Structural, electrical and magnetic characterization of the double perovskites Sr2CrMO6 (M=Mo, W): B′ 4d-5d system

We report on the preparation and characterization of the variation of B′-site transition metal in Sr₂CrMO₆ (M=Mo, W) with double perovskites structure. The magnetic susceptibility shows that Sr₂CrMoO₆ and Sr₂CrWO₆ are antiferromagnets with T_N=40 and 30 K at H=1 T, respectively. In addition, a large magnetoresistance ratio (MR) of ∼38% (H=3 T) at 5 K was observed in the Sr₂CrWO₆ compound. However, the Sr₂CrMoO₆ compound does not show any significant MR even at high fields (MR∼4%; H=3 T and 5 K). The measured O K-edge X-ray absorption is in agreement with the calculated O p-density of states for both compounds.     

Enhancement of Curie temperature and room-temperature magnetoresistance in double perovskite (Sr1.6Ba0.4)FeMoO6

The effects of A-site average cation size 〈r_A〉 and anti-site defects on Curie temperature (T_C) and room-temperature magnetoresistance (MR) in (Sr_2−xBa_x)FeMoO₆ (x=0, 0.4 and 1.6) have been investigated. By Ba doping, not only the room-temperature MR but also the T_C have been enhanced. The larger MR in the Ba-doped samples compared with the prototype Sr₂FeMoO₆ is associated with the lower saturation field. The optimization of T_C and MR in (Sr_1.6Ba_0.4)FeMoO₆ other than in the reported (Sr_0.4Ba_1.6)FeMoO₆ can be understood according to the two competing effects: anti-site defects and chemical pressure.     

Synthesis,magnetic and electrical transport properties of magnetoresistance material Sr2FeMoO6 by microwave sintering

Magnetoresistance material Sr₂FeMoO₆ with double perovskite structure was synthesized by microwave sintering method using SrCO₃, Fe₂O₃ and MoO₃ as raw materials, with MnO₂ for microwave absorber. The phase structure, magnetic and electrical transport properties were investigated by X-ray powder diffraction (XRD) and vibrating-sample magnetometer. XRD analysis shows that the as-synthesized sample is Sr₂FeMoO₆ with tetragonal crystal structure and I4/mmm space group. The unit cell parameters are a=0.5587 nm, c=0.7894 nm, volume=0.2464 nm³. The calculated grain size of the sample is 31.62 nm, which is obtained by the Scherrer formula using the diffraction data. Magnetism testing results show that the sample Sr₂FeMoO₆ is ferromagnetic with the magnetic transition temperature of about 380 K. Under 1.0 T magnetic field, the saturation and spontaneous magnetization of Sr₂FeMoO₆ is 1.25 μ_B/f.u. and 1.00 μ_B/f.u. at room temperature. The magnetoresistance ratio of the sample is 28%. Electrical transport properties testing results indicate that the sample exhibits typical semiconductor behavior. The conductive mechanism of Sr₂FeMoO₆ is highly dependent on temperature: within the temperature range of 100–300 K, the mechanism is attributed to the small polaron variable-range hopping model; while it is ascribed to the adiabatic small polaron model within the temperature range of 80–100 K.     

Magnetic and magneto-transport properties of double perovskite Ba2−xSrxFeMoO6 system

The structural magnetic and magneto-transport properties of double perovskite system Ba_2−xSr_xFeMoO₆ (0?x?1.0) prepared in bulk polycrystalline form are reported in this paper. X-ray diffraction analysis showed that samples are single phase and the lattice constants decreases with increase in the Sr content. The degree of Fe-Mo ordering has been found decreasing in the series with an increase in the Sr content. Parent compound Ba₂FeMoO₆ exhibits saturation magnetic moment value of 3.54 μ_B/f.u. at 85 K in a magnetic field of 6000 Oe. Temperature dependence of resistivity shows metallic behavior for all the samples. The magneto-resistance (MR) of the compound with x=0.4 is higher than that of the other samples. At room temperature this system shows a saturation magnetization value of 1.73 μ_B/f.u. and MR value of 7.08% (1 T). The observed variations in the structural and magnetic properties are attributed to the change of chemical pressure due to the substitution of Sr in place of Ba. The effect of antisite disorder (ASD) defects on magneto-transport properties is studied in more detail.     

