Improvement of refrigerant capacity of La0.7Ca0.3MnO3 material with a few percent Co doping

The influence of first and second order magnetic phase transitions on the magnetocaloric effect (MCE) and refrigerant capacity or relative cooling power (RCP) of La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials has been investigated. Large low-field-induced magnetic entropy changes are observed in La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials. The La_0.7Ca_0.3MnO₃ material experiences a large entropy change with a first-order magnetic phase transition at the Curie temperature, T_C. On the other hand, La_0.7Ca_0.3Mn_0.95Co_0.05O₃ displays a smaller entropy change with a second order phase transition. While a first-order magnetic transition material induces a larger MCE (7.528 J/kg K at 5 T) at T_C, this is limited to a narrow temperature range, resulting in a relatively small RCP (218 J/kg), while the Co-doped second-order magnetic transition material induces a smaller MCE (7.14 J/kg K for 5 T), but it is spread over a broader temperature range, resulting in a larger RCP (308 J/kg). The maximum magnetoresistance (MR, defined as ρ(0)/ρ(H)-1) under a field of 5 T is about 206% and 333% for La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃, respectively. The refrigeration capacity (RCP) is enhanced in La_0.7Ca_0.3Mn_0.95Co_0.05O₃ (by about 41%) due to small changes from Co doping. The magnetocaloric features of these materials at lower magnetic fields (MCE=3.163 for La_0.7Ca_0.3Mn_0.95Co_0.05O₃ and 4.63 J/kg K for La_0.7Ca_0.3MnO₃ at 1 T), and the high RCP and MR can provide some ideas for exploring novel magnetic refrigerants that can operate with permanent magnets rather than superconducting ones as the magnetic field source.     

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.     

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     

Synthesis of magnetoresistive La0.7Sr0.3MnO3 nanoparticles by an improved chemical coprecipitation method

La_0.7Sr_0.3MnO₃ nanoparticles were prepared by a simple chemical coprecipitation route. Structural, magnetoresistance (MR), and magnetic properties were investigated. Rietveld refinement of X-ray powder diffraction result shows that the sample is single-phase with the space group of R3¯C. The result of field-emission scanning electronic microscopy shows that most of the grain sizes are distributed from 50 to 200 nm. The composition determined by energy-dispersive spectroscopy is the stoichiometry of La_0.7Sr_0.3MnO₃. The ferromagnetic to paramagnetic transition is sharp with Curie temperature T_C=367 K, which further confirms that the sample is single-phase. The steep change in MR at low fields is attributed to the alignment of the magnetization, while the high-field MR is due to the grain boundary effect.     

Coexistence of large positive and negative magnetoresistance in La0.7Ca0.3MnO3 films with microcracks

The coexistence of large positive and negative low-field magnetoresistance (LFMR) in the ferromagnetic La_0.7Ca_0.3MnO₃ thin films with ordered microcrack (MC) distributions is reported. For the films with the highest linear density of MC, the negative LFMR can be up to −60% and rapidly changes to the positive value of 25% at 200 Oe field with the increase of temperature. We discuss the effect based on the spin-polarized tunneling and inhomogeneous magnetic state induced by the natural formations of MC in the films.     

Influence of microstructures on exchange bias behaviors of La0.7Sr0.3MnO3/La0.33Ca0.67MnO3 bilayers

Ferromagnetic La_0.7Sr_0.3MnO₃ (LSMO) and antiferromagnetic La_0.33Ca_0.67MnO₃ (LCMO) layers were grown on SrTiO₃ (STO) substrates by the pulsed laser deposition technique. LSMO films had rougher surfaces and larger grain sizes than LCMO films. Fully strained bilayers, in which each layer was as thin as 10 nm, were prepared by changing their stacking sequences, i.e. LSMO/LCMO/STO and LCMO/LSMO/STO. The former had higher T_C (350 K) than the latter (300 K), and exchange bias effects were only observed in the former bilayers. This revealed that microstructures could play an important role in the transport and magnetic properties of manganese oxide thin films.     

机械合金化La0.7Ca0.3MnO3的晶化动力学及磁电阻研究

通过机械合金化方法制备了单相La_0.7Ca_0.3MnO₃化合物.球磨形成的非晶态结构在920K退火时转变为钙钛矿型相结构.根据质量作用定律,讨论了非晶晶化动力学行为,其晶化转变激活能约为265kJ/mol.同时研究了化合物的电阻特性,发现低温下样品的电阻ρ与温度T的关系为ρ∝T²,随退火温度的升高,ρ-T²曲线斜率下降.在远离居里温度处的低温磁电阻可用Δρ/ρ₀=p₁-p₂T^3/2-p₃T描述. 关键词：     

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.     

