Research on charge-ordering state in La0.5Sr0.5MnO2.88 and La0.5Sr0.5Mn0.5Ti0.5O3 systems

The structural, magnetic and transport properties of La_0.5Sr_0.5MnO_2.88 and La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ samples have been investigated systematically. Indeed, this series has been considered to understand the influence of physical parameters such as oxygen deficiency and titanium doping effect in undoped La_0.5Sr_0.5MnO₃ sample. Ceramic material based on La_0.5Sr_0.5MnO_2.88 exhibits interesting behaviours of charge-ordering (CO), ferromagnetic (FM) states and a good conductivity down to the lowest temperatures. The substitution of Ti for Mn destroyed drastically the CO, damaged the motion of itinerant e_g electrons and changed the local parameters of perovskite cell. A change of the structure from tetragonal to rhombohedral symmetry is observed causing a weakening of double-exchange interaction. The experiment results show that the suppression of the CO is sensitive to the variety of Mn³⁺/Mn⁴⁺ ratio. In a field of 8 T at 10 K, FM and CO phase can be evaluated to be ∼20:80 according to the μ_exp/μ_cal ratio for La_0.5Sr_0.5MnO_2.88, whereas the CO state is suppressed for La_0.5Sr_0.5Mn_0.5Ti_0.5O₃ sample, FM and anti-ferromagnetic (AFM) phase are coexisted and evaluated to be ∼54:46, respectively.     

Inelastic magnetic X-ray scattering from highly correlated electron systems: La1.2Sr1.8Mn2O7, La0.7Sr0.3MnO3 and Fe3O4

Magnetic Compton profiles have been measured for the colossal magnetoresistance manganites La_1.2Sr_1.8Mn₂O₇ and La_0.7Sr_0.3MnO₃, and for magnetite Fe₃O₄, along various crystallographic directions, over a wide range of temperatures and magnetic fields. The experimental results are interpreted via first-principles computations for the double layer manganite, La_1.2Sr_1.8Mn₂O₇, and by using a simple model involving atomic d-orbitals and free electrons for the other two compounds. For all three materials a preference for the occupation of e_g orbitals is found, particularly, for orbitals of dx²−y² symmetry. An itinerant electron contribution is adduced at all temperatures in magnetite; such a contribution also appears in La_1.2Sr_1.8Mn₂O₇, but it is present only at low temperatures in La_0.7Sr_0.3MnO₃.     

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.     

Electrical conductivity and complex impedance analysis of 20% Ti-doped La0.7Sr0.3MnO3 perovskite

The electrical conductance of 20% Ti-doped La_0.7Sr_0.3MnO₃ (LSMO) was measured using admittance spectroscopy over a wide temperature and frequency ranges. The impedance plane plot shows semicircle arcs at different temperatures and an electrical equivalent circuit has been proposed to explain the impedance results. Activation energy inferred from conductance spectrum matches very well with the value estimated from relaxation time indicating that relaxation process and conductivity have the same origin. The electrical conductance of La_0.7Sr_0.3Mn_0.8Ti_0.2O₃ is found to be dependent on temperature and frequency. Also, the electronic conduction appears to be dominated by thermally activated hopping of small polaron (SPH) at high temperatures and by variable range hopping (VRH) at low temperatures.     

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.     

钙钛矿锰氧化物La0.7Sr0.3MxMn1-xO3(M=Cr,Fe)的巨磁电阻效应与磁性

研究了溶胶-凝胶法制备氧化物巨磁电阻材料的工艺,制备了La_0.7Sr_{0.3< /sub>CrxMn1-xO3(x=0,0.10,0.15)和La0.7Sr0.3FexMn1-xO3(x=0.05,0.10,0.16)两 系列的单相钙钛矿锰氧化物多晶样品,并研究了Cr,Fe替代La0.7Sr0.3MnO3中部分Mn后对其结构、磁性和巨磁电阻性质的影响.观察到La0.7 Sr0.3Cr0.15Mn0.85O3和La0. 7Sr0.3Fe0.05Mn0.95O3两个样品的 电阻-温度曲线都出现了双峰.定性讨论了可能产生双峰的机制.随Cr(或Fe)替代量的增加, 材料的居里温度很快下降,铁磁性减弱,导电性降低,巨磁电阻效应增强.但与Fe掺杂相比 ,相同数量的Cr掺杂对材料的影响要小. 关键词： 巨磁电阻效应 溶胶-凝胶工艺 电阻-温度曲线 金属绝缘体转变}     

