Electronic structure of Sr2FeMoO6

We have used electron spectroscopies to investigate the electronic structure of the double perovskite Sr₂FeMoO₆. The valence-band photoemission spectra present a well-defined cut-off at the Fermi level, indicative of the metallic character of the material. The O 1s X-ray absorption spectrum presents three peaks, which are in good correspondence with the main structures in the unoccupied density-of-states of DF-LDA calculations. The electron energy-loss spectra present two structures which are also interpreted in terms of transitions between the bands obtained in the DF-LDA calculations.     

Density functional studies of LaMnO3 under uniaxial strain

We study the electronic and magnetic properties of tetragonal LaMnO₃ (LMO) under uniaxial strain, appropriate for epitaxially grown LMO heterostructures, from density functional calculations. The optimized tetragonal structure without strain has volume, magnetic order, and Jahn-Teller distortions similar to the bulk LMO, which forms in the orthorhombic structure. Strain affects the relative magnitudes of these distortions and changes the magnetic and conduction properties. While unstrained LMO is a type A antiferromagnet and insulating, we find that it changes to a ferromagnetic metal under tensile strain condition (c-axis stretched). The latter is the result of a diminishing magnitude of the Jahn-Teller distortion with strain, which in turn reduces the splitting of the Mn-e_g orbitals, eventually leading to a metallic state, and finally to a ferromagnet due to the double exchange interaction. The calculated Poisson's ratio from geometry optimization agrees with the experimental values for the bulk.     

A DISCRETE VARIATIONAL METHOD STUDY ON THE ELECTRONIC STRUCTURES OF CaMnO3 AND LaMnO3

The electronic structures of the perovskite oxides, LaMnO₃ and CaMnO₃, with various magnetic structures are studied using the first-principles discrete variational (DV) cluster method based on ab initio local-spin-density approximation (LSDA). The ground states of different magnetic phases (including ferromagnetic (FM), A-type antiferromagnetic (A-AFM), and G-type antiferromagnetic (G-AFM)) have been described in this work. The cubic CaMnO₃ with observed G-AFM magnetic order is found to have a 0.1 eV calculated gap. Both FM CaMnO₃ and LaMnO₃ have "half-metallic" character, which is in agreement with other works. LaMnO₃ with both A-type and G-type antiferromagnetic order have metallic band structures. Part of Jahn-Teller (JT) distortion (Q₂ type) has been taken into consideration for A-AFM LaMnO₃. Under Q₂ type JT distortion, the occupied and unoccupied states of O 2p and Mn 3d states move farther away from the Fermi energy. It is also found that the distortion can further stabilize the structure. The density of states and the binding energy of the distorted A-AFM LaMnO₃ are given in this paper.     

Effect of Sn doping on the magnetic and transport properties of LaMnO3+δ

We report the influence of the Sn doping on the magnetotransport properties of the LaMnO_3+δ perovskite. Two series of samples with nominal LaSn_xMn_1−xO_3+δ (I series) and La_{(1−x)/(1+x)}Sn_xMn_1−xO_3+δ (II series) compositions (x=0, 0.025, 0.05 and 0.10) were prepared at T_s=750°C. The M(T) data under 0.01 and 0.5 T for the I series reveal a depressed magnetization as the Sn content increases suggesting the presence of magnetic clusters with a superparamagnetic behavior. Resistivity measurements indicate an insulator material for all Sn content independently of the applied magnetic field. On the contrary, for the II series the M(T) and M(H) data reveal FM behavior and an improvement of the magnetization as Sn increases. These samples show magnetoresistance. The magnetotransport properties are discussed in terms of the presence of A-site cation vacancies.     

Charge ordering and structural transitions in Pr0.5Sr0.41Ca0.09MnO3

The structural and magnetic transitions in Pr_0.5Sr_0.41Ca_0.09MnO₃ have been investigated by neutron diffraction and electron microscopy. Two structural transitions, Imma to I4/mcm and I4/mcm to Pmmn, are observed by decreasing the temperature. Two magnetic transitions, from a paramagnetic insulating to a ferromagnetic metallic and from a ferromagnetic metallic to an antiferromagnetic insulating states at T_C=250 K and T_N=180 K, respectively, are also observed. The structures of these three forms have been determined from neutron powder diffraction data. The first important result concerns the low temperature antiferromagnetic CE type and charge ordered structure, which has been refined in the Pmmn space group, without any constraint. This structure is completely long range ordered, with two Mn-sites, Mn³⁺ in tetragonally elongated octahedra, and Mn⁴⁺, off-centered in nearly regular octahedra. The second important point concerns the abrupt character of the structural transition from the I4/mcm to the Pmmn structure, without any appearance of incommensurability. The magnetic and transport properties of this compound are compared with those of Pr_0.5Sr_0.5MnO₃.     