Electrical properties and enhanced room temperature magnetoresistance in La0.7Ca0.2Sr0.1MnO3/Pd composites prepared by chemical plating

A series of bulk polycrystalline La_0.7Ca_0.2Sr_0.1MnO₃ (LCSMO)/Pd composites were prepared by chemical plating and structural, electrical, magnetic, and magnetoresistance (MR) properties were investigated. It is found that Pd additions are uniformly distributed on the grain boundaries of the LCSMO grains, which decrease the resistivity and the saturation magnetic moment of the matrix. An interesting phenomenon is observed that at a given field, when the plating time increases, the MR increases at low addition level (0>t (plating time)<40 min) and decreases at high addition level (t>40 min), indicating an optimal plating time of 40 min, at which the MR value is maximum. Our analysis suggests that the improvement of grain boundaries originating from Pd addition plays an important role in enhancing the MR.     

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.     

Magnetic phase coexistence in Tb- and Sr-doped La0.7Ca0.3MnO3 manganite:A temperature-dependent neutron diffraction study

We report the results of the temperature-dependent neutron diffraction measurements on the nearly half-doped (La_0.325Tb_0.125)(Ca_0.3Sr_0.25)MnO₃ manganite sample. The simultaneous doping of magnetic Tb³⁺ and divalent Sr²⁺ in the La_0.7Ca_0.3MnO₃ system results into a large A-site size disorder. Rietveld refinement of neutron diffraction data reveal that the single phase sample crystallizes in a distorted orthorhombic structure. Increased 〈r_A〉 value affects the transport behavior that results into an insulating-like behavior of the sample. Under application of 1 T field sample exhibit insulating-like behavior while insulator-metal transition (T_IM) is exhibited under 5 and 8 T fields. Variable range hoping (VRH) mechanism of charge carriers is exhibited in the insulating region. Field cooled and zero field cooled magnetization measurement shows the Curie temperature (T_C)~47 K. The refinement of the ND data collected at various temperatures below 300 K shows that there is no structural phase transition in the compound. Around 100 K, a magnetic peak appears at lower angle that can be ascribed to the presence of the A-type antiferromagnetic (AFM) phase. Two more peaks are observed around 50 K at lower angles that can be fitted in CE-type antiferromagnetic phase. Splitting of the peaks at lower temperatures is the signature of orbital ordering in the presently studied nearly half-doped manganite system. Results of the detailed structural analysis of the temperature-dependent ND measurements on (LaTb)_0.45(CaSr)_0.55MnO₃ sample has been discussed in the light of coexisting A-type and CE-type antiferromagnetic phases present in the sample at low temperature.     

Metastable structure and properties of (La0.73Bi0.27)0.67Ca0.33MnO3

The electrical transport and magnetic properties of high Bi doped (La_0.73Bi_0.27)_0.67Ca_0.33MnO₃ are studied at the temperature and magnetic field ranges from 10 to 300 K and 0 to 3 T. Significant temperature and magnetic field hystereses are observed in both resistivity and magnetization measurements. Meanwhile, an enhanced magnetoresistance effect, within a wide temperature window, is obtained in the (La_0.73Bi_0.27)_0.67Ca_0.33MnO₃. The hysteresis and enhanced magnetoresistance are discussed based on an inhomogeneous metastable structure related to the Bi dopant.     

Co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature in nanocrystalline La0.7Te0.3MnO3

Sol-gel prepared nanocrystalline La_0.7Te_0.3MnO₃ has rhombohedral crystal structure (space group R3¯C) at room temperature and orders ferromagnetically at ∼280 K (T_C). A large magnetic entropy change of ∼12.5 J kg⁻¹ K⁻¹ is obtained near T_C for a field change of 50 kOe. This magnetocaloric effect could be explained in terms of Landau theory. The temperature dependence of electrical resistivity shows metal-insulator transition at T_C and a giant magnetoresistance of ∼52% in 50 kOe. The co-existence of giant magnetoresistance and large magnetocaloric effect near room temperature makes nanocrystalline La_0.7Te_0.3MnO₃ a promising material for magnetic refrigeration and spintronic device applications.     

Epitaxial growth La0.67Ca0.33MnO3 thin film by radio frequency sputtering method

Perfect epitaxial growth of La_0.67Ca_0.33MnO₃ (LCMO) thin film has been achieved on (1 0 0) LaAlO₃ (LAO) single crystal substrate by radio frequency sputtering method. X-ray diffraction (XRD) and electron diffraction analysis indicates that La_0.67Ca_0.33MnO₃ film grows epitaxially on LaAlO₃ along [1 0 0] direction of the substrate. The resistivity variation with temperature of the film shows a sharp metal to semiconductor transition peak around 253 K, which is close to that of the target. The magnetoresistance (MR) also reveals high quality epitaxy film characteristic at low temperatures and near the metal to semiconductor transition temperature.     

