Evidence of ferromagnetic domains in the perovskite La0.7Sr0.3Co0.9Mn0.1O3

The magnetic and electronic ground states of the polycrystalline perovskite compound La_0.7Sr_0.3Co_0.9Mn_0.1O₃ have been studied using AC susceptibility, resistivity and neutron depolarization techniques. Results of neutron depolarization study establish the existence of ferromagnetic domains of ∼3 μm size below 180 K. The substitution of 10 at% Mn ions at the Co site in the compound La_0.7Sr_0.3CoO₃ reduces the effective e_g electron transfer and suppresses the double exchange interaction. The competition between the reduced ferromagnetic double exchange interaction and the coexisting antiferromagnetic interaction along with the random nature of substitution leads to a randomly canted ferromagnetic ground state for the substituted compound. Resistivity study confirms that the randomly canted ferromagnetic ground state is insulating.     

Maximum magnetic entropy change modulated toward room temperature in perovskite manganites La0.7−xNdx(Ca,Sr)0.3MnO3

With Nd³⁺ doping and Ca²⁺, Sr²⁺ modulating in the sol–gel technique, a series of polycrystalline perovskite samples La_0.7?xNd_x(Ca,Sr)_0.3MnO₃ (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25) was prepared, their maximum magnetic entropy changes were tuned to room temperature (ΔS_H = ?1.47 J/kg K at 298 k for La_0.45Nd_0.25(Ca,Sr)_0.3MnO₃), an enhancement of the maximum magnetic entropy change (ΔS_H = ?1.89 J/kg K at 315 k) and its refrigerant capacity (about 45.3 J/kg) had also been obtained under 9 kOe magnetic field variation for La_0.55Nd_0.15(Ca,Sr)_0.3MnO₃ contrast to La_0.7(Ca,Sr)_0.3MnO₃.     

Magnetic entropy change in perovskite manganites La0.65Nd0.05Ca0.3Mn0.9B0.1O3 (B=Mn,Cr, Fe)

We have investigated the effect of B-site dopant on magnetic entropy change in perovskite manganite samples of La_0.65Nd_0.05Ca_0.3MnO₃, La_0.65Nd_0.05Ca_0.3Mn_0.9Cr_0.1O₃, and La_0.65Nd_0.05Ca_0.3Mn_0.9Fe_0.1O₃ prepared by sol–gel technique. The maximum ΔS_H is in the order of −1.68 J/kg K and peaks at Curie temperature for La_0.65Nd_0.05Ca_0.3MnO₃ upon 10 kOe applied field change. For the sample with B-site dopant, a decrement of the maximum magnetic entropy change has been observed.     

Exchange interaction between ferromagnetic and antiferromagnetic phases in La1/3Nd1/3Ca1/3MnO3

Magnetization measurements of a La_1/3Nd_1/3Ca_1/3MnO₃ perovskite at magnetic field up to 6 T have revealed an anomalous behaviour – above 130 K the material exhibits a loop displacement about a field of 2 T. We assume that this is the result of an exchange interaction between ferromagnetic and antiferromagnetic phases in a magnetically inhomogeneous compound. At about 115 K a transition from a semiconducting to a metallic-like state has been observed.     

An electron paramagnetic resonance study of phase segregation in Nd0.5Sr0.5MnO3

We present results of an electron paramagnetic resonance (EPR) study of Nd_1−xSr_xMnO₃ with x=0.5 across the paramagnetic to ferromagnetic, insulator to metal transition at 260 K (T_c) and the antiferromagnetic, charge ordering transition (T_N=T_co) at 150 K. The results are compared with those on Nd_0.45Sr_0.55MnO₃ which undergoes a transition to a homogeneous A-type antiferromagnetic phase at T_N=230 K and on La_0.77Ca_0.23MnO₃ which undergoes a transition to coexisting ferromagnetic metallic and ferromagnetic insulating phases. For x=0.5, the EPR signals below T_c consist of two Lorentzian components attributable to the coexistence of two phases. From the analysis of the temperature dependence of the resonant fields and intensities, we conclude that in the mixed phase ferromagnetic and A-type antiferromagnetic (AFM) phases coexist. The x=0.55 compound shows a single Lorentzian throughout the temperature range. The signal persists for a few degrees below T_N. The behaviour of the A-type AFM phase is contrasted with that of the two ferromagnetic phases present in La_0.77Ca_0.23MnO₃. The comparison of behaviour of A-type AFM signal observed in both Nd_0.5Sr_0.5MnO₃ and Nd_0.45Sr_0.55MnO₃ with the two FM phases of La_0.77Ca_0.23MnO₃, vis-à-vis the shift of resonances with respect to the paramagnetic phases and the behaviour of EPR intensity as a function of temperature conclusively prove that the Nd_0.5Sr_0.5MnO₃ undergoes phase separation into A-type AFM and FM phases.     