希夫碱配合物M3L3(NO3)6(H3O)2的合成与光谱性质

以4-氨基-1,2,4-三氮唑与对二甲氨基苯甲醛为原料, 在冰醋酸催化下合成了配体4-氨基-1,2,4-三氮唑缩对二甲氨基苯甲醛（L）。 然后利用L与过渡金属硝酸盐［M(NO3)2·xH2O(M=Cu,　Co,　Zn,　Cd; x=3～6)］在无水乙醇中反应, 制得固态配合物M3L6(NO3)6(H2O)2。 通过元素分析、 红外光谱、 紫外光谱、 荧光光谱等手段对合成的配体及配合物进行了表征。 实验结果表明, 该物质是一种多晶粉末状的发光材料,　在紫外光的激发下,　在乙醇溶液体系中的荧光发射峰在416 nm处,　为蓝色荧光, 色纯度高,　荧光量子效率高, 而配合物M3L6(NO3)6(H2O)2的荧光发射峰则红移至445 nm左右, 同时荧光强度显著增强。　M3L6(NO3)6(H2O)2中与M(Ⅱ)发生配位作用的基团是配体中三氮唑环上的氮原子。     

Strong charge carrier effect on the magnetic coupling of La-doped CaMnO3

The exchange interactions in polycrystalline samples of Ca_1−xLa_xMnO₃ (0.00x0.05) are studied by means of Raman scattering and electron paramagnetic resonance. Dramatic reductions in the spin-phonon interactions and magnetic correlations are observed for La doping levels as small as 2–3%. These results show that the charge carriers play an important role in the overall exchange coupling in the electron-doped manganites, even at very low doping levels.     

Structural relaxation and Jahn-Teller distortion of LaMnO3 (0 0 1) surface

We studied in detail the structural relaxation and Jahn-Teller distortion in LaMnO₃ (0 0 1) surface of the orthorhombic phase by means of classical atomistic simulation. It is found that MnO₂-terminated surface is more energetically favorable than LaO-terminated surface by 0.34 eV. The standard deviation of Mn-O bond lengths of MnO₆ octahedra and Jahn-Teller distortion oscillate in LaMnO₃ (0 0 1) surface. Our simulated atomic displacements in the surface are compared with some ab initio studies.     

Electrical transport of (1−x)La0.7Ca0.3MnO3+xAl2O3 composites

We report the resistivity (ρ)-temperature (T) patterns in (1-x)La_0,7Ca_0,3MnO₃+xAl₂O₃ composites (0≤x≤0.05) over a temperature regime of 50-300 K. Al₂O₃ addition has increased the resistivity of these composites. The Curie temperature (T_C) is almost independent on the Al₂O₃ content and is about 250 K for all the samples, while the metal-insulator transition temperature (T_MI) decreases with increasing Al₂O₃ content. Based on the phenomenological equation for conductivity under a percolation approach, which is dependent on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the experimental data (ρ−T) from 50 to 300 K and find that the activation barrier increases as Al₂O₃ content increases.     

Cation inter-diffusion between LaMnO3 and LaCoO3 materials

Cation inter-diffusion between polycrystalline LaMnO₃ and LaCoO₃ pellets has been studied at 1373-1673 K in air by electron microprobe analysis. Inter-diffusion coefficients were evaluated by the Boltzman-Matano method from Mn³⁺ to Co³⁺ concentration profiles. The cation inter-diffusion is thermally activated and follows Arrhenius behaviour. The activation energies have been calculated and the mechanism for the B-site cation diffusion in La(Mn,Co)O₃ solid solution suggested. Cation diffusion coefficients in the end members LaMnO₃ and LaCoO₃ were estimated. Cation mobility in LaMnO₃ is higher than in LaCoO₃. It is suggested that higher cation diffusion in LaMnO₃ is due to the specific defect chemistry of this material, caused by the relative stability of manganese in a higher oxidation state (Mn⁴⁺). The results are compared to previous reports on cation diffusion in perovskite oxides.     

Silver addition in thick films of La2/3Ca1/3MnO3 perovskite

Thick films of La_2/3Ca_1/3MnO₃ with 10 wt% of silver are grown on single crystal SrTiO₃ by using the paint-on method. The electrical properties of the films are quite different compared to the pristine counterpart. The samples with silver addition exhibit a very low resistivity and the insulator to metal transition occurs at higher temperature (270 K) than the undoped samples. The resistance versus temperature dependence in these films is very sharp and the magnetoresistance ratio is restricted to a narrow temperature range, close to the electric transition for both cases. The improved properties of the thick films are associated with the improvement of the connectivity between the grains, although microstructural effects are not ruled out.     

Electron diffraction evidence of charge-ordering at room-temperature in La1−xCaxMnO3 (0.55≤x≤0.67)

Temperature dependent electron diffraction of La_1−xCa_xMnO₃ for 0.55≤x≤0.67 using transmission electron microscope (TEM) has been carried out in the temperature range of 106-300 K to study the melting of charge-ordering across the transition temperature. Clear signature of charge-ordering as evident by the presence of diffuse super-lattice spots persist even at room temperature. This has been consistently observed for four different samples with compositions within the range of 0.55≤x≤0.67. The results indicate emergence of some degree of itinerancy in the localized charge carriers as temperature rises.     

