen was detected in the samples with higher niobium content. Furthermore, TGA disclosed stability for all oxynitrides at T≤400 °C. Diffuse reflectance spectroscopy indicated a continuous decrease of the band gap’s width from 3.24 eV (SrTi_0.95Nb_0.05 (O,N)₃) to 1.82 eV (SrTi_0.05Nb_0.95(O,N)₃) caused by the increasing amount of nitrogen towards the latter composition.     

Structure, Stoichiometry, and Properties of the Chimney-Ladder Phases Ru2Ge3+x (0<x<1)

The preparation and physical characterization of non-stoichiometric Ru₂Ge_3+x (0≤x≤1) are reported for the first time. The defect TiSi₂-type chimney-ladder structure is maintained for the full stoichiometry range. The resistivity of Ru₂Ge_3+x increases systematically with x from 300 mΩ cm, x=0 -3 Ω cm, x=1 at 300 K. The temperature dependence is consistent with a variable range-hopping mechanism for x≥0.6. The Seebeck coefficients of samples do not evolve simply with x. A low thermal conductivity (κ_{300 K}=0.03 W/K cm) suggests that Ru₂Ge₃ has some of the properties of a phonon-glass-electron-crystal. The low value of the thermoelectric figure of merit ZT=3.2×10⁻³ (T=300 K) calculated for Ru₂Ge₃ is due primarily to a low conductivity.     

Magnetic properties related to structure and complete composition analyses of nanocrystalline La1−xMn1−yO3 powders

Structural and magnetic properties were studied on La_1−xMnO_3±δ nanocrystalline powders exhibiting different La/Mn ratios. These compounds were prepared using a gel combustion method based on a cation solution soaking by acrylamide polymerization. Structural properties were studied both by transmission electron microscopy and X-ray diffraction (XRD). Complete chemical composition analyses were performed by induced coupled plasma spectroscopy and by iodometric titration. Proportions of parasitic phases in samples, as La₂O₃ or Mn₃O₄, and actual compositions of La_1−xMnO_3±δ phases were then determined from refinements of XRD data and sample chemical compositions. As a result, perovskite structure is not any more stable for La/Mn<0.9 as it decomposes into a mixing of La_0.9MnO₃ and of Mn₃O₄ phases, in agreement with results on thermodynamic equilibrium in the La-Mn-O phase diagram. For La/Mn>0.9, a high oxygen excess is observed and leads to consider the creation of vacancies on both lanthanum and manganese sites, whose concentrations are evaluated. Magnetic properties agree well with the proposed structures and sample compositions since for La/Mn<0.9, for which a La_0.9MnO₃ phase is always found, the Curie temperature remains constant and equal to 295 K (the highest temperature never observed before in such series of compositions), while for La/Mn>0.9, there is a formation of Mn vacancies giving rise to a lowering of Curie temperature resulting of a frustration of ferromagnetic interactions.     

Magnetic properties of the chemically delithiated LixMn2O4 with 0.07≤x≤1

Magnetism for the Li_xMn₂O₄ samples with 0.07≤x≤1, which are prepared by a chemical reaction in HNO₃ solution, is investigated by direct current susceptibility (χ) and muon-spin rotation/relaxation (μSR) measurements. The effective magnetic moment (μ_eff) of Mn ions decreases monotonically with decreasing x, indicating that Mn³⁺ ions with S=2 () are oxidized to Mn⁴⁺ ions with S=3/2 () with decreasing x. On the other hand, as x decreases from 1 to 0.6, the Curie-Weiss temperature (Θ_p) increases monotonically from ∼−260 to −100 K, and then levels off to −100 K with further decreasing x. This indicates that the antiferromagnetic interaction is dominant in the whole x range. For the x=0.48 sample, the temperature dependence of χ in field-cooling mode clearly deviates from that in zero-field-cooling mode below ∼63 K (=T_m). Furthermore, the hysteresis loop is observed in the magnetization vs. field curve at 5 K. Since the zero-field μSR spectrum is well fitted by a strongly damped oscillation function, the Mn moments for the x=0.48 sample are in a highly disordered fashion down to the lowest temperature measured.     

Lattice crossover and mixed valency in the LaCo1−xRhxO3 solid solution

The full LaCo_1−xRh_xO₃ solid solution was investigated utilizing structural, electrical transport, magnetic, and thermal conductivity characterization. Strong evidence for at least some conversion of Rh³⁺/Co³⁺ to Rh⁴⁺/Co²⁺ is found in both structural and electrical transport data. The crystal structure is that of a rhombohedrally distorted perovskite over the range 0.0≤x≤0.1. The common orthorhombic distortion of the perovskite structure is found over the range 0.2≤x≤1.0. A crossover of all three orthorhombic cell edges occurs at x=0.5 giving the appearance of a cubic structure, which actually remains orthorhombic. The octahedra in the orthorhombic structure must be distorted for x values less than 0.5, and the observed distortion suggests orbital ordering for Co²⁺. Electrical resistivity measurements as a function of temperature show semiconducting-like regions for all compositions. There is a steady increase in electrical resistivity as the Rh content increases. Large positive thermopower values are generally obtained above 475 K. With increasing Rh substitution there is a decrease in thermal conductivity, which slowly rises with increasing temperature due to increased electrical conductivity. The electronic part of the thermal conductivity is suppressed significantly upon Rh substitution. A thermoelectric figure-of-merit (ZT) of about 0.075 has been achieved for LaCo_0.5Rh_0.5O₃ at 775 K, and is expected to reach 0.15 at 1000 K.