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.     

Magnetocaloric effect in La0.75Sr0.25MnO3 manganite

The polycrystalline manganite La_0.75Sr_0.25MnO₃ prepared by an alternative carbonate precipitation route reveals the rhombohedral perovskite structure. Magnetization isotherms measured up to 2 T are used to determine Curie temperature of 332 K by means of Arrott plot. Maximum of magnetic entropy change is found at Curie temperature. The relative cooling power equal to 64 J/kg for 1.5 T magnetic field, is superior as compared to the manganite with the same chemical composition from the sol-gel method.     

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.     

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.     

Direct measurement of the magnetocaloric effect in La0.67Ca0.33MnO3

Polycrystalline perovskite La_0.67Ca_0.33MnO₃ was synthesized by a sol–gel method. Its adiabatic temperature change ΔT_ad induced by a magnetic field change was measured directly. At 268 K, near its Curie temperature T_C, ΔT_ad of La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T reaches 2.4 K. The latent heat Q and magnetic entropy change −ΔS_M induced by a magnetic field change were calculated from the temperature dependence of ΔT_ad and zero-field heat capacity C_p. The maximum values of Q and −ΔS_M in La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T are 1.85 J g⁻¹ and 6.9 J kg⁻¹ K⁻¹, respectively. The former is larger than the phase transition latent heat of heating or cooling, which is about 1.70 J g⁻¹.     

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.     

La0.8-xCa0.2MnO3纳米颗粒的居里温度与磁热效应

采用溶胶凝胶法制备了系列La_0.8-xCa_0.2MnO₃多晶样品,用X射线衍射分析确定了样品的钙钛矿结构,用透射电子显微镜观察了样品的形貌及粒径分布情况,用PAR155型振动样品磁强计测量了样品的磁性随外场和温度的变化,确定样品的居里温度并计算了各样品的磁熵变.磁测量及计算结果表明制备的各样品的居里温度在180—260K的范围内且随焙烧温度和La³⁺离子空位浓度的不同而变化,不同温度焙烧的样品均有较大的磁熵变值,其中1100℃焙烧的La_0.77Ca_0.2MnO₃,多晶样品在240.5K,H=1.0T的外场下的磁熵变达3.76J/kg·K,对实验结果做了定性的分析.该材料具有较高的居里温度和较大的磁熵变,所需外场强度适中,电阻率高,性能稳定,适合做高温磁制冷材料. 关键词： 钙钛矿 居里温度 磁热效应     

Magnetic, resonance and transport properties of nanopowder of La0.7Sr0.3MnO3 manganites

X-ray powder diffraction, magnetization, transport and magnetic resonance measurements of nanosize La_0.7Sr_0.3MnO₃ (LCMO) manganites have been performed. The nanosize manganites were synthesized with a co-precipitation method at different (600, 700, 800 and 1000 °C) temperatures. The crystal structure of the nanopowders obtained was determined to be perovskite-like with a rhombohedral distortion (the space group R3¯c). The average size of synthesized nanoparticles (from 17 to 88 nm) was estimated using the X-ray diffraction and low temperature adsorption of argon methods. All the nanosize manganites show ferromagnetic-like ordering. Both the Curie temperature and magnetization decrease with reducing the particle size. The decrease of magnetization is due to the disordered surface shell of particles. The disordered surface layer is a source of the surface anisotropy and is responsible for the increase of coercivity. Temperature dependences of the magnetic resonance spectra parameters have allowed obtaining information on dynamics of magnetic properties in the nanoparticle systems. The resistivity was established to become higher by reducing the particles’ size and increases to a great extent in nanoparticles with the smallest average size at low temperatures. The magnetic entropy was shown to be smaller for the small particles. Using the temperature dependence of magnetic entropy the relative cooling power of the nanosize samples studied was evaluated.     

Magnetotransport and magnetoelastic effects in Co-doped La0.7Sr0.3MnO3 nanocrystalline perovskites

La_0.7Sr_0.3Mn_1−xCo_xO₃ (x=0, 0.05, 0.1) nanoparticles, prepared by sol-gel method, were studied by means of X-ray diffraction, transmission electron microscopy, resistivity, magnetoresistance, thermal expansion and magnetostriction measurements. Results show that partial substitution of Mn by Co leads to a reduction in lattice parameters, enhancement of resistivity and room temperature magnetoresistance MR, decrease of metal-insulator transition temperature T_MI and T_C, an increase in thermal expansion coefficient, volume magnetostriction and anisotropic magnetostriction. The latter increases about one order of magnitude with 10% Co substitution. In comparison with Mn ions, the Co ions possess higher anisotropy energy, larger magnetostriction effect, smaller ionic size and spin state transitions with increase in temperature and magnetic field; this suggests that Co substitution leads to double-exchange interaction weakening, resulting in suppression of ferromagnetic long-range order and metallic state and increase of magnetic anisotropy. Furthermore, our samples have a relatively lower T_MI and T_C, higher resistivity and MR, compared with the reported values for similar compounds with larger particle sizes. This is attributed to the nanometric grain size and spin-polarized tunneling between neighboring grains.     