Determination of antisite defects in double perovskite Sr2FeMoO6 by diffraction method: Simulation studies

The crystal structure of double perovskite Sr₂FeMoO₆ synthesized via solid-state reaction at 1280 °C under a reduction atmosphere is refined by Rietveld technique based on X-ray powder diffraction (XRD) data in 2θ range of 15-140°. An antisite content (AS), i.e. Fe on the Mo sites (=Mo on the Fe sites), of 12.1(1)% is derived. In reference to the refinement results, a series of X-ray and neutron powder diffraction (NPD) data with different antisite contents, ranging from 0 (completely ordered) to 50% (completely disordered), are generated with a Poisonian noise added and subjected to Rietveld refinements with the same initial values for the refinable parameters. The AS is reproduced satisfactorily from the refinement of XRD data and the combined refinement of XRD and NPD data with a relative deviation smaller than 4%, whereas the relative deviation of AS derived from the refinement of NPD data can be as large as 50%. However, the atomic occupancies and isotropic temperature factors of all the atoms can be reasonably reproduced from the refinement of NPD data and the combined refinement of XRD and NPD data, whereas these data can be reproduced only for cations (Sr, Fe, Mo) from the refinement of XRD data. The present simulation studies shed light on understanding the controversial statements derived from XRD and NPD work regarding the antisite defects in Sr₂FeMoO₆, which in turn is indispensable for understanding the mechanism of large room temperature low-field magnetoresistance of the compound.     

The structure and magnetotransport properties of La2/3Sr1/3MnO3/Ba(La)TiO3 composites

The effect of Ba(La)TiO₃ doping on the structure and magnetotransport properties of La_2/3Sr_1/3MnO₃(LSMO)/xBa(La)TiO₃ (x=0.0, 1.0, 5.0 mol%) have been investigated. The X-ray diffraction patterns and microstructural analysis show that BaTiO₃ and LSMO phases exist independently in BaTiO₃-doped composites. The metal-insulator transition temperature (T_MI) decreases whereas the maximum resistivity increases very quickly by the increase of BaTiO₃ doping level. The partial substitution of Ba by La(0.35 mol%) results in a decrease in resistivity of LSMO/xBa(La)TiO₃ composites. Magnetoresistance of BaTiO₃-doped composites decreases monotonously in the temperature range 200-400 K in a magnetic field of 5 T, which is completely different from that of LSMO compound. The value of MR decreases at low field (H<1 T) and increases at high fields (H>1 T) with increasing the BaTiO₃ doping level at low temperatures below 280 K. These investigations reveal that the magnetotransport properties of LSMO/xBa(La)TiO₃ composites are dominated by spin-dependent scattering and tunneling effect at the LSMO/BaTiO₃/LSMO magnetic tunnel junction.     

Crystallographic and magnetic structures of Y0.8Sr2.2Mn2GaO8−δ: a new vacancy-ordered perovskite structure

The anion-deficient perovskite Y_0.8Sr_2.2Mn₂GaO_8−δ (where δ∼0.1) has been synthesised and the crystal and magnetic structures determined by Rietveld analysis of neutron powder diffraction (NPD) data. The material has body-centred tetragonal symmetry (I4/mmm, a=7.6373(3) Å and c=15.6636(10) Å) and consists of alternating layers of octahedral and tetrahedral polyhedra, the layers being perpendicular to [001]. The octahedral layers are preferentially occupied by manganese and the tetrahedral layers are a mixture of manganese and gallium. The precise cation distribution depends critically on preparative conditions. An unusual structural feature of these materials is the arrangement of oxygen vacancies in the tetrahedral layers: in the basic structure, isolated squares of corner-linked tetrahedra are formed instead of the chains that are observed in brownmillerite phases. Additional oxide ions in this layer probably allow the Mn ions to achieve distorted square pyramidal coordination. Low temperature NPD and magnetisation data indicate antiferromagnetic ordering below 100 K.     

Magnetoresistive properties of Zn1−xCoxFe2O4 ferrites

The magnetic and magnetoresistive properties of spinel-type Zn_1−xCo_xFe₂O₄ (x=0, 0.2 and 0.4) ferrites are extensively investigated in this study. A large negative magnetoresistance (MR) effect is observed in Zn_1−xCo_xFe₂O₄ ferrites of spinel structure. These materials are either ferrimagnetic or paramagnetic at room temperature, and show a spin-(cluster) glass transition at low temperatures, depending on the chemical compositions. The MR curves as a function of magnetic fields, MR(H), are parabolic at all temperatures for paramagnetic polycrystalline ZnFe₂O₄. The MR for ZnFe₂O₄ at 110 K in the presence of 9 T applied magnetic field is 30%. On the other hand, MR(H) are linear for x=0.2 and 0.4 ferrimagnetic Zn_1−xCo_xFe₂O₄ samples up to 9 T. The MR effect is independent of the sintering temperatures, and can be explained with the help of the spin-dependent scattering and the Yafet–Kittel angle of Zn_1−xCo_xFe₂O₄ mixed ferrites.     

