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.     

Magnetic and magnetocaloric properties of Pr0.6−xEuxSr0.4MnO3 manganese oxides

Studies of the structural, magnetic and magnetocaloric properties of polycrystalline Pr_0.6−xEu_xSr_0.4MnO₃ (0≤x≤0.15) perovskite manganites were carried out. Substitution for praseodymium with europium, with smaller ionic radius, induces local distortion in the 〈Mn–O–Mn〉 bonds and consequently causes a random distribution in the magnetic exchange interactions. The competition between magnetic interactions leads to the appearance of an inhomogeneous magnetic state in our samples. Pr_0.6−xEu_xSr_0.4MnO₃ (x=0, 0.05, 0.1 and 0.15) polycrystalline samples were prepared using the solid–solid reaction method at high temperature. The compounds yielded are single phase and crystallize in the orthorhombic system with the Pnma space group. The substitution of Eu for Pr leads to a decrease of the Curie temperature T_C from 303 K for x=0.00 to 260 K for x=0.15. All of our compounds exhibit a large magnetic entropy change with a maximum around 2.2 J/kg K under a magnetic applied field change of 2 T for all compounds.     

Electroresistance effect in La1−xCaxMnO3 (0<x<1) ceramics

Electroresistance (ER) effects were investigated for a full series of manganite ceramics La_1−xCa_xMnO₃ (0<x<1), synthesized by solid state reaction. The results indicate that while the ER effects are large only in the presence of electrically active, high E-field boundaries, the equilibrium or metastable electronic-magnetic states in the adjoining domains are also significant, as a large ER occurs only at x=0.51 and x=0.17; those compositions are both near a two-phase coexistence region, i.e. close to a compositional regime where equilibrium insulating/metallic phase domains and interfaces would occur spontaneously.     

Giant magnetoimpedance and colossal ac magnetoresistance of a Cu coil wound on La0.67Sr0.33MnO3

We observed the giant magnetoimpedance and colossal ac magnetoresistance for a Cu coil wound on La_0.67Sr_0.33MnO₃ under low dc magnetic fields. Even though the dc magnetoresistance for La_0.67Sr_0.33MnO₃ plate is only −2.4% under H=12 kOe, a Cu coil wound on La_0.67Sr_0.33MnO₃ plate exhibits a colossal ac magnetoresistance of −93% at 10 MHz and a giant magnetoimpedance of −59% in a wide frequency range of 500 kHz-10 MHz under a longitudinal field . The transverse magnetoimpedance is weaker than the longitudinal one. The giant magnetoimpedance and colossal ac magnetoresistance for a Cu coil wound on La_0.67Sr_0.33MnO₃ are connected with the variation of permeability induced by dc magnetic field.     

Current density and intrinsic electroresistance of the Sm1−xSrxMnO3 manganite

We experimentally investigate the role of geometry on the current and current density dependencies of the intrinsic electroresistance of Sm_1−xSr_xMnO₃ of two compositions (x=0.40 and x=0.45). It is found that for each composition, the plot of the intrinsic electroresistance versus current density for samples with different dimensions and resistances coincide whereas this does not happen in the case of the electroresistance versus the magnitude of the current. These results confirm that the current density is indeed the relevant “universal” parameter for controlling the intrinsic electroresistance of these manganites.     

The effects of Cu doping on the magnetoresistive behavior of perovskites La0.7Ca0.3MnO3

The electronic and magnetic properties of Cu-doped perovskite La_0.7Ca_0.3Mn_1−xCu_xO₃ obtained by doping Cu on its Mn sites have been studied. The perovskite structure was found to remain intact up to the highest doping level of x=0.20. At low Cu concentration (x=0.05) the temperature-dependence of resistivity of the material exhibited up to two peaks corresponding to the magnetic transitions from the PM to the FM phase, and from the FM to the AFM phase. In general, the doping level was found to suppress the ferromagnetic ordering of the material, increase its resistivity, and produce large values of magnetoresistance near the resistivity peak. These results were explained as due to the formation of the antiferromagnetic phase.     