Giant magneto-caloric effect around room temperature at moderate low field variation in La0.7(Ca1−xSrx)0.3MnO3 perovskites

Among the perovskite manganites, a series of La_1?xCa_xMnO₃ has the largest magneto-caloric effect (MCE) (|ΔS_m|_max=3.2–6.7 J/kg K at ΔH=13.5 kOe), but the Curie temperatures, T_C, are quite low (165–270 K). The system of LaSrMnO₃ has quite high T_C but its MCE is not so large. The manganites La_0.7(Ca_1?xSr_x)_0.3MnO₃ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25) have been prepared by solid state reaction technique with an expectation of large MCE at room temperature region. The samples are of single phase with orthorhombic structure. The lattice parameters as well as the volume of unit cell are continuously increased with the increase of x due to large Sr²⁺ ions substituted for smaller Ca²⁺ ions. The field-cooled (FC) and zero-field-cooled (ZFC) thermomagnetic measurements at low field and low temperatures indicate that there is a spin-glass like (or cluster glass) state occurred. The Curie temperature T_C increases continuously from 258 K (for x=0) to 293 K (for x=0.25). A large MCE of 5 J/kg K has been observed around 293 K at the magnetic field change ΔH=13.5 kOe for the sample x=0.25. The studied samples can be considered as giant magneto-caloric materials, which is an excellent candidate for magnetic refrigeration at room temperature region.     

Electrical and magnetic behavior of La0.7Ca0.3MnO3/La0.7Sr0.2Ca0.1MnO3 composites

The electrical transport properties and the magnetoresistance of La_0.7Ca_0.3MnO₃/La_0.7Sr_0.2Ca_0.1MnO₃ composites are investigated as a function of sintering temperature. On the basis of an analysis by X-ray powder diffraction and scanning electron microscopy we suggest that raising the sintering temperature enhanced the interfacial reaction and creates interfacial phases at the boundaries of the La_0.7Ca_0.3MnO₃ and La_0.7Sr_0.2Ca_0.1MnO₃. Results also show that in 3 kOe, and at the Curie temperature, the magnetoresistance value of 14% was observed for the composite sintered at 1300 °C. Based on 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 experimental resistivity—temperature data from 50-300 K and find that the activation barrier decreases as temperature is increased.     

Experimental evidence for a magnetic two-phase state in manganites

It is found that samples of manganites La_0.9Sr_0.1MnO₃ (single crystal), Eu_0.7A_0.3MnO₃ (A=Ca, Sr; ceramics), and La_0.1Pr_0.6Ca_0.3MnO₃ and La_0.84Sr_0.16MnO₃ (thin epitaxial films) that are either field-cooled (in a magnetic field) or zero-field-cooled differ in low-temperature magnetization, and the hysteresis loop of field-cooled samples exhibits a displacement. This displacement signifies that a ferro-antiferromagnetic state occurs in these samples. The exchange integral J～10^?6 eV is calculated from this displacement, which describes the exchange Mn-O-Mn coupling through the interface ferromagnetic droplet-antiferromagnetic matrix. The magnetoresistance and volume magnetostriction of La_1?x Sr_xMnO₃ single crystals exhibit similar dependences on x, temperature, and the magnetic field in the vicinity of the Curie point, which points to the fact that these dependences are due to the same reason, namely, the occurrence of a magnetic two-phase ferro-antiferromagnetic state caused by strong s-d exchange.     

La0.7Sr0.3MnO3 film prepared by dc sputtering on silicon substrate: Effect of working pressure

La_0.7Sr_0.3MnO₃ films were prepared by dc sputtering on Si (100) substrate at different working pressure. The possibility of controlling the magnetic and transport properties of colossal magnetoresistance film is investigated, which has attracted great research interest for practical application. The as-grown film shows different magnetic, transport and magnetoresistance change at different working pressure at room temperature, which is quite attractive from technological point of view. Maximum magnetoresistance (MR) of ?5.56%, Curie temperature (T_c) of 325 K and metal insulator transition temperature (T_MI) of 278 K was achieved at room temperature.     

Properties of thin manganite films grown on semiconducting substrates for spintronics applications

La_0.7Sr_0.3MnO₃ (LSMO) manganite thin films were grown by pulsed plasma deposition on silicon (Si) and gallium arsenide (GaAs) substrates covered by an amorphous oxide. Manganite films are characterized by polycrystalline structure. Ferromagnetic transition is above room temperature and for 50 nm thick film the Curie temperature was as high as 325 K and 305 K for LSMO/SiO_x/Si and LSMO/AlO_x/GaAs, respectively.     