Thermal expansion and structure of orthorhombic CaMnO3

The structure of CaMnO₃ has been studied from room temperature to 800 °C by high-resolution synchrotron X-ray powder diffraction. It is concluded that CaMnO₃ remains orthorhombic in Pbnm over the entire temperature range, with the expansion in the cell volume well fitted to the expression Vol=207.37(2)+0.00563(8)T+1.17(9)×10^-6T². The magnitude of the MnO₆ tilts is estimated from the refined structural parameters and these progressively reduce as the temperate is increased.     

Enhanced low-field-magnetoresistance and electro-magnetic behavior of La0.7Sr0.3MnO3/BaTiO3 composites

We report the structural, magentoresistance and electro-magnetic properties of ferromagnet–ferroelectric–type (1−x)La_0.7Sr_0.3MnO₃/xBaTiO₃ (with x=0.0%, 3.0%, 6.0%, 12%, 15.0% and 18.0%, in wt%) composites fabricated through a solid-state reaction method combined with a high energy milling method. The insulator–metal transition temperature shifts to a lower temperature and resistivity increases while the feromagnetic–paramagnetic transition temperature remains almost unchanged with the increase of BaTiO₃ content. Magnetoresistance of the composites at an applied magnetic field H=3 kOe is enhanced in the wide temperature ranges with the introduction of BaTiO₃, which could be explained by the enhanced spin polarized tunneling effect induced by the introduction of BaTiO₃. The low-field magnetoresistance of the composite is analyzed in the light of a phenomenological model based on the spin polarized tunneling at the grain boundaries. Furthermore, the temperature dependence of resistivity for this series has been best-fitted by using the adiabatic small polaron and variable range hopping models. These models may be used to explain effect of BTO on the electronic transport properties on high temperature paramagnetic insulating region.     

Low temperature magnetotransport properties of La0.55Ho0.15Sr0.3MnO3

Magnetotransport data measured in thin films of La_0.55Ho_0.15Sr_0.3MnO₃ down to very low temperatures (0.25 K) are reported. The samples presented colossal magnetoresistance with a T_C close to 200 K. A minimum in the resistance vs. T curve and a drop in the ZFC magnetization were also observed. It was also found a T-dependent relaxation effect after the magnetic field was either applied or removed. These results can be understood within the framework where electronic scattering occurs across magnetic domain walls in a reentrant spin-glassy-like phase.     

Anomalous aging and strain induced time dependent phenomena in ultra-thin La0.65Ca0.35MnO3 films

We have shown that ultra-thin La_0.65Ca_0.35MnO₃ films exhibit strong metastable behavior. The resistance can vary with time significantly, suggesting that a state of dynamic phase separation exists whereby one phase grows at the expense of another. Physical properties associated with the metastable behavior have been investigated on the films grown on different substrates. We have found that ultra-thin films age much faster than the thicker counterparts and more interestingly the metastability in the resistance of these films enhanced when aged.     

Spinel LiMn2O4 active material with high capacity retention

Heating the mixture of LiMn₂O₄ and NiO at 650 °C was employed to enhance the cyclability of spinel LiMn₂O₄. The results of scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy analyses implied that a LiNi_xMn_2−xO₄ solid solution was formed on the surface of LiMn₂O₄ particles. And charge-discharge tests showed that the enhancement of the capacity retention of modified LiMn₂O₄ is significant, maintained 97.2% of the maximum capacity after 100 cycles at charge and discharge rate of C/2, while the pure one only 75.2%. The modified LiMn₂O₄ also results in a distinct improvement in rate capability, even at the rate of 12C. The improvement of electrochemical cycling stability is greatly attributed to the suppression of Jahn-Teller distortion at the surface of spinel LiMn₂O₄ particles.     

Fitting of transport measurements in polycrystalline La2/3Ca1/3MnO3

Using a previous qualitative explanation to describe the transport properties of polycrystalline La_2/3Ca_1/3MnO₃ thick films, we achieved a good fit of the temperature dependence of the resistance R(T). Depending on the sample, we have observed different metal–insulator (MI) transitions while the magnetic behavior is always similar. Small regions of depleted T_c adjacent to the grain boundary could have an important resistance contribution without affecting the magnetic properties in an appreciable manner. In this work, we achieve a quantitative explanation for the different transport behaviors that we have observed experimentally.     

Correlation between magnetic and transport properties of phase-separated La0.5Ca0.5MnO3

The effect of low-magnetic fields on the magnetic and electrical transport properties of polycrystalline samples of the phase-separated compound La_0.5Ca_0.5MnO₃ is studied. The results are interpreted in the framework of the field-induced ferromagnetic fraction enlargement mechanism. A fraction expansion coefficient _f, which relates the ferromagnetic fraction f with the applied field H, was obtained. A phenomenological model to understand the enlargement mechanism is worked out.