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.     

Magnetic entropy change in perovskite manganites La0.6Pr0.1Pb0.3MnO3 with double metal-insulator peaks

Following the double metal-insulator peaks found in series of perovskite manganites La_0.7−xPr_xPb_0.3MnO₃ (x=0, 0.05, 0.1), the magnetic entropy change of La_0.6Pr_0.1Pb_0.3MnO₃ was carefully investigated as a representative. The maximum magnetic entropy change (ΔS_H=−1.7 J/kg K at 300 K) and the expanded refrigerant capacity (about 123.8 J/kg) had been obtained under 10 kOe magnetic field variation, though the double peak of maximum magnetic entropy change had not occurred since the comparative faint magnetic signal from the Pr ions inhomogeneity existed in the octahedral frame submerged in the strong magnetic signal originated from the dominating octahedral frame both in the double exchange mechanism, but the width at half maximum in the magnetic entropy change comparatively broadened.     

EMR study of magnetic inhomogeneities in crystalline bulk and nanometer-sized La0.7Ca0.3MnO3

Electron magnetic resonance (EMR) was studied on crystalline bulk and nanometer-sized samples of the same La_0.7Ca_0.3MnO₃ manganite compound aiming to compare their magnetic homogeneities. The results obtained show that single-crystalline bulk sample is less homogeneous than the nanocrystalline one. Except for higher homogeneity, the nanometer-sized sample also demonstrates a weaker magnetic anisotropy. As a result, well-pronounced coexistence of different magnetic phases (coexistence of ferromagnetic and paramagnetic resonance signals) is observed in the bulk sample, while it is absent in the nanocrystalline one. It is suggested that such strong difference is directly connected to the difference in structural state of the samples.     

Magnetic resonances spectroscopy of nanosize particles La0.7Sr0.3MnO3

Using a co-precipitation method, perovskite-type manganese oxide La_0.7Sr_0.3MnO₃ nanoparticles (NPs) with particle size 12 nm were prepared. Detailed studies of both ⁵⁵Mn nuclear magnetic resonance and superparamagnetic resonance spectrum, completed by magnetic measurements, have been performed to obtain microscopic information on the local magnetic structure of the NP. Our results on nuclear dynamics provide direct evidence of formation of a magnetically dead layer, of the thickness ≈2 nm, at the particle surface. Temperature dependences of the magnetic resonance spectra have been measured to obtain information about complex magnetic properties of La_0.7Sr_0.3MnO₃ fine-particle ensembles. In particular, electron paramagnetic resonance spectrum at 300 K shows a relatively narrow sharp line, but as the temperature decreases to 5 K, the apparent resonance field decreases and the line width considerably increases. The low-temperature blocking of the NPs magnetic moments has been clearly observed in the electron paramagnetic resonances. The blocking temperature depends on the measuring frequency and for the ensemble of 12 nm NPs at 9.244 GHz has been evaluated as 110 K.     

The influence of the sintering temperature on the structural and the magnetic properties of doped manganites: La0.95Ag0.05MnO3 and La0.75Ag0.25MnO3

La_1−xAg_xMnO₃ samples were synthesized by standard sol-gel method with Ag concentrations of x=0.05 and 0.25. The samples from each concentration were pressed and sintered at 1000, 1200 and 1400 °C for 24 h in air for a systematic study. They were examined structurally by Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS) and X-ray Diffraction (XRD) and magnetically by Magnetic Properties Measurements System (MPMS). AFM and SEM analyses show that surface morphology changes with Ag concentration and sintering temperature (T_S). It was observed that high temperature sintering leads Ag to leave material as determined from EDS analyses. XRD spectra exhibited that the crystal structure changes with Ag concentration while showing pronounced change with the sintering temperature. From the magnetic measurements, the Curie temperatures (T_C) and the isothermal magnetic entropy changes (−ΔSM) were calculated. It was observed that T_C increases with Ag concentration and decreases with T_S. The maximum −ΔSM was calculated to be 7.2 J/kg K under the field change of 5 T for the sample sintered at 1000 °C with x=0.25.     

Hydrothermal synthesis and Magnetocaloric effect of La0.5Ca0.3Sr0.2MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.5Ca_0.3Sr_0.2MnO₃ have been studied. The La_0.5Ca_0.3Sr_0.2MnO₃ can be produced as phase-pure, crystalline powders in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 513 K in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped particles in typical dimension of 4.0×2.5×1.6 μm. Heat treatment can improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change ΔS_M for the as-prepared sample is 0.88 J kg⁻¹ K⁻¹ at 315 K for a magnetic field change of 2.0 T. It increases to 1.52 J kg⁻¹ K⁻¹, near its Curie temperature (317 K) by annealing the sample at 1473 K for 6 h. The hydrothermal synthesis method is a feasible route to prepare high-quality perovskite material for magnetic refrigeration application.     