A Magnetic resonance study of La1−x SrxMnO3 manganites

Single crystals of La_0.9Sr_0.1MnO₃ and La_0.8Sr_0.2MnO₃ manganites are examined using magnetic resonance in the temperature range 80–370 K. It is found that magnetostatic oscillations arise near the Curie temperature. The possible reasons for the appearance of additional lines in the ferromagnetic resonance (FMR) spectrum are considered, and the anisotropy field and the type of crystalline magnetic anisotropy in the La_0.8Sr_0.2MnO₃ compound are determined. It is shown that the crystalline magnetic anisotropy in the La_0.9Sr_0.1MnO₃ compound exhibits specific features associated with its type of crystal structure.     

Performance of perovskite-related oxide cathodes in contact with lanthanum silicate electrolyte

The cathodic performance of selected mixed-conducting electrodes, including perovskite-type SrMn_0.6Nb_0.4O_3 ? δ, Sr_0.7Ce_0.3Mn_0.9Cr_0.1O_3 ? δ and Gd_0.6Ca_0.4Mn_0.9Ni_0.1O_3 ? δ, and Ruddlesden–Popper La₂Ni_0.5Cu_0.5O_4 + δ, LaSr₂Mn_1.6Ni_0.4O_7 ? δ, La₄Ni_3 ? xCu_xO_10 ? δ (x = 0–0.1) and La_3.95Sr_0.05Ni₂CoO_10 ? δ, was evaluated in contact with apatite-type La₁₀Si₅AlO_26.5 solid electrolyte at 873–1073 K and atmospheric oxygen pressure. The electrochemical activity of porous nickelate-based layers was found to correlate with the concentration of mobile ionic charge carriers and bulk oxygen transport, thus lowering in the series La₄Ni_2.9Cu_0.1O_10 ? δ > La₄Ni₃O_10 ? δ > La_3.95Sr_0.05Ni₂CoO_10 ? δ and decreasing on copper doping in K₂NiF₄-type La₂Ni_1 ? xCu_xO_4 ? δ. The relatively high overpotentials of nickelate-based cathodes, varying in the range ? 240 to ? 370 mV at 1073 K and current density of ? 200 mA/cm², are primarily associated with surface diffusion of silica from La₁₀Si₅AlO_26.5, which partially blocks the electrochemical reaction zone. As compared to the intergrowth nickelate materials, the manganite-based electrodes exhibit substantially worse electrochemical properties, in correlation with the level of oxygen-ionic and electronic conduction in Mn-containing phases. The effects of cation interdiffusion between the cell components as a performance-deteriorating factor are briefly discussed.     

Transport and magnetic properties of La1.48Nd0.4Sr0.12CuO4/La0.67Sr0.33MnO3 bilayer

We have grown La_1.48Nd_0.4Sr_0.12CuO₄/La_0.67Sr_0.33MnO₃ (LNSCO/LSMO) bilayer structure on SrTiO₃ (0 0 1) substrate. Both temperature dependences of resistivity and magnetization curves show anomalies between 60 < T < 80 K, where a low-temperature orthorhombic (LTO) to low-temperature tetragonal (LTT) structural transition is observed in LNSCO bulk crystal. It is suggested that the formation of domains in LSMO layer can relax the strains caused by the LTO–LTT transition in LNSCO layer.     

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.     

Magnetocaloric effect in polycrystalline (La0.5Gd0.2)Sr0.3MnO3

In this paper, we present a study of magnetocaloric effect in the colossal magnetoresistance material (La_0.5Gd_0.2)Sr_0.3MnO₃. From the measurements of isothermal magnetization at different temperatures, we have discovered a large magnetic entropy change with a broad peak around Curie temperature (270.5 K) in (La_0.5Gd_0.2)Sr_0.3MnO₃ polycrystalline sample. Moreover, the maximum of magnetic entropy change exhibits a nearly linear dependence with applied high magnetic field. These results suggest that this material is a suitable candidate as working substance in magnetic refrigeration near room temperature.     