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     

Magnetic disorder induced enhanced magneto-resistance in La0.5Sr0.5Co1−xRuxO3

We observe a sharp increase in negative magneto-resistance ratio up to 40% for x=0.1, in La_0.5Sr_0.5Co_1−xRu_xO₃ which is due to the magnetic disorder induced by an anti-ferromagnetic interaction between Co and Ru ions. We also observe a metal to insulator and a ferromagnetic to anti-ferromagnetic transition for 0≤x≤0.3. Ruthenium (IV) ion disrupts an intermediate spin state of cobalt (Co³⁺:t_2g⁵e_g¹), forcing a double exchange mediated ferromagnetic state to an anti-ferromagnetic spin state for x≥0.2.     

Possible anisotropy gap in La1.35Sr1.65Mn2O7 and La1.5Sr0.5NiO4 detected through specific heat and magnetization measurements

Magnetization and specific heat measurements, as a function of temperature, were performed on single crystals of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄, under different applied magnetic fields (H). The specific heat in La_1.35Sr_1.65Mn₂O₇ was decreased for H=9 T parallel to the crystal c axis, compared with H=0, possibly due to a suppression of spin-wave excitations (magnons) in that ferromagnetic bilayer structure. On the other hand, the applied magnetic field had no effect in the specific heat of the antiferromagnetic La_1.5Sr_0.5NiO₄. For H=9 T and below the temperature of 4 K the specific heat data, for each crystal, was well fitted by an exponential decay law. This allowed the calculation of energy gaps around 1 meV for both compounds, in close agreement with Δ=2μ_BH for an expected energy gap in the magnon spectrum. Detailed magnetization measurements showed monotonic variations below 4 K and a steep increase close to 2 K. Both magnetization and specific heat measurements suggest the existence of an anisotropy gap in the energy spectrum of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄.     

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.     

CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF La1.2Sr1.8-xCaxMn2O7

The effect of divalent cation substitution on the structure and magnetic properties of La_1.2Sr_1.8-xCa_xMn₂O₇ (x = 0－0.900) is investigated in this paper. Partly replacing divalent cation Sr²⁺ by Ca²⁺ ions results in the weakening and then disappearance of long-range ferromagnetic ordering, and the formation of spin canting and low-temperature spin-glass. Based on structural analysis by Rietveld profile fitting, we suggest that this variation of magnetic property be related to a Jahn－Teller-type attice distortion of MnO₆ octahedra due to the introduction of the smaller sized Ca²⁺ ions.     

The effect of transition element doping on the electronic and magnetic properties of La1.4Sr1.6Mn2O7

The effect of transition element (TE=Cr, Fe, Co, Ni, Cu, Zn) doping on the electronic transport and magnetic properties in the bilayer manganite La_1.4Sr_1.6Mn₂O₇ is studied for the same dopant concentration fixed at 2%. Doping does not cause change in structure but different behavior in magnetic and transport properties. Except for Cr, all the other dopings significantly shift the magnetic transition temperature (T_C) to a lower temperature. Associated with such a decrease, the insulator-metal transition temperature (T_IM) decreases and the peak resistivity (ρ_p) at T_IM increases. Cr doping enhances T_C and T_IM as well as decreases ρ_p. Fe doping apparently has a stronger effect than Co and Ni doping. It is also indicated that Cu doping causes an anomalously large increase in ρ_p. These behaviors are compared with those observed in other bilayer manganites such as La_1.2Sr_1.8Mn₂O₇ as well as in La_0.7Ca_0.3Mn_1−xTE_xO₃.     

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.     