Study on the phase separation of La0.7Sr0.3MnO3 nanoparticles by electron magnetic resonance

In this work, the technique of electron magnetic resonance (EMR) is used to measure the magnetic resonant spectra of La_0.7Sr_0.3MnO₃ nanoparticles synthesized by sol–gel routes with three different gelation agents (S1: Urea+citric acid; S2: citric acid, and S3: Urea+tri-sodium citrate). The purpose of this study is to investigate the influence of synthesis conditions on the magnetic properties of nanoparticles. Our ESR results show that Curie temperatures of La_0.7Sr_0.3MnO₃ nanoparticles with different gelation agents are slightly different (T_c∼340 to 360 K) and possess both paramagnetic (PM) and ferromagnetic (FM) phases in the temperature below T_c. Besides, a sharp FM–PM transition indicates that the combined agent of Urea+tri-sodium citrate creates a better quality in CMR nanomagnets.     

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.     

Low-temperature transport properties of chemical solution deposited polycrystalline La0.7Sr0.3MnO3 ferromagnetic films under a magnetic field

Polycrystalline La_0.7Sr_0.3MnO₃ (LSMO) films were prepared on SiO₂/Si (001) substrates by chemical solution deposition technique. Electrical and magnetic properties of LSMO were investigated. A minimum phenomenon in resistivity is found at the low temperature (<50 K) under magnetic fields from 0 T to 3 T. Kondo-like spin dependent scattering, which includes both spin polarization and grain boundary tunneling, was observed in the low-temperature electrical transport for the LSMO polycrystalline films. The temperature-dependent resistivity at low temperatures can be well fitted in the framework of elastic scattering, electron-electron (e-e) interaction, Kondo-like spin dependent scattering, and electron-phonon (e-ph) interaction.     

Spin polarized La0.7Sr0.3MnO3 thin films on silicon

La_0.7Sr_0.3MnO₃ polycrystalline manganite thin films were grown on silicon (Si) substrates covered by SiO_x amorphous native oxide. Curie temperatures of about 325 K were achieved for 70-nm-thick films. Strong room temperature XMCD signal was detected indicating high spin polarization at the surface. Cross-sectional TEM images show sharp interface between SiO_x and manganite without signature of chemical reaction at the interface. Unusual sharp splitting of the manganite film was observed: on the top of a transition layer characterized by low crystalline order, a magnetically robust layer is formed.     

Domain wall pinning in polycrystalline perovskite La0.7Sr0.3MnO3

Reversible and irreversible domain wall (DW) motions have been investigated in La_0.7Sr_0.3MnO₃ ceramic samples using frequency-response complex permeability with various amplitudes of AC field. We also examine the effects of temperature in the range from 293 to 368 K and transverse DC magnetic field with a maximum of 4.40×10⁵ A/m on the real part of permeability (μ′). Two relaxations corresponding to reversible wall motions and domain rotations occur in low and high frequency regions, respectively. The irreversible DW displacements can be activated as the amplitude larger than the pinning field of 3 A/m, leading to an increase in μ′. The μ′ obeys a Rayleigh law at the temperature below 343 K or under DC field of less than 4.22×10⁴ A/m. The Rayleigh constant η increases from 5.45×10⁻² to 1.54×10⁻¹ (A/m)⁻¹ as the temperature rises from 293 to 343 K, and η decreases from 5.58×10⁻² to 3.67×10⁻² (A/m)⁻¹ with increasing DC field from 1.99×10³ to 4.22×10⁴ A/m.     

Uncompensated magnetization and exchange-bias field in La0.7Sr0.3MnO3/YMnO3 bilayers: The influence of the ferromagnetic layer

We studied the magnetic behavior of bilayers of multiferroic and nominally antiferromagnetic o-YMnO₃ (375 nm thick) and ferromagnetic La_0.7Sr_0.3MnO₃ and La_0.67Ca_0.33MnO₃ (8…225 nm), in particular the vertical magnetization shift M_E and exchange-bias field H_E for different thickness and magnetic dilutions of the ferromagnetic layer at different temperatures and cooling fields. We have found very large M_E shifts equivalent to up to 100% of the saturation value of the o-YMO layer alone. The overall behavior, including XMCD magnetization shift measured at the Mn-L edge of the LSMO layer only, indicates that the properties of the ferromagnetic layer contribute substantially to the M_E shift and that this does not correlate straightforwardly with the measured exchange-bias field H_E.     