Tuning the magnetocaloric properties of La0.7Ca0.3MnO3 manganites through Ni-doping

The effect of Ni²⁺ doping on the magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ manganites synthesized via the auto-combustion method is reported. The aim of studying Ni²⁺-substituted La_0.7Ca_0.3Mn_1 ? xNi_xO₃ ($x=0,0.02,0.07$, and 0.1) manganites was to explore the possibility of increasing the operating temperature range for the magnetocaloric effect through tuning of the magnetic transition temperature. X-ray diffraction analysis confirmed the phase purity of the synthesized samples. The substitution of Mn³⁺ ions by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice was also corroborated through this technique. The dependence of the magnetization on the temperature reveals that all the compositions exhibit a well-defined ferromagnetic to paramagnetic transition near the Curie temperature. A systematic decrease in the values of the Curie temperature is clearly observed upon Ni²⁺ doping. Probably the replacement of Mn³⁺ by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice weakens the Mn³⁺–O–Mn⁴⁺ double exchange interaction, which leads to a decrease in the transition temperature and the magnetic moment in the samples. By using Arrott plots, it was found that the phase transition from ferromagnetic to paramagnetic is second order. The maximum magnetic entropy changes observed for the $x=0,0.02,0.07$, and 0.1 composites was 0.85, 0.77, 0.63, and 0.59 J/kg?K, respectively, under a magnetic field of 1.5 T. In general, it was verified that the magnetic entropy change achieved for La_0.7Ca_0.3Mn_1 ? xNi_xO₃ manganites synthesized via the auto-combustion method is higher than those reported for other manganites with comparable Ni²⁺-doping levels synthesized via standard solid state reaction. The addition of Ni²⁺ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (～60 J/kg) is found for a Ni-doping level of 2% around 230 K in a field of 1.5 T.     

Structural and magnetic ordering in La0.6Ca0.4MnO3

The structural and magnetic ordering in La_0.6Ca_0.4MnO₃ has been studied by neutron powder diffraction as a function of temperature between 15 and 300 K. The para-ferromagnetic transition at T∼250 K is accompanied by significant structural distortions in the form of octahedral Mn–O₆ rotations. At 15 K, the total refined ferromagnetic moment on the Mn site was obtained as 3.1 μ_B, in reasonable agreement with the total expected average moment of mixed Mn³⁺/Mn⁴⁺ matrix.     

Electrochemical characterization of mixed conducting and composite SOFC cathodes

The electrochemical performance of La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (L58SCF), La_0.9Sr_1.1FeO_4−δ (LS2F) and LSM (La_0.65Sr_0.3MnO_3−δ)/LSM–YSZ (50 wt.% LSM–50 wt.% ZrO₂ (8 mol% Y₂O₃)) cathode electrodes interfaced to a double layer Ce_0.8Gd_0.2O_2−δ (CGO)/YSZ electrolyte was studied in the temperature range of 600 to 850 °C and under flow of 21% O₂/He mixture, using impedance spectroscopy and current density–overpotential measurements. The L58SCF cathode exhibited the highest electrocatalytic activity for oxygen reduction, according to the order: LS2F/CGO/YSZ ≤ LSM/LSM–YSZ/CGO/YSZ < L58SCF/CGO/YSZ.     

Determination of the ionic conductivity of Sr-doped lanthanum manganite by modified Hebb–Wagner technique

The Hebb–Wagner polarization method with the electron blocking electrode has been discussed in this paper in aim to determine a partial ionic conductivity of Sr-doped lanthanum manganite. The “limiting current” in the proposed system was measured using the two-point DC technique with additional Pt electrode between LSM and blocking electrode. The electrochemical model based on bulk diffusion processes and Boltzmann statistics has been also described. The ionic conductivity calculated with the use of proposed model for La_0.7Sr_0.3MnO_3+δ was 5.3×10⁻⁴ S cm⁻¹ at 800 °C and the activation energy of ionic conductivity was found to be (0.60±0.02) eV. This result is in agreement with previous literature reports and indicates the workability of the modified Hebb–Wagner system.     

Magnetic studies of colossal magnetoresistance perovskites on macroscopic,mesoscopic and microscopic length scales

We have investigated magnetic correlations in various CMR manganites on macroscopic, mesoscopic and microscopic length scales by carrying out DC magnetization, neutron depolarization, and neutron diffraction measurements. We present here the effect of substituting Mn with Fe and La with Dy in the ferromagnetic La_0.7−xCa_xMnO₃ (x ∼ 0.3–0.33) compounds. Neutron diffraction has been used in order to characterize the long-range magnetic order and its gradual suppression by the substitution. Neutron depolarization study has been carried out in order to bridge the gap in our understanding regarding the nature of magnetic correlation obtained from the macroscopic and microscopic measurements. In particular, our study on La_0.67Ca_0.33Mn_0.9Fe_0.1O₃ has established the fact that a true double exchange mediated spin-glass is insulating. In another study of La-site ionic size effect and its disorder in (La_1−x Dy _x )_0.7Ca_0.3MnO₃, we have investigated the evolution of the length scale of magnetic ordering with a possible microscopic explanation and the results have been compared with that for the light rare earth substituted compounds.