Dielectric loss of half-doped manganite La_(0.5)Ca_(0.5)MnO_3

The dielectric loss tanδ of half-doped manganite La 0.5 Ca 0.5 MnO 3 is investigated using Green's function technique. The La 0.5 Ca 0.5 MnO 3 is described by the Kondo-lattice model in the double exchange limit, taking into account the Jahn-Teller distortion and the super-exchange interaction between the localized electrons. It is found that the intensity of tanδ decreases with increasing | ε JT |, V, and U. It is also observed that the transition temperature T P rises as | ε JT | and U increase. It is worth noting that T P remains unchanged and the strength of tanδ increases with increasing g. The calculated dielectric loss results are explained theoretically, and these behaviors are in qualitative agreement with the experimental results.     

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.     

The static and dynamic lattice effects in La1−xCaxMnO3

The structural and magnetic behavior of the perovskite insulator La_0.9Ca_0.1MnO₃ were studied as a function of temperature from 15 to 300 K by neutron powder diffraction. Although this compound shows an anomalous response of the lattice parameters around T_c (150 K), the behavior of the oxygen/manganese Debye-Waller factors is in clear contrast to its “colossal magnetoresistance” (CMR) counterpart La_0.65Ca_0.35MnO₃. We speculate that the difference is intimately associated with the metal-insulator transition in the latter compound.     

Role of the interfacial state: a comparison of Co/Al2O3/NiFe and La0.7Ca0.3MnO3/Al2O3/La0.7Ca0.3MnO3 tunnel junctions

Two junctions of Co/Al₂O₃/NiFe (J₁) and La_0.7Ca_0.3MnO₃/Al₂O₃/La_0.7Ca_0.3MnO₃ (J₂) were prepared to compare their tunneling magnetoresistance (TMR) in consideration of interfacial state effects. The structural and transport properties of the layered samples were characterized by X-ray and magnetic measurements, showing indeed an interfacial state dependence. The influences such as from a CoO sublayer in J₁ and from interfacial coherence in J₂ were discussed. The largest TMR observed amounts to 16% (290 K) for J₁ and 65% (40 K) for J₂.     

Anelastic relaxation of Pr1/2Ca1/2MnO3 at low and medium frequencies in the 350–500 K range

In previous works (Jornadas SAM 2000; J. Magn. Magn. Mater. 226–230 (2001) 988) the low-frequency anelastic effects of two manganite perovskites of La_2/3Sr_1/3MnO₃ and La_2/3Ca_1/3MnO₃ were studied at 1 Hz and temperatures above those of the metal–insulator transition. An important internal friction peak (P1) appears at 414 and 419 K, respectively, with a modulus variation and no appreciable contribution to electrical resistivity. Another compound Pr_1/2Ca_1/2MnO₃ of the same family has been studied by anelastic mechanical spectroscopy in order to add new data which could elucidate the (P1) peak mechanism. The measurements were made in a sub-resonant forced pendulum (0.1–20 Hz) and in a vibrating reed equipment (kHz range). A stable (P1) peak has been detected at 410 K (1 Hz), with a corresponding modulus step. The appearance of this relaxation peak in the Pr_1/2Ca_1/2MnO₃ compound, and its high activation energy value, similar to the other compounds measured, indicates that the microscopic origin of this relaxation does not correspond to an oxygen jump (characteristic activation energy0.8–0.9 eV).     

Magnetic transition behavior of perovskite manganites Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 polycrystalline

A polycrystalline sample Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 is prepared by the conventional solid state reaction method. The structure and magnetic properties are investigated with x-ray diffraction(XRD) patterns, a superconducting quantum interference device(SQUID), and electron spin resonance(ESR). The sample is in single phase with the space group Pbnm symmetry. With the decrease of temperature, Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 undergoes three magnetic transitions: ferromagnetic transition at TC≈ 210 K, charge-ordering at TCO≈ 175 K, and antiferromagnetic transition at TN= 155 K. In addition, the activation energy Ea ≈ 52.78 me V can be extracted by curve fitting.     