Electronic excitations in hole-doped La1−xSrxMnO3 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study on perovskite manganese oxides La_1−xSr_xMnO₃ (x=0, 0.2, and 0.4) at Mn K-absorption edge. Hole-doping effect on the electronic excitations in the strongly correlated electron systems is elucidated by comparing with undoped LaMnO₃. The scattering spectra of metallic La_0.6Sr_0.4MnO₃ show that a salient peak appears in low energies indicating the persistence of the Mott gap. At the same time, the energy gap is partly filled by doping holes and the spectral weight shifts toward lower energies. Though the peak position of the excitations shows weak dispersion in momentum dependence, RIXS intensity changes as a function of the scattering angle (2θ), which is related to the anisotropy. Furthermore, anisotropic temperature dependence is observed in La_0.8Sr_0.2MnO₃ which shows a metal-insulator transition associated with a ferromagnetic transition. We consider that the anisotropy in the RIXS spectra is possibly attributed to the correlation of the orbital degrees of freedom. The anisotropy is large in LaMnO₃ with long-range orbital order, while it is small but finite in hole-doped La_1−xSr_xMnO₃ which indicates persistence of short-range orbital correlation.     

Magnetic and magnetocaloric properties of Gd1−xScxNi2 solid solutions

Magnetic and heat capacity measurements have been carried out on the polycrystalline Gd_1−xSc_xNi₂ solid solutions (0≤x≤1), which crystallize in the cubic C15 Laves phases superstructure (space group F4?3m). These solid solutions are ferromagnetic with a Curie temperature below 76 K. Their Curie temperature decreases from 75.4 K for GdNi₂ to 13.6 K for Gd_0.2Sc_0.8Ni₂. At high temperatures, all solid solutions, except ScNi₂, are Curie-Weiss paramagnets. The Debye temperature as well as phonon, conduction electron and magnetic contributions to the heat capacity have been determined from heat capacity measurements. The magnetocaloric effect has been estimated both in terms of isothermal magnetic entropy change and adiabatic temperature change for selected solid solutions in magnetic fields up to 3 T.     

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.     

The static and dynamic lattice effects in La1−xCaxMnO3

The structural and magnetic behavior of the perovskite insulator La_0.9Ca_0.1MnO₃ were studied as a function of temperature from 15 to 300 K by neutron powder diffraction. Although this compound shows an anomalous response of the lattice parameters around T_c (150 K), the behavior of the oxygen/manganese Debye-Waller factors is in clear contrast to its “colossal magnetoresistance” (CMR) counterpart La_0.65Ca_0.35MnO₃. We speculate that the difference is intimately associated with the metal-insulator transition in the latter compound.     

Magnetoresistance in La1−xCaxMnO3 (0≤x<0.4)

The magnetic and transport properties of La_1−xCa_xMnO₃ (0≤x<0.4) have been systematically studied. The magnetoresistance (MR) maximum appears at x=0.2-0.25 and the temperature dependence of MR for x>0.25 shows a much broader profile than that of samples for x=0.2-0.25. Based on a scenario in which there is a short-range charge ordering (CO) state coexisting in the ferromagnetic state matrix for x>0.25, and the least or even no short-range CO state exists in samples for x=0.2-0.25, the above observations can be understood.     

Evolution from relaxor-like dielectric to ferroelectric in Ba[(Fe0.5Nb0.5)1−xTix]O3 solid solutions

Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ (x=0.2,0.4,0.6,0.8,0.85,0.9 and 0.95) solid solutions were synthesized by a standard solid-state reaction technique. X-ray diffraction at room temperature and dielectric characteristics over a broad temperature and frequency range were evaluated systematically. The structure of Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ solid solutions changed from cubic to tetragonal with increasing x. A Debye-like dielectric relaxation following the Arrhenius law similar to that in Ba(Fe_0.5Nb_0.5)O₃ was observed at lower temperature in the composition range 0.2≤x≤0.8, while the relaxor ferroelectric, diffused ferroelectric and normal ferroelectric behavior were observed for x=0.85,0.9 and 0.95, respectively. The process of the evolution of relaxor-like dielectric to ferroelectric suggested the changing from dilute polar micro-domains to polar micro-domains, polar micro/macro-domains and then polar macro-domains in the present ceramics.     

Magnetic and transport properties of SmCoAsO1−xFx

A series of SmCoAsO_1−xF_x (with x=0, 0.05, 0.1, and 0.2) samples have been prepared by solid state reactions. X-ray powder diffraction proved that all samples can be indexed as a tetragonal ZrCuSiAs-type structure. A clear shrinkage of the lattice constants a and c with increasing F content indicated that F has been doped into the lattice. The magnetic and transport properties of the samples have been investigated. Parent SmCoAsO compound exhibited complicated magnetism including antiferromagnetism, ferromagnetism, and ferrimagnetism. For the fluorine doped samples, the antiferromagnetic Néel temperatures were almost independent of the F content and metamagnetic transitions were observed below antiferromagnetic Néel temperatures. With increasing F content, high temperature (below 142 K) ferrimagnetic state gradually changed to ferromagnetic state. In the resistivity result, metallic conduction in the region of 2-300 K and Fermi liquid behavior at low temperatures were shown in all samples. Transport properties at applied magnetic fields showed anomalies at low temperatures.     

Orbital ordering in Mott-insulators La2O3Fe2Se2 and La2O3Co2Se2

The electronic structure and magnetic properties of new layered oxyselenide compounds La₂O₃Fe₂Se₂ and La₂O₃Co₂Se₂ are studied by first-principles calculations. Our results indicate that both compounds are Mott-insulators with orbital ordering. The ground states of both compounds are the checkerboard antiferromagnetic states, which are different from the iron pnictide superconductors, although their structures are similar to those of the Fe-As-based superconductors.     

Structural stability and magnetic properties of Bi1−xLa(Pr)xFeO3 solid solutions

In this work, X-ray diffraction data taken on Bi_1−xLa_xFeO₃ solid solutions are used to verify the following structural phase transitions: “polar rhombohedral-antipolar orthorhombic” at x≈0.16 and “commensurate-incommensurate” within the orthorhombic phase at x≈0.18. In contrast, in the Bi_1−xPr_xFeO₃ series, the polar rhombohedral phase transforms into an antipolar orthorhombic one at x≥0.13. The polar rhombohedral phase near the morphotropic phase boundary exhibits an isothermal transformation into an antipolar orthorhombic phase, though the transformation occurs much faster in the case of La-doped compounds. The incommensurate structural phase was not detected in Bi_1−xPr_xFeO₃ solid solutions. The ternary structural phase diagram is constructed for (Bi,La,Pr)FeO₃ systems. In addition, the polar rhombohedral phase exhibits a magnetic field-induced transition from the modulated antiferromagnetic state into a homogeneous weak ferromagnetic state whereas the antipolar phase is a weak ferromagnetic state in the absence of an external field.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Chiral optical absorption bands in [ ]Cd1−x Mnx Ga2S4 semiconducting compound

[ ]Cd_1−x Mn_x Ga₂S₄ is a semimagnetic semiconductor and it has revealed an exceptional property namely ‘optical activity‘. Therefore, a spectroscopic investigation of chiral absorption bands has been carried out with the view to examine the role of d*-d states of manganese atoms. It has been found that inner transitions of Mn⁺⁺ dominate the spectral region with a special feature, indicating that these transitions show the presence of a substantial contribution from the magnetic dipole moment which rotates the electric vector of the incident polarized radiation. The origin is associated to the lack of a symmetry center caused by the ordered vacancies in this defect compound.     

Linear and nonlinear critical magnetic properties and transport in Nd0.75Ba0.25MnO3 single crystal: evidence for its anomalous critical behavior near TC

The data on the resistance and magnetoresistance (MR) as well as measurements of the linear and nonlinear susceptibilities are presented for a Nd_0.75Ba_0.25MnO₃ single crystal with the Curie temperature T_C≈129 K. Although this compound remains insulating in the ferromagnetic state, its resistance has an anomaly near T_C and it reveals the colossal magnetoresistance. The data on the magnetic response are well described by the dynamic scaling theory for 3D isotropic ferromagnets in the paramagnetic critical region at τ>τ^*≈0.11, τ=(T−T_C)/T_C. Below τ^* an anomalous critical behavior is found that suggests the coexistence of two magnetic phases. This behavior is discussed in terms of a phase separation which can occur in the moderately doped manganites exhibiting an orbital ordering.     

Evolution of electronic structure in Eu1−xLaxFe2As2

We report an angle-resolved photoemission spectroscopy study of electronic structures of Eu_1−xLa_xFe₂As₂ single crystals, in which the spin density wave transition is suppressed with La doping. In the paramagnetic state, the Fermi surface maps are similar for all dopings, with chemical potential shifts corresponding to the extra electrons introduced by the La doping. In the spin density wave state, we identify electronic structure signatures that relate to the spin density wave transition. Bands around M show that the energy of the system is saved by the band shifts towards high energies, and the shifts decrease with increasing doping, in agreement with the weakened magnetic order.