The effect of Cu substitution on the A1g mode of La0.7Sr0.3MnO3 manganites

We report on the first Raman data of Cu substituted La_1−ySr_yMn_1−xCu_xO₃ (0≤x≤0.10 and 0.17≤y≤0.3, accordingly in order to have the same Mn⁴⁺/[Mn⁴⁺+Mn³⁺] ratio), collected in the frequency range 100-900 cm⁻¹ and at room temperature, with parallel (e_i∥e_s) and crossed (e_i⊥e_s) polarizations of the incident (e_i) and scattered (e_s) light. Spectra were fitted with a Drude-Lorentz model, and peaks at 190-220 and 430 cm⁻¹, together with two broad structures centered at near 500 and 670 cm⁻¹, have been found. We also have observed that the A_1g mode is substantially shifted with increasing Cu substitution. The A_1g phonon shift is a linear function of the tolerance factor t and the rhombohedral angle α_r, thus following the structural changes of the MnO₆ octahedra in the system.     

Electron spin resonance study of the Ba-doping manganite Nd0.5Sr0.5MnO3

We have performed magnetization measurements and electron spin resonance （ESR） on polycrystalline manganites of Nd0.5Sr0.5-xBaxMnO3 （x = 0.1）. Phase separation and phase transitions are observed from the susceptibility and the ESR spectra data. Between 260 K （～ Tc） and 185 K （～ TN）, the system coexists of the paramagnetic phase and the ferromagnetic （FM） phase. Between 185 K and 140 K, the system coexists of the FM phase and the antiferromagnetic （AFM） phase. These results indicate that the system has a very complex magnetic state due to the origin of the instability stemming from manganite Nd0.5Sr0.4Ba0.1MnO3 by partially substituting the larger Ba^2＋ ions for the smaller Sr^2＋ ions.     

Magnetocaloric effect in La0.67Sr0.33MnO3 manganite above room temperature

The La_0.67Sr_0.33MnO₃ composition prepared by sol-gel synthesis was studied by dc magnetization measurements. A large magnetocaloric effect was inferred over a wide range of temperature around the second-order paramagnetic-ferromagnetic transition. The change of magnetic entropy increases monotonically with increasing magnetic field and reaches the value of 5.15 J/kg K at 370 K for Δμ0H=5 T. The corresponding adiabatic temperature change is 3.3 K. The changes in magnetic entropy and the adiabatic temperature are also significant at moderate magnetic fields. The magnetic field induced change of the specific heat varies with temperature and has maximum variation near the paramagnetic-ferromagnetic transition. The obtained results show that La_0.67Sr_0.33MnO₃ could be considered as a potential candidate for magnetic refrigeration applications above room temperature.     

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.     

Strain effects in epitaxially grown La0.7Sr0.3MnO3 thin films

We report here on an X-ray absorption study of La_0.7Sr_0.3MnO₃ films epitaxially grown on SrTiO₃ substrate. The local organization around Mn in oriented films with 600 Å in thickness was investigated by polarized Extended X-ray Absorption Fine Structure. The angle between electric field vector and film surface was set equal to 5° and 70° to investigate almost independently the contribution of the manganese neighbors situated in and out of the film plane. The first neighboring shell oxygen is found to be the same in both geometries, but small changes in the next neighboring contribution are observed. These changes are associated with variation in the Mn–Mn bond length. A small in-plane elongation (3%) is observed in the constrained films with respect to the unconstrained case.     

A simple thermal decomposition synthesis, magnetic properties, and cytotoxicity of La0.7Sr0.3MnO3 nanoparticles

This study reports the new and simple synthesis of magnetic La_0.7Sr_0.3MnO₃ (LSMO) nanoparticles by thermal decomposition method using acetate salts of La, Sr and Mn as starting materials. To obtain the LSMO nanoparticles, thermal decomposition of the precursor is carried out at the temperatures of 600, 700, 800, 900, and 1000°C for 6 hours. The synthesized LSMO nanoparticles were characterized by XRD, FT-IR, TEM and SEM. Structural characterization shows that the prepared particles consisted of two phases of LaMnO₃ (LMO) and LSMO with crystallite sizes ranging from 18 to 55 nm. All the prepared samples have a perovskite structure which changes from cubic to rhombohedral with the increase in the thermal decomposition temperature. Basic magnetic characteristics such as saturation magnetization (M _S) and coercive field (H _C) are evaluated by sample vibrating magnetometry at room temperature (20°C). The samples show soft ferromagnetic behavior with M _S values of ∼9–55 emu/g and H _C values of ∼8–37 Oe, depending on the crystallite size and thermal decomposition temperature. The relationship between the crystallite size and the magnetic properties is presented and discussed. The cytotoxicity of synthesized LSMO nanoparticles was also evaluated with NIH 3T3 cells and the result showed that the synthesized nanoparticles were not toxic to the cells as determined from cell viability in response to the liquid extraction of LSMO nanoparticles.