High hydrostatic pressure effect on magnetic state of anion-deficient La0.70Sr0.30MnOx perovskite manganites

The magnetic state of La_0.70Sr_0.30MnO_x (x=2.85, 2.80) anion-deficient manganites is studied experimentally under hydrostatic pressure up to 5.2 GPa. These materials possessing the properties of a spin-glass state. The La_0.70Sr_0.30MnO_2.85 exhibits a coexistence of the rhombohedral (R3¯c) and tetragonal (I4/mcm) crystal structures and below T_f 50 K the spin-glass state is formed. The La_0.70Sr_0.30MnO_2.80 exhibits the tetragonal (I4/mcm) crystal structure. For this compound a phase-separated magnetic state below T_f is formed, involving coexistence of C-type antiferromagnetic (AFM) clusters within spin-glass matrix. In both compounds the crystal structure and magnetic states remain stable upon compression. Under the hydrostatic pressure up to 1 GPa, the La_0.70Sr_0.30MnO_2.85 is a spin glass with a smeared phase transition to the paramagnetic state. The freezing temperature T_f of the magnetic moments of the ferromagnetic clusters increases at a rate of 4.30 K/GPa and the magnetic ordering temperature T_MO increases at a rate of 12.90 K/GPa. The enhancement of the ferromagnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite under hydrostatic pressure is explained by the redistribution of oxygen vacancies and a decrease in the unit cell parameters.     

Origin of cathodic degradation and new phase formation at the La0.9Sr0.1MnO3/YSZ interface

New phase formation at the La_0.9Sr_0.1MnO₃/YSZ interface and its effects on the cathodic performances were studied at 900 °C in air. The resistance caused by the interfacial product layer kept increasing with time to reach up to 40% of the total resistance after 500 h. The interfacial product was identified as La₂Zr₂O₇ by XRD measurement. The electrical conductivity of La₂Zr₂O₇ (2.4 × 10⁻⁵ S cm⁻¹ at 1000 °C), measured by AC impedance and current interruption methods, was 4 to 7 orders of magnitude smaller than those of La_0.9Sr_0.1MnO₃ electrode or YSZ electrolyte. Either the electronic conductivity or the electrochemical O₂ reduction activity of La₂Zr₂O₇ was negligible. Combining these results, a conclusion was made that the cathodic degradation comes mainly from the growth of interfacial product layer and its contribution to the cell resistance increment is ohmic in nature.     

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.     

Field-induced insulator-metal-insulator transitions in low-energy H_2~+ ion-irradiated epitaxial La_(2/3)Ca_(1/3)MnO_3 thin films

Epitaxial La 2/3 Ca 1/3 MnO 3 thin films grown on LaAlO 3 (001) substrates were irradiated with low-energy 120-keV H 2 + ions over doses ranging from 10 12 ions/cm 2 to 10 17 ions/cm 2 . The irradiation suppresses the intrinsic insulator-metal (I-M) transition temperature and increases the resistance by reducing the crystallographic symmetry of the films. No irradiation-induced columnar defects were observed in any of the samples. The specific film irradiated at a critical dose around 8 × 10 15 ions/cm 2 is in a threshold state of the electric insulator where the I-M transition is absent. In an external field of 4 T or higher, the I-M transition is restored and thus an enormous magnetoresistance is observed, while a negative temperature coefficient resumes as the temperature is reduced further. Magnetic relaxation behavior is confirmed in this and other heavily irradiated samples. The results are interpreted in terms of the displacement of oxygen atoms provoked by ion irradiation and the resulting magnetic glassy state, which can be driven into a phase coexistence of metallic ferromagnetic droplets and the insulating glass matrix in a magnetic field.     

Isotopically driven transitions in LaPrCaMnO system

The effect of oxygen isotope substitution on transport and magnetic properties is studied for (La_1−yPr_y)_0.7Ca_0.3MnO₃ ceramics and thin films. The temperature dependence of electrical resistivity reveals the metal–insulator transition induced by the ¹⁶O→ ¹⁸O substitution at y=0.75 (ceramics) and y=0.5 (films on LaAlO₃). Neutron powder diffraction at y=0.75 demonstrates a striking difference between magnetic structures in the samples with ¹⁶O and ¹⁸O. Measurements of AC magnetic susceptibility allow us to analyze the magnetic phase diagram and its changes related to the isotope substitution.     

Structural and electrical characterisation of La0.5Ca0.5MnO3 thin films grown by pulsed laser deposition

Thin films of perovskite manganite, with nominal composition La_0.5Ca_0.5MnO₃, have been prepared by pulsed laser deposition on (1 0 0) SrTiO₃, (1 0 0) LaAlO₃, (1 0 0) Si and YSZ/CeO₂-buffered (1 0 0) Si substrates. Structural and electrical characterisation was performed on the films. The magneto-transport properties of all the thin films depart from the bulk behaviour. The LCMO film grown on buffered Si shows an insulator–metallic transition around 130–150 K while the one deposited directly on Si displayed a similar behaviour under a melting field of 1 T. However, that transition is absent in the films grown on LAO and STO. We suggest that appropriate stress values induced by the substrate favour the formation of metallic percolative paths.     