Ferromagnetism and metallicity in the modulated Sr1−xThxCoO3−δ oxygen deficient perovskites with x∼0.1

The Th⁴⁺ for Sr²⁺ substitution in SrCoO_3−δ is found to be an efficient way to stabilize an oxygen deficient perovskite. The structural study reveals a Th⁴⁺ solubility limited to ∼10% so that the chemical formula, Sr_0.9Th_0.1CoO_2.79, is obtained. The comparison to the Y³⁺ for Sr²⁺ substitution shows that a lower oxygen content is obtained for the former according to the Sr_0.75Y_0.25CoO_2.55 formula. The higher oxygen content reached with Th⁴⁺ has a strong impact on the physical properties: Sr_0.9Th_0.1CoO_2.79 is an itinerant ferromagnet (T_C∼200 K, ρ_5 K=2 mΩ cm) whereas Sr_0.75Y_0.25CoO_2.55 is a robust insulating antiferromagnet (T_N∼320 K, ρ_5 K=10⁵ Ω cm). Clearly, the substitution of a tetravalent cation for Sr²⁺ appears to be a promising route to synthesize SrCoO_3−δ itinerant ferromagnets without the use of high oxygen pressure nor electrochemical oxidation.     

Large magnetoresistance in low temperature metallic region of manganite compounds (La0.7−2xEux)(Ca0.3Srx)MnO3 (0.05≤x≤0.15)

Magnetoresistance (MR) and magnetization (dc and ac) measurements have been carried out on the manganites, (La_0.7−2xEu_x)(Ca_0.3Sr_x)MnO₃ (0.05≤x≤0.15), in the temperature range of 5-320 K. At 5 K, an unusually large MR of almost 98% is observed in the x=0.15 sample, nearly up to fields of 4-5 T. This large high-field MR occurs in the metallic region, far below the insulator-metal transition temperature, and does not vary linearly with applied field. The unusual magnetoresistance is explained in the light of various possibilities such as phase segregation, cluster spin-glass behavior, etc.     

Influence of V substitution for Fe on the transport and magnetic properties of Sr2FeMoO6

We have investigated the crystal structure, magnetization and magnetoresistance of the double perovskite compounds Sr₂(Fe_1−xV_x)MoO₆ (0≤x≤0.1). The lattice constants and the cation ordering decrease monotonously with the V content. The Curie temperature, saturation magnetization and low field magnetoresistance of the compounds decrease with increasing x due to the reduced degree of ordering. The resistivity of Sr₂FeMoO₆ and lightly doped samples shows semiconductive behavior, while the samples with higher doping levels exhibit a semiconductor-metal transition around 80 K.     

Structural and magnetic properties of SmCo7−xMox alloys

Phase structure and magnetic properties of the as-cast and as-milled/annealed SmCo_7−xMo_x (x=0, 0.1, 0.2, 0.3, 0.4) alloys have been systematically studied. It is found that all the as-cast series alloys are composed of the CaCu₅-type and Th₂Zn₁₇-type phases. Saturation magnetization of the samples decreases with the Mo content increasing. Intrinsic coercivities (_iH_c) of no more than 0.06 T are observed in these as-cast samples, due to their rather coarse grain microstructures with an average grain size of 50 μm. The as-milled/annealed SmCo_7−xMo_x powders crystallize in the disordered TbCu₇-type (1:7) structure with very fine nanograins, and a minor Co₃Mo phase appears in the samples with x=0.1-0.4. High _iH_c (?0.95 T) are achieved in these samples, with a maximum of 1.26 T located at x=0.2, which can be primarily attributed to strong pinning of the domain wall motion at the nanograin boundaries. The temperature coefficient (β) of the _iH_c is about −0.22%/°C in the temperature range of 25-400 °C for the as-milled/annealed samples.     