Structure and magnetic order in La0.7Ca0.3Mn0.5Co0.5O3 and La0.8Sr0.2Mn0.5Co0.5O3 perovskites

In this paper we report the study of the perovskites La_0.7Ca_0.3Mn_0.5Co_0.5O₃ and La_0.8Sr_0.2Mn_0.5Co_0.5O₃ by neutron powder diffraction at various temperatures and magnetization measurements in zero applied field and at low cooling regimes. The replacement of half Mn by Co in La_0.7Ca_0.3MnO₃ and La_0.8Sr_0.2MnO₃ destroys their long-range ferromagnetism exhibiting a cluster glass ferromagnetic order similar to the one observed in many cobaltites.     

Particle size effects on La0.7Ca0.3MnO3: size-induced changes of magnetic phase transition order and magnetocaloric study

The structure, magnetic properties, and magnetocaloric effect of La_0.7Ca_0.3MnO₃ ceramics with different particle sizes have been investigated. It is found that the Curie temperature increases first, and then decreases as particle size decreases and the type of magnetic phase transition changes from first-order to second-order, which may be attributed to surface pressure effects. The maximum magnetic entropy change and relative cooling power (RCP) show non-monotonic behaviors with decreasing the particle size. However, for the 3400 nm sample, the magnetic entropy change −ΔS_M reaches the maximum values of 6.41 and 8.63 J/kg K for the field changes of 2.0 and 4.5 T, respectively. Furthermore, the estimated large RCP values under lower magnetic fields in La_0.7Ca_0.3MnO₃ are comparable with those of typical magnetic refrigerant materials in the corresponding temperature range, suggesting those compounds might be promising candidates for magnetic refrigeration.     

Low-field transport properties of (1−x)La0.7Ca0.2 Sr0.1MnO3+x(ZnO) composites

Composite samples (1−x)La_0.7Ca_0.2Sr_0.1MnO₃(LCSMO)+x(ZnO) with different ZnO doping levels x have been investigated systematically. The structure and morphology of the composites have been studied by the X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The XRD and SEM results indicate that no reaction occurs between LCSMO and ZnO grains, and that ZnO segregates mostly at the grain boundaries of LCSMO. The magnetic properties reveal that the ferromagnetic order of LCSMO is weakened by addition of ZnO. The results also show that ZnO has a direct effect on the resistance of LCSMO/ZnO composites, especially on the low-temperature resistance. With increase of the ZnO doping level, T_P shifts to a lower temperature and the resistance increases. It is interesting to note that an enhanced magnetoresisitance (MR) effect for the composites is found over a wide temperature range from low temperature to room temperature in an applied magnetic field of 3 kOe. The maximum MR appears at x=0.1. The low field magnetoresistance (LFMR) results from spin-polarized tunneling. However, around room temperature, the enhanced MR of the composites is caused by magnetic disorder.     

Large magnetoresistance induced by surface ferromagnetism in A-type antiferromagnetic La0.4Sr0.6MnO3 nanoparticles

Grain size effects on magnetic and transport properties for heavily Sr-doped A-type antiferromagnetic La_0.4Sr_0.6MnO₃ ceramics were studied. It was observed that with decrease in grain size, surface ferromagnetism could be introduced due to bond-breaking at surfaces. With decrease in grain size, the surface ferromagnetism was enhanced, and the phase transition order distinguished from the Arrott plot was a second one. The surface-induced ferromagnetism was insulating as judged from transport properties. With decrease in grain size, magnetoresistance was largely improved for both high magnetic and low magnetic fields. Under a 500 Oe magnetic field, the magnetoresistance is improved from 0.2%, 0.1%, 0.03% and 0.02% for the sample with grain size of 150 nm at 10, 100, 200 and 300 K, respectively, to 3%, 2.3%, 0.43% and 0.12% for the sample with grain size of 20 nm at 10, 100, 200 and 300 K. It was interesting to find that large magnetoresistance could be induced due to the surface ferromagnetism in A-type antiferromagnetic La_0.4Sr_0.6MnO₃ nanoparticles, which suggested that it was possible to search for manganites with relatively high low-field magnetoresistance in nanostructured A-type antiferromagnetic materials.     

Pr0.7Ca0.3MnO3陶瓷晶界势垒的交流特性

采用固相烧结方法制备了Pr1-xCaxMnO3(x=0.3)钙态矿结构锰氧化物陶瓷样品,对其在磁场和电场下的直、交流输运性质做了系统研究.通过测量加磁场和零场下的Ⅰ-Ⅴ曲线,得到其居里温度为150K,与VSM测试结果一致.通过测量加磁场与零场下交流的阻抗频谱,发现加磁场后样品的晶界电阻明显减小,而晶粒电阻几乎保持不变,表明Pr1-xCaxMnO3陶瓷多晶样品的CMR效应源于样品的晶界.为确定晶界处的势垒高度,测量了样品在不同频率下的阻抗温谱,根据Arrhenius定律拟合得出势垒高度为117 meV,与用直流R-T数据拟合得出的激活能一致.     

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.