Effect of inhomogeneity on magnetic, magnetocaloric, and magnetotransport properties of La0.6Pr0.1Ca0.3MnO3 single crystal

The effect of magnetic inhomogeneity on magnetic, magnetocaloric, and transport properties of the colossal magnetoresistance manganites with first order ferromagnetic-to-paramagnetic phase transition is studied. The experiments were performed on the single-crystalline samples of La_0.6Pr_0.1Ca_0.3MnO₃. The inhomogeneity is described by the Curie temperature distribution function, which is found from the magnetization data. The temperature dependence of the magnetic field induced change in the entropy is shown to be determined by the distribution function and the shift of the transition temperature in a magnetic field. Similarly, magnetoresistance in the transition region is determined by the resistivity at H=0 and the shift of the transition temperature. The maximum entropy change as well as maximum magnetoresistance can be achieved in the magnetic field of order δT_C/B_M where δT_C is the transition width and B_M is the rate of change of the Curie temperature with magnetic field.Our approach to analysis of the effects of inhomogeneity is general and therefore can be used for all compounds with the first order magnetic phase transition.     

Effects of ZnO film thickness on electrical and magnetoresistance characteristics of La0.8Sr0.2MnO3/ZnO heterostructures

The La_0.8Sr_0.2MnO₃/ZnO heterostructures with different thicknesses of ZnO films are fabricated by using RF magnetron sputtering technique. The heterojunctions exhibit excellent rectifying properties at 300 K. At low temperatures the temperature dependent junction resistance exhibits a metal-insulator transition like behavior. A magnetic field strongly impacts on electrical characteristics of La_0.8Sr_0.2MnO₃/ZnO p-n junctions, i.e., depressing the junction resistance greatly and driving the metal-insulator transition temperature (T_MI) towards higher temperatures. Large magnetoresistance is observed below T_MI, and it increases with increasing magnetic field and almost saturates at 5 T, i.e., above −90% at 100 K and 5 T.     

Effect of Ca doping on the magnetic properties of Nd0.5Sr0.5MnO3 studied by electron spin resonance

The magnetic properties of Ca-doped Nd_0.5Sr_0.5MnO₃ have been studied by electron spin resonance (ESR) and dc magnetization measurements. The antiferromagnetic order and charge order are found to occur separately at T_N=200 K and T_co=150 K, respectively. Compared to the undoped Nd_0.5Sr_0.5MnO₃, the ferromagnetic correlations are suppressed by doping of the small Ca²⁺ ion. In addition, the antiferromagnetic transition temperature is enhanced to 200 K, which can be explained by an increase of superexchange interaction between Mn³⁺ and Mn⁴⁺ ions as their distance decreases.     

Current induced metastable states and abnormal electroresistance effect in epitaxial thin films of La0.8Ca0.2MnO3

By applying an electric current to La_0.8Ca_0.2MnO₃ films at 20 K, a high-resistive state is excited near the Curie point. Such a current induced metastable state turns out to be extremely sensitive to weak measuring currents. When the measuring current changes from 1 to 20 μA, the peak resistance near the metal-insulator transition temperature is reduced from 366 to , showing a remarkably enhanced electroresistance effect (ER=[R(0)−R(I)]/R(0)=70%). Also, in contrast to the previous reports, the metal-insulator transition shifts to a higher temperature. Our experiments show that the high-resistive state is metastable and cannot be removed by reversing the current direction. These behaviors yield a possibility to modulate the metal-insulator phase transition by using electric currents.     

Studies on the resistance switching properties of the La0.5Ca0.5MnO3/Nb : SrTiO3 heterojunction

In this study, we have investigated the resistance switching behavior of the La_0.5Ca_0.5MnO₃/Nb:SrTiO₃ heterojunction. The junction shows a negative resistance switching ratio (ER) below 140 K. When , the ER goes from negative to positive with increasing bias voltage. When T>220 K, the junction shows a positive ER. This variation from a negative to a positive value indicates that the ER is determined primarily by two phenomena: (a) the negative ER value can be attributed to a disruption of the charge-ordered insulating domains in La_0.5Ca_0.5MnO₃ under large electric fields, and (b) the positive ER value at high temperatures is due to the modulation of the interface barrier width driven by the electrochemical migration of oxygen vacancies.     

Electron spin resonance study of Fe doping effect in La0.67Ca0.33MnO3

Electron spin resonance (ESR) study was carried out on La_0.67Ca_0.33Mn_1−xFe_xO₃ (x=0.0, 0.04) samples. The temperature dependence of the ESR spectra indicates the presence of phase separation above and below T_C in x=0.0 and 0.04 sample, respectively. The increase of the g-value in the high-temperature region indicates the existence of local spin correlations even in the paramagnetic state. The activation energy obtained from both the temperature dependence of the ESR intensity and linewidth exhibits a smaller value in the Fe-doped sample. Our study suggests that the ferromagnetic spin correlations would be significantly weakened by a slight doping of Fe ions on Mn sites.     

Investigation of magnetocaloric effect in La0.45Pr0.25Ca0.3MnO3 by magnetic,differential scanning calorimetry and thermal analysis

We investigated magnetocaloric effect in La_0.45Pr_0.25Ca_0.3MnO₃ by direct methods (changes in temperature and latent heat) and indirect method (magnetization isotherms). This compound undergoes a first-order paramagnetic to ferromagnetic transition with T_C=200 K upon cooling. The paramagnetic phase becomes unstable and it transforms into a ferromagnetic phase under the application of magnetic field, which results in a field-induced metamagnetic transition (FIMMT). The FIMMT is accompanied by release of latent heat and temperature of the sample as evidenced from differential scanning calorimetry and thermal analysis experiments. A large magnetic entropy change of ΔS_m=−7.2 J kg⁻¹ K⁻¹ at T=212.5 K and refrigeration capacity of 228 J kg⁻¹ are found for a field change of ΔH=5 T. It is suggested that destruction of magnetic polarons and growth of ferromagnetic phase accompanied by a lattice volume change with increasing magnetic field is responsible for the large magnetocaloric effect in this compound.     

Sound velocity in La0.5Ca0.5MnO3

In this Letter the microscopic theory of the relative change in velocity of sound with temperature of La_0.5Ca_0.5MnO₃ is reported. The phonon Green function is calculated using the Green function technique of Zubarev in the limit of zero wave vector and low temperature. The lattice model electronic Hamiltonian in the presence of the phonon interaction with hybridization between the conduction electrons and the l-electrons is used. The relative change in velocity of sound at various temperatures is studied for different model parameters namely the position of the l-level, the effective phonon coupling strength and hybridization strength. The phonon anomalies observed experimentally at different temperatures are explained theoretically. An abrupt change in velocity at Neel temperature (TN) is observed clearly. It is observed that different parameters influence the velocity of sound.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Ti/Pr0.7Ca0.3MnO3/La0.67Sr0.33MnO3/Pt异质结电致电阻效应的改善

采用脉冲激光沉积技术制备了Ti/Pr_0.7Ca_0.3MnO₃/Pt和Ti/Pr_0.7Ca_0.3MnO₃/La_0.67Sr_0.33MnO₃/Pt异质结并研究了La_0.67Sr_0.33MnO₃功能插层对异质结电致电阻特性的影响. 实验结果表明La_0.67Sr_0.33MnO₃功能层的引入有效提高了器件的电阻转变特性,尤其是电阻转变率和疲劳性得到了极大的改善. 对La_0.67Sr_0.33MnO₃插层改善电致电阻转变特性的机理进行了定性的分析. 关键词： 电致电阻效应 电阻转变比率 疲劳特性     

Magnetocaloric effect in (La0.47Gd0.2)Sr0.33MnO3 polycrystalline nanoparticles

In this paper, nanosized particles of (La_0.47Gd_0.2)Sr_0.33MnO₃ perovskite-type oxides were successfully synthesized at a relatively low calcinated temperature at 800 °C for 10 h using amorphous molecular alloy as precursor. X-ray diffraction (XRD) and electron diffraction (ED) revealed that the resulting product is of pure single-phase rhombohedral structure. The Curie temperature T_C and magnetic entropy change (MCE) in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline nanoparticles are determined and compared to those of similar systems prepared by the conventional solid-state reaction method. The Curie temperature T_C is shifted to 298 k, and a relatively large MCE with a broad peak around Curie temperature is observed in (La_0.47Gd_0.2)Sr_0.33MnO₃ polycrystalline particles. These results suggested that this material is a suitable candidate as working substance in magnetic refrigeration near room temperature.