Magnetocaloric properties in the Cr-doped La0.7Sr0.3MnO3 manganites

Single-phase polycrystalline samples of La_0.7Sr_0.3Mn_1-xCr_xO₃ with nominal composition of x=0.00, 0.20, 0.40 and 0.50 were prepared by a conventional solid-state reaction method in air. Investigations of magnetization were carried out in the temperature range 5-400 K and magnetic field range 0-8 T. It was found that the Curie temperature T_C decreases with increasing x and the maximum magnetic entropy change (−ΔS_M) for x=0.20 is ∼1.203 and ∼2.653 J/kg K, respectively for 2 and 6 T magnetic field near the temperature of 280 K.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

Thermal diffusivity of double perovskite Sr2MMoO6 (M=Fe, Mn and Co) and La doping effects studied by mirage effect

The thermal diffusivity has been investigated in double perovskite Sr₂MMoO₆ (M=Fe, Mn and Co) by means of the mirage effect. We have found that the thermal diffusivity of metallic Sr₂FeMoO₆ is 0.39 cm²/s, which is larger than that (0.33 cm²/s) of insulating Sr₂MnMoO₆ and Sr₂CoMoO₆. We further investigate the substitution effects of the La³⁺ ions for the Sr²⁺ ions in Sr₂FeMoO₆ and Sr₂MnMoO₆, and have found that the thermal diffusivities of both samples significantly increase with the La concentration. Such an enhancement of the thermal diffusivities has been ascribed to occupation of the extra itinerant electrons on the conduction Mo4d band.     

Infrared absorption and reflectivity of double perovskite Sr2FeWO6

In this work we present temperature dependent infrared reflectivity and absorption of Sr₂FeWO₆ between 700 and 17 K measured from 40 to 10000 cm⁻¹. The reflectivity spectra show well defined phonon bands peaking at 143, 227, 377 and 625 cm⁻¹ assigned to overlapping vibrational modes split from those active in cubic perovskite. We have also verified that this compound is structurally stable in the whole temperature range and that its optical gap at ∼750 cm⁻¹ (95 meV) undergoes only a minor high temperature decrease ascribed to new thermally accessible levels.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Hall effect in a GdBa2Cu3O7−δ/La0.75Sr0.25MnO3 perovskite bilayer

We present results on the Hall coefficient R_H in the normal state for a GdBa₂Cu₃O_7−δ/La_0.75Sr_0.25MnO₃ bilayer and a La_0.75Sr_0.25MnO₃ film grown by dc magnetron sputtering on (1 0 0) SrTiO₃. We find that the electric transport on the bilayer can be qualitatively described using a simple parallel layers model. The GdBa₂Cu₃O_7−δ layer presents a carrier density approximately equal to that reported for 7 − δ = 6.85 oxygen doping. Also we observe an unexpected presence of two Hall resistivity regimes, effects that may be associated with the internal magnetic field induced on the superconducting layer by the ferromagnetic layer.     

Effect of pressure and magnetic field on bilayer La1.25Sr1.75Mn2O7 single crystal

We report the temperature dependence of susceptibility for various pressures, magnetic fields and constant magnetic field of 5 T with various pressures on La_2−2xSr_1+2xMn₂O₇ single crystal to understand the effectiveness of pressure and magnetic field in altering the magnetic properties. We find that the Curie temperature, T_c, increases under pressure (dT_c/dP=10.9 K/GPa) and it indicates the enhancement of ferromagnetic phase under pressure up to 2 GPa. The magnetic field dependence of T_c is about 26 K for 3 T. The combined effect of pressure and constant magnetic field (5 T) shows dT_c/dP=11.3 K/GPa and the peak structure is suppressed and broadened. The application of magnetic field of 5 T realizes 3D spin ordered state below T_c at atmospheric pressure. Both peak structure in χ_c and 3D spin ordered state are suppressed, and changes to 2D-like spin ordered state by increase of pressure. These results reveal that the pressure and the magnetic field are more competitive in altering the magnetic properties of bilayer manganite La_1.25Sr_1.75Mn₂O₇ single crystal.     

Possible anisotropy gap in La1.35Sr1.65Mn2O7 and La1.5Sr0.5NiO4 detected through specific heat and magnetization measurements

Magnetization and specific heat measurements, as a function of temperature, were performed on single crystals of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄, under different applied magnetic fields (H). The specific heat in La_1.35Sr_1.65Mn₂O₇ was decreased for H=9 T parallel to the crystal c axis, compared with H=0, possibly due to a suppression of spin-wave excitations (magnons) in that ferromagnetic bilayer structure. On the other hand, the applied magnetic field had no effect in the specific heat of the antiferromagnetic La_1.5Sr_0.5NiO₄. For H=9 T and below the temperature of 4 K the specific heat data, for each crystal, was well fitted by an exponential decay law. This allowed the calculation of energy gaps around 1 meV for both compounds, in close agreement with Δ=2μ_BH for an expected energy gap in the magnon spectrum. Detailed magnetization measurements showed monotonic variations below 4 K and a steep increase close to 2 K. Both magnetization and specific heat measurements suggest the existence of an anisotropy gap in the energy spectrum of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄.