Structure and magnetocaloric properties of La1−xKxMnO3 manganites

A technology of obtaining the single-phase ceramic samples of La_1−xK_xMnO₃ manganites and the dependence of their structural parameters on the content of potassium has been described. Magnetocaloric effect (MCE) in the obtained samples has been measured by two independent methods: classical direct methodic and a method of magnetic field modulation. The values of MCE obtained by both methods substantially differ. The explanation of the observed divergences is given. The correlation between the level of doping and MCE value has been defined. The value of T_C determined by the MCE maximum conforms with the literature data obtained by other methods.     

Electrical and magnetic properties of non-stoichiometric (La0.8Sr0.2)1−xMnO3 perovskites

The structure, transport and magnetic properties of (La_0.8Sr_0.2)_1−xMnO₃ (0≤x≤0.30) polycrystalline perovskite manganites have been investigated. For all the samples the Curie temperatures, T_c, remain nearly unchanged (329±3 K). Resistivity versus temperature curves for the samples show a double-peak behavior. A significant magnetoresistance (MR) effect and different temperature dependences of the MR ratios of the samples are observed. The shapes of the MR-T curves of the samples can be adjusted by changing x. For the x=0.30 sample, a nearly constant MR ratio of (9.5±0.5)% is obtained over the temperature range from 205 to 328 K.     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Spray-pyrolysis deposition of LaMnO3 and La1−xCaxMnO3 thin films

Ethylene glycol solutions of La-Mn(II) and La-Ca-Mn(II) citric complexes has been used as a starting material for spray-pyrolysis deposition of LaMnO₃ and La_1−xCa_xMnO₃ thin films on β-quartz, fused quartz, Si(0 0 1) and SrTiO₃(1 0 0) substrates heated during the deposition at 380 °C. At suitable post-deposition heating conditions highly uniform films, 0.1-1 μm in thickness, with good crystal structure were obtained. Highly textured LaMnO₃ films are obtained on SrTiO₃(1 0 0) substrate. Interaction between the layer and Si-containing substrates is observed during the post-deposition heating in static air.     

Magnetic properties and Griffiths singularity in La0.45Sr0.55 Mn1−xCoxO3

The magnetic properties and the Griffiths singularity were investigated in Mn-site doped manganites of La_0.45Sr_0.55Mn_1−xCo_xO₃ (x=0, 0.05, 0.10 and 0.15) in this work. The parent sample La_0.45Sr_0.55MnO₃ undergoes a paramagnetic-ferromagnetic transition at T_C=290 K and a ferromagnetic-antiferromagnetic transition at T_N=191 K. The doping of Co ions enhances the ferromagnetism and suppresses the antiferromagnetism. The enhanced ferromagnetism results from the fact that the Co doping enhances the Mn³⁺-Mn⁴⁺ double-exchange interaction and induces the Co²⁺-Mn⁴⁺ ferromagnetic superexchange interaction. Detailed investigation on the magnetic behavior above T_C exhibits that the Griffiths singularity takes place in this series of Mn-site doped compounds. The correlated disorder induced by the Co ionic doping, together with the phase competition from the ferromagnetic and the antiferromagnetic interactions among Mn ions, is responsible for the Griffiths singularity.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Atomistic computer simulation studies of La1−xSrxVO3

Static computer simulation techniques have been employed for structural investigation of the La_1−xSr_xVO₃ series. Potential parameters for V³⁺-O²⁻ and V⁴⁺-O²⁻ have been derived which reproduces the crystal structures of end members with sufficient accuracy. Variations of lattice parameters and bond distances with Sr concentration have been studied. The calculated lattice parameters decrease with increase in the Sr concentration. A structural phase transition from orthorhombic to cubic is observed at 50% Sr doping level.     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Structure, transport and magnetic properties in La2xSr2−2xCo2xRu2−2xO6

The perovskite solid solutions of the type La_2xSr_2−2xCo_2xRu_2−2xO₆ with 0.25≤x≤0.75 have been investigated for their structural, magnetic and transport properties. All the compounds crystallize in double perovskite structure. The magnetization measurements indicate a complex magnetic ground state with strong competition between ferromagnetic and antiferromagnetic interactions. Resistivity of the compounds is in confirmation with hopping conduction behaviour though differences are noted especially for x=0.4 and 0.6. Most importantly, low field (50 Oe) magnetization measurements display negative magnetization during the zero field cooled cycle. X-ray photoelectron spectroscopy measurements indicate the presence of Co²⁺/Co³⁺ and Ru⁴⁺/Ru⁵⁺ redox couples in all compositions except x=0.5. Presence of magnetic ions like Ru⁴⁺ and Co³⁺ gives rise to additional ferromagnetic (Ru-rich) and antiferromagnetic sublattices and also explains the observed negative magnetization.     

Structure and magnetic properties of Sn1−xMnxO2

The microstructure and magnetic properties have been investigated systematically for Sn_1−xMn_xO₂ polycrystalline powder samples with x=0.02-0.08 synthesized by a solid-state reaction method. X-ray diffraction revealed that all samples are pure rutile-type tetragonal phase and the cell parameters a and c decrease monotonously with the increase in Mn content, which indicated that Mn ions substitute into the lattice of SnO₂. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism. Furthermore, magnetic investigations demonstrate that magnetic properties strongly depend on doping content, x. The average magnetic moment per Mn atom decreases with increase in the Mn content, because antiferromagnetic super-exchange interaction takes place within the neighbor Mn³⁺ ions through O²⁻ ions for the samples with higher Mn doping. Our results indicate that the ferromagnetic property is intrinsic to the SnO₂ system and is not a result of any secondary magnetic phase or cluster formation.     

Lanthanum deficiency effect in magnetic transition and transport property of La0.8−δCa0.2MnO3

The evolution of magnetic and electrical phases in La_0.8−δCa_0.2MnO₃ was investigated in terms of La deficiency. We found that the increase of the La deficiency tends to raise the Curie temperature (T_C) in La_0.8−δCa_0.2MnO₃. The FM clusters formed in compounds with large La deficiency provide percolation paths above T_C. With increasing the La defect, the transport property changes from insulating to metallic state, which is in association with the crossover from a second order to a first order magnetic phase transition in the vicinity of T_C.     

The correlation between structure and magnetic properties in the manganites La0.7Ca0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Ca_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show an orthorhombic structure (O′-Pbnm) at room temperature. It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase in the Te content. All samples exhibit an insulator-metal (I-M) transition and the resistivity increases with the increase in the Te-doping level. Additionally, the Curie temperature T_c decreases and the transition becomes broader with increasing Te-doping level, in contrast, the magnetization of Te-doping samples at low temperatures decrease with increasing x as x≤0.10 and then increase with further increasing x to 0.15. The results are discussed in terms of Jahn-Teller (JT) vibrational anisotropy Q₃/Q₂ and the opening of the new DE channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ ions for Ca²⁺ ions.     

Enhanced ferroelectric, magnetic and magnetoelectric properties of Bi1−xCaxFe1−xTixO3 solid solutions

We report on the enhanced electromechanical, magnetic and magnetoelectric properties of Bi_1−xCa_xFe_1−xTi_xO₃ solid solutions. The crystal structure of the x≈0.25 compounds are close to the rhombohedral-orthorhombic phase boundary, and the solid solutions are characterized by increased electromechanical properties due to the polarization extension near the polar-nonpolar border. The homogenous weakly ferromagnetic state is established at x>0.15 doping. The chemical doping shifts the magnetic transition close to room temperature, thus enlarging the magnetic susceptibility of the compounds. The solid solutions at the morphotropic phase boundary exhibit a nearly twofold increase in piezoelectric response, whereas the magnetoelectric coupling shows five times enhancement in comparison with the parent bismuth ferrite.     

Structural, magnetic and transport properties in the manganites La0.7Sr0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Sr_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show a rhombohedral structure with the space group . It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase of Te content. The Curie temperature T_C decreases with increasing Te-doping level, in contrast, the magnetization magnitude of Te-doping samples at low temperatures increase with increasing x as x≤0.05 and then decrease with further increasing x to 0.15. The results are discussed in terms of the combined effects of the opening of the new double exchange (DE) channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ for Sr²⁺ and the reduction of the transfer integral b due to the decrease of the Mn-O-Mn bond angle.     

Superconducting properties of SmFeAsO1−x prepared under high-pressure condition

Synthetic conditions such as stoichiometries, temperature and pressure are optimized to achieve a high quality oxygen deficient SmFeAsO_0.6 superconductor. Both electric and magnetic measurements show a sharp superconducting transition at about 55 K. Several important physical parameters are deduced. The apparent superconducting gap observed in heat capacity with 2Δ_o/k_BT_c of 4.57 larger than that of previous fluorine replaced samples indicate that this superconductivity will not strongly conflict with the phonon-mediated BCS mechanism. The mean free length ?=18.8 nm and the coherent length ξ=2.3-3.3 nm show that the superconductivity is in the clean limit.     

Electronic transport and magnetic studies of La1−xCax−0.08Sr0.04Ba0.04MnO3

Lanthanum based mixed valence manganite system La_1−xCa_x−0.08Sr_0.04Ba_0.04MnO₃ (LCSBMO; x=0.15, 0.24 and 0.33) synthesized through the sol-gel route is systematically investigated in this paper. The electronic transport and magnetic susceptibility properties are analyzed and compared, apart from the study of unit cell structure, microstructure and composition. Second order phase transition is observed in all the samples and significant difference is observed between the insulator to metal transition temperature (T_MI) and paramagnetic (PM) to ferromagnetic (FM) transition temperature (T_C). In contrast to the insulating FM behaviour usually observed in La_1−xCa_xMnO₃ (LCMO) for x=0.15, a clear insulator to metal transition is observed for LCSBMO for the same percentage of lanthanum. The temperature dependent resistivity of polycrystalline pellets, when obeying the well studied law ρ=ρ_o+ρ₂T² for T<T_MI, is observed to differ significantly in the values of ρ_o and ρ₂, with the electrical conductivity increasing with x. The variable range hopping model has been found to fit resistivity data better than the small polaron model for T>T_MI. AC magnetic susceptibility study of the polycrystalline powders of the manganite system shows the highest PM to FM transition of 285 K for x=0.33.     

Structure and magnetic properties of perovskite Sr2CuNbO6−δ

Single phase perovskite Sr₂CuNbO_6−δ with a high proportion of Cu¹⁺ ions and oxygen vacancies was synthesized by solid-state reaction. The structure was determined by Rietveld method with space group Pm3m. Isotropic g value was evaluated from electron spin resonance (ESR) measurements. The ESR result is consistent with that of magnetic susceptibility.     

Density functional calculation of effective Coulomb interaction in La1−xCaxMnO3

The electronic structures of perovskite oxides La_2/3Sr_1/3MnO₃ are studied with density functional methods. Our calculations indicated that the strong electron correlation, which has evident influence on the split of Mn 3d-orbitals and the forming of double exchange, is very important to get the correct densities of states (DOS) of La_2/3Sr_1/3MnO₃. In addition, results show that 4.1 eV is a good choice for the on-site Coulomb parameter U.