Preparation and low field magnetoresistance of double layered manganite La1.4Ca1.6Mn2O7

Double layered manganite of La_1.4Ca_1.6Mn₂O₇ (DLCMO) was prepared using solid state reaction method and had a metal-insulator transition temperature (T_MI) of 125 K. The short range 2D-feerromagnetic ordering (T_C2) starts growing when T<168 K and it gets converted into 3D-ferromagnetic ordering (T_C1) at 114 K. Low field magnetoresistance (MR) behaviour of the DLCMO was investigated and compared with an infinite layered manganite La_0.7Ca_0.3MnO₃ (LCMO). For DLCMO, in the temperature range between T_C1 and T_C2, the MR showed a gradual increase with the magnetic field. The observed MR and R-T behaviour of double layered manganite for T_C1<T<T_C2 has been explained in the frame work of the two phase model [ferromagnetic (FM) domains and paramagnetic (PM) regions] and percolative behaviour of transport in FM-PM mixture.     

Effect of Mo doping on magnetic and transport properties of La0.5Sr0.5CoO3

The substitutional effect of Mo on the magnetic and transport properties of double exchange ferromagnets, La_0.5Sr_0.5Co_1−x Mo_xO₃ (0?x?0.2) has been investigated. Substitution of 10% Mo at the Co-site of La_0.5Sr_0.5CoO₃ decreases the Curie temperature by ∼60 K than that of the parent compound and the long-range ferromagnetic ordering disappears for x?0.2. The Mo-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_c. The insulating state is found to obey Mott's variable range hopping of conduction. The effect of Mo substitution is attributed to the factors namely, (i) the dilution of magnetic Co sublattice, (ii) the reduction of Co⁴⁺/Co³⁺ ratio resulting in a reduced carrier concentration and (iii) disruption of the intermediate spin structure of Co, namely Co³⁺: t_2g⁵e_g¹.     

Microstructural characterization of La0.4Sr0.6Co0.8Fe0.2O3-δ films deposited by dip coating

The dip-coating method has been successfully used for depositing porous electrodes of La_0.4Sr_0.6Co_0.8Fe_0.2O_3-δ (LSCF) films. Perovskite oxide cobaltites powders have been prepared by an acetic acid-based gel route. Then, cathode films were deposited onto ceramic substrates of the usual electrolyte Cerium Gadolinium Oxide (CGO) by dip coating. The structure and morphology of the powders and films were characterized by X-ray, diffraction (XRD) and scanning electron microscopy (SEM) respectively, to study the correlation between microstructure and deposition parameters. Optimum parameters for obtaining continuous, homogeneous and crack free LSCF films were determined.     

Observation of mixed-phase behavior in the Mn-doped cobaltite La0.7Sr0.3Co1−xMnxO3 (x=0-0.5)

Studies on La_0.7Sr_0.3Co_1−xMn_xO₃ (x=0-0.5) compounds evidence that the interaction between Mn and Co ions in this system is antiferromagnetic super-exchange and not ferromagnetic (FM) double-exchange (DE). As a result, antiferromagnetism and magnetic glassiness develop steadily with increasing Mn content and the system becomes a spin glass at x∼0.1. Analyses of high-field magnetization data indicate that the system consists of two major phases: a metallic FM phase which magnetically saturates in rather low field, and an insulating non-FM phase which has a linear dependence of magnetization on magnetic field. In the low doping regime, the fraction of the non-FM component expands with temperature at the expense of the FM phase and becomes maximal at T_C. Ferromagnetism reappears in highly doped (x≥0.2) compounds due to the presence of DE interaction between the Mn ions. The small volume fraction of the FM phase derived from the M(H) data in high-field region supports the coexistence of insulating and FM behaviors in the highly doped samples.     

Chemical pressure effect on the magnetic order of the La1.4Sr1.6Mn2O7 bilayered manganite

In this paper we have studied, by means of high-resolution neutron powder diffraction, the structural and magnetic feature of pure La_1.4Sr_1.6Mn₂O₇ and Sr-doped (25%) La_1.4Sr_1.6Mn₂O₇.Our data reveal the stabilization of the A-type AFM long-range order for the La_1.4Sr_1.6Mn₂O₇ bilayered manganites induced by the partial replacement of the Sr with the smaller Ca, keeping constant the hole doping. This can be in turn due to the change in the orbital character of the e_g electrons as a function of Ca-doping.     

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.     

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.