Oxygen vacancy doping effect on the electrical and magnetic behavior of Ba5−xLaxNb4−xTixO15

We report electric and magnetic properties of oxygen deficient Ba_5−xLa_xNb_4−xTi_xO_15−δ phases, which have been prepared by solid-state reaction method followed by a controlled reduction process under hydrogen atmosphere. The extra electrons added by the formation of the oxygen vacancies (δ) introduce localized spins and the magnetic susceptibility can be described by a temperature-independent contribution and a Curie-Weiss term associated to the Ti³⁺ ion formation. Besides, the experimental resistivity (ρ) data of these four reduced compounds are well described in a wide temperature range with the equation , which suggests the presence of small polarons in the system. Although, all samples present electrical insulating behavior, the electrical resistivity decreases four orders of magnitude for intermediate x values. We interpreted this fact as a consequence of the mix between the localized bands of the Nb and Ti ions, which favors the promotion of carriers due to reduction of the band gap.     

Short- and long-range order in La1−xSrxCoO3 and La1−xBaxCoO3

The short- and long-range order correlations of the crystal structure in the distorted perovskites La_1−xSr_xCoO₃ and La_1−xBa_xCoO₃ (0.0?x?0.5) have been studied by the neutron powder diffraction (NPD) and the Co K-edge X-ray absorption spectroscopy (XAS) measurements. The results of XAS and NPD indicate a local distortion around the Co³⁺ ions in LaCoO₃ at room temperature. The substitution of the La³⁺ ions by the Sr²⁺(Ba²⁺) ions leads to a gradual increase of the Co-O-Co angle and is accompanied by an increase of the mean square relative displacement (MSRD) of the Co-O bond. These results correlate with an increase of the oxygen amplitude vibration in the direction perpendicular to the Co-O bond. The possible explanation of the observed changes of the crystal and electronic structures in the above-mentioned cobaltites is discussed.     

Defect formation and transport in mixed-conducting La0.90Sr0.10Al0.85−xFexMg0.15O3−δ

The redox behavior of perovskite-type La_0.90Sr_0.10Al_0.85−xFe_xMg_0.15O_3−δ (x=0.20-0.40) mixed conductors was analyzed by the Mössbauer spectroscopy and measurements of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10⁻²⁰ to 0.5 atm at 1023-1223 K. The results combined with oxygen-ion transference numbers determined by the faradaic efficiency technique in air, were used to calculate defect concentrations, mobilities, and partial ionic and p- and n-type electronic conductivities as a function of oxygen pressure. The redox and transport processes can be adequately described in terms of oxygen intercalation and iron disproportionation reactions, with the thermodynamic functions independent of defect concentrations. No essential delocalization of the electronic charge carriers was found. The oxygen non-stoichiometry values estimated from the conductivity vs. p(O₂) dependencies, coincide with those evaluated from the Mössbauer spectra.     

Dielectric properties of lanthanum-doped CaCu3Ti4O12 synthesized by semi-wet route

Effect of La³⁺ doping at Ca²⁺ site in CaCu₃Ti₄O₁₂ has been examined. Compositions with x=0.10, 0.20 and 0.30 were synthesized in the system Ca_(1−3x/2)La_xCu₃Ti₄O₁₂ by semi-wet method. Powder X-ray diffraction confirmed the formation of monophasic compounds. The structure remains cubic similar to CaCu₃Ti₄O₁₂. Lattice parameter increases slightly with increasing La³⁺ concentration. Microstructure has been studied using scanning electron microscopy (SEM). Average grain size is in the range 2-4 μm for various compositions. Energy-dispersive spectrometer (EDS) studies confirm the stoichiometry of the synthesized materials. Dielectric constant, dielectric loss and conductivity of the samples decrease with increasing lanthanum concentrations.     

Magnetic phase diagram of double-layered La2−2xCa1+2xMn2O7 manganite

Double-layered manganite La_2−2xCa_1+2xMn₂O₇ have been synthesized for compositions ‘x’=0.0, 0.1, 0.2, 0.3, 0.4 and 0.5 by solid state reaction method. From X-ray diffraction study, their crystal structures were found to be tetragonal perovskite with lattice parameters decreasing with increasing ‘x’. The decreasing lattice parameters affect the balance between in-plane, intra-bilayer and inter-bilayer exchange interactions, which is reflected on magnetotransport properties. The metal-to-insulator transition temperature is found to vary with composition and peaked around ‘x’=0.3. From ac-susceptibility study, 2D-ferromagnetic ordering was observed at higher temperatures for all compositions whereas 3D-ferromagnetic ordering was observed at quite low temperatures. In low-temperature region, decreasing susceptibility shows antiferromagnetic state for all compositions. On the basis of electrical and magnetic properties, a magnetic phase diagram is given.     

Thermodynamic and kinetic properties of Ho1−xTixCo2-hydrogen system

The hydrogen absorption behavior of Laves phase Ho_1−xTi_xCo₂ (x=0.1-0.6) alloys has been investigated by pressure-concentration (PC) isotherms and cyclic-, temperature- and pressure-dependent absorption kinetics. The PC isotherms and kinetics of hydrogen absorption have been studied in the pressure range 0.01-1 bar and temperature range 50-200 °C using Sievert's-type apparatus. The drastic changes in the induction period and particle size during the activation process have been discussed based on the kinetics of repeated hydrogenation cycles and scanning electron microscopy (SEM) images of the hydrides at different hydriding cycles, respectively. The experimental results of kinetic curves are interpreted using the Johnson-Mehl-Avrami (JMA) model, and the reaction order and reaction rate have been determined. The α-, (α+β)- and β-phase regions in Ho_1−xTi_xCo₂-H have been identified from the different slope regions of the first-order-type kinetic plots. The dependence of the reaction rate parameter on hydriding pressure and temperature in the (α+β)-phase region has been discussed.     

The role of substitution-induced micro-structural defects on the redox behavior and catalytic activity of LaxTh1−x(VO3−δ)4 mixed oxide catalysts

The catalytic properties and reduction behavior of mixed metal oxides with nominal compositions of La_xTh_1−x(VO_3−δ)₄, where 0.0 ≤ x ≤ 1.0, have been investigated as a function of the value of x. These compositions were synthesized by ceramic route and characterized using powder X-ray diffraction, differential thermal analysis, and temperature-programmed reduction/oxidation/desorption techniques. The substituted samples were comprised of two distinct phases, one corresponding to tetragonal thorium metavanadate with partial substitution at A-sites, i.e. La_xTh_1−x(VO_3−δ)₄, and the other a new phase identified as LaV₄O_11+δ. Both these phases exhibited considerable oxygen non-stoichiometry, depending upon the extent of substitution. Nevertheless, no significant change was observed in their respective crystal symmetry. Further, the substituted samples showed more reproducible redox behavior and also an improved catalytic activity for CO oxidation reaction. A definite correlation is found to exist between the micro-structural defects generated in the above-mentioned two phases because of the oxygen ion vacancies, resultant enhancement in thermal diffusitivity of lattice oxygen, and finally the catalytic activity of the substituted mixed oxides. It is envisaged that a kind of synergism between the micro-structural defects existing in the two inter-grown phases generated simultaneously during the synthesis may control the catalytic properties of composite metal oxide systems.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Preparation, electrical and gas-sensing properties of perovskite-type La1−xMgxFeO3 semiconductor materials

The La_1−xMg_xFeO₃ powder was prepared by sol-gel method using citric acid. The compounds crystallized were perovskite phase with orthorhombic structure. The Mg-doping restrains the growth of the grain size. The conductivity and gas sensing of La_1−xMg_x FeO₃-based sensors were investigated. We found the La_0.92Mg_0.08 FeO₃-based sensors have the best response and selectivity to ethanol gas. Great differences on the conductance-temperature curves of La_0.92Mg_0.08 FeO₃-based sensors between in ethanol gas and air or other gas such as H₂, CO and CH₄ were also found. The conductance in ethanol gas decreased with temperature from 130 to 240 °C. But in air and other gas such as H₂, CO and CH₄ the conductance increases all the time. It indicates that at 240 °C the conductance difference between air and ethanol was the biggest and the response reach the maximum.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

Ferromagnetism of epitaxially grown CaRu1−xMxO3 (M=Ti, Mn) films

Epitaxial thin films of CaRu_1−xM_xO₃ (M=Ti, Mn) were fabricated on a (0 0 1)-SrTiO₃ substrate by spin-coat method using organometallic solutions (metal alkoxides). Results of X-ray diffraction and transmission electron microscopy indicate that the epitaxial films were grown pseudomorphically so as to align the [0 0 l] axis of the CaRu_1−xM_xO₃ films perpendicular to the (0 0 1) plane of the SrTiO₃ substrate. Ferromagnetism and metal-insulator transition are induced by the substitution of transition metal ions. The occurrence of ferromagnetism was explained qualitatively assuming a TiRu₆ cluster model for CaRu_1−xTi_xO₃ film and a mixed valence model for CaRu_1−xMn_xO₃ film. Ferromagnetism was also observed for layered CaRuO₃/CaMnO₃ film and CaRuO₃/CaMnO₃/CaRuO₃/CaMnO₃ multilayer film and the magnetism was explained by an interfacial exchange interaction model with magnetic Mn³⁺, Mn⁴⁺, and Ru⁵⁺ ions.     

Magnetic properties of electron-doped Y1−xCexMnO3 compounds

Cerium-doped Y_1−xCe_xMnO₃ compounds have been prepared in single-phase form for x=0 to 0.10. X-ray diffraction (XRD) patterns could be analyzed by using P6₃cm space group. Temperature variations of ac susceptibility and magnetization measurements show that these Ce-doped materials exhibit weak ferromagnetic transition. The observed ferromagnetic transition is attributed to the double exchange ferromagnetic interaction between Mn²⁺ and Mn³⁺ ions due to electron doping. The M–H loops exhibit hysteresis along with linear contribution and were analyzed based on bound magnetic polaron (BMP) model. Increase in saturation magnetization and decrease in BMP concentrations have been observed with increase in Ce doping.     

Magnetic and transport properties in Sr1−xLaxFe1−xMnxO3

The magnetic and transport properties in the perovskite Sr_1−xLa_xFe_1−xMn_xO₃ have been explored. As x rises, the systemic ferromagnetism increases gradually and cluster-spin-glass state occurs in the low-temperature region. For 0.3?x?0.7, the ferromagnetic phase separation from the paramagnetic phase was observed from the results of electron-spin-resonance measurement. Although all samples show a semiconducting behavior, their transport properties are dominated by two different mechanisms, namely, the electronic transport of x?0.5 samples is realized by thermal activation but the variable-range hopping is applied in x?0.7 ones. The different transport mechanism can be understood from the Mn/Fe ions interaction.     

Dielectric properties of valence compensated Ca1−xBixTi1−xCrxO3 perovskite prepared using the sol-gel process

Ca_1−xBi_xNb_1−xCr_xO₃ (x=0.01-0.5) ceramic powders were synthesized using the sol-gel process. The single-phase solids can be presented at x=0.01 and 0.03. The coexistence of orthorhombic perovskite and the secondary phase of BiCrO₃ was verified, as presented for x=0.05-0.5. Grains with a micro-cube topography were obtained for x=0.3-0.5. The average grain size is about 0.4 and 1.1 μm for x=0.3 and 0.5, respectively. The highest dielectric constant peak was measured at around 55 °C for x=0.5 and at 75 °C for x=0.3. The high dielectric constant was caused by the formation of barrier layers at the interface of the bi-phase mixed ceramics. Space charge polarization contributed to the observed behavior.     

Synthesis and investigation of magnetic properties of substituted ferrite nanoparticles of spinel system Mn1−xZnx[Fe2−yLy]O4

Superparamagnetic nanoparticles of the spinel ferrite four-element system Mn_1−xZn_x[Fe_2−yL_y]O₄ (where L:Gd³⁺, La³⁺, Ce³⁺, Eu³⁺, Dy³⁺, Er³⁺,Yb³⁺) were synthesized by the co-precipitation method. The magnetic moments of the 10 nm diameter nanoparticles were comparable to the ones of Fe₃O₄ nanoparticles. A comparatively low T_C (∼52–72 °C) was observed for some of the compositions. The heating mechanism of the superparamagnetic particles in the AC magnetic field at radiofrequency range is discussed and especially the absence of the hysteresis loop in the M–H curve at room temperature. One possible explanation—spontaneous particle agglomeration—was experimentally verified.     

Raman spectra of Ba6−3xSm8+2xTi18O54 solid solution

Raman spectra of Ba_6−3xSm_8+2xTi₁₈O₅₄ solid solution were investigated as the function of x and sintering time. Reasonable explanations were provided about the Raman shifts and their intensities at 1013, 590, 751, 280, 232 cm⁻¹. 1013 cm⁻¹ demonstrates the existence of BaCO₃ phase in solid solution, 590 cm⁻¹ is the symmetric stretching mode of the basal oxygens of the octahedral; 280 and 232 cm⁻¹ are the symmetric stretching modes resulted from the tilt of octahedral when large cation sites are Sm³⁺ and Ba²⁺. The shoulder peak appearing around 302 cm⁻¹ is related to the vacancy produced by the unequal valence of Sm³⁺ and Ba²⁺.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).     

Coexistence of superconductivity and magnetism in the La0.87−xLnxSr0.13FeAsO (Ln=Sm, Gd, Dy) system

The interplay between the superconducting phase and spin density wave order phase was studied. We report the magnetic and superconducting properties of the hole-doped FeAs-based superconducting compound La_0.87−xLn_xSr_0.13FeAsO (Ln=Sm, Gd, Dy; 0≤x≤0.06). Both resistivity and magnetic susceptibility measurements show that the superconducting transition temperature decreases with increase in composition of magnetic ions. The hysteresis loop of the La_0.87−xLn_xSr_0.13FeAsO sample shows a superconducting hysteresis in addition to a paramagnetic background. The experiment demonstrates that the magnetism and superconductivity coexist in hole-doped FeAs-based superconducting compounds. Among these three magnetic rare-earth elements, the influence of Dy³⁺ doping on superconductivity is more evident than that of Gd³⁺ doping, while the influence of Sm³⁺ doping is the weakest. The trend is consistent with the variation of the lattice parameter along c-axis.