Structural study and magnetoresistance effect of epitaxial La0.67Sr0.33MnO3–δ and Pr0.7Ca0.3MnO3−δ multilayer films

La_0.67Sr_0.33MnO_3−δ (LSMO) and Pr_0.7Ca_0.3MnO_3−δ (PCMO) multilayer epitaxial films, which were fabricated with different LSMO and PCMO layer thickness on LaAlO₃ single crystal substrates of (0 0 1) orientation by a direct current magnetron sputtering technique, were studied further, after the structure, magnetoresistance effect and magnetic properties of LSMO/PCMO/LSMO (LPL) trilayer epitaxial films were systemically studied. The superlattice structures of multilayer films were observed according to the diffraction peaks of X-ray diffraction patterns at small angles. The metal–insulator transition temperature (T_P) and peak resistivity (ρ_max) obviously changed when we altered the thickness of PCMO middle layer and the intra-field related with the thickness of those layers and their interaction. Considering the effect of the distribution of electrical field and current, and the interaction among the layers of LSMO and PCMO, an effective fact n* was introduced to replace n (the number of layer). All the calculated values of ρ (the resistivity of multilayer films) accorded with the experimental values.     

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.     

Properties of nonstoichiometric Pr0.6−xSr0.4MnO3 as the cathodes of SOFCs

A series of samples Pr_0.6−xSr_0.4MnO₃ (x=0, 0.01, 0.05, 0.1, 0.15, 0.2) were synthesized by a solid state reaction method. Pr deficiency at the A site has a great effect on the properties of Pr_0.6−xSr_0.4MnO₃ as the cathode of SOFCs (solid oxide fuel cells). Compared to the commonly used La_0.6Sr_0.4MnO₃ and La_0.55Sr_0.4MnO₃ cathode, Pr_0.6−xSr_0.4MnO₃ is better in the properties of conductivity, overpotential and impedance. In all the samples, the one with x=0.05, Pr_0.55Sr_0.4MnO₃, revealed the best performance in the measured temperature range.     

Charge ordering characteristics in Y0.5Ca0.5MnO3 manganite

The charge ordering characteristics in Y_0.5Ca_0.5MnO₃ manganite, prepared by sol–gel process, have been investigated experimentally. It is found that the superlattice diffractions appear in the electron diffraction patterns recorded at low temperatures, while only basic Brag diffraction spots can be observed when temperature is higher than 300 K. This provides direct evidence for the existence of charge ordering in Y_0.5Ca_0.5MnO₃. The magnetization and specific heat measurements indicate the charge ordering temperature of Y_0.5Ca_0.5MnO₃ is 290 K, around which both the magnetization and specific heat reveal anomalous behaviors. We also observed that the MnO bond length changed remarkably and the effective number of carriers reduced prominently with decreasing temperature around charge ordering temperature through transform infrared spectra measurements.     

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.     

Surface atomic imaging of La2CuO4 and superconducting Tl2Ba2Ca2Cu3O10

Surface structures of the high T_c oxide superconductors Tl₂Ba₂Ca₂Cu₃O₁₀ and La₂CuO₄ have been studied by high resolution electron microscopy. In addition to the single atomic layer of La on the (113) surface observed previously, several atomic layers of the C-form of La₂O₃ were found to coat the (001) surfaces of La₂CuO₄. Surface reconstruction with the incorporation of excess Ba on the (110) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ has been observed together with a stepped (11l) surface produced by a combination of the (110) and (001) planes. The (001) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ was also found to terminate with a Ba-O layer. Possible mechanisms for the formation of these surface structures are discussed.     

航天用热致变色材料低太阳吸收率研究

La_0.7Ca_0.2Sr_0.1MnO₃热致变色材料是一种发射率随温度变化的热控功能材料,不足的是这种材料的太阳吸收率过大。针对此问题,本文从多层薄膜理论和最优化理论出发,获得了基于多层薄膜的低太阳吸收率热致变色材料。根据计算得到的膜系结构参数,采用电子束蒸发法在热致变色材料表面沉积了多层薄膜,并对设计计算与实验测试结果进行研究和分析。研究表明:多层薄膜结构的设计能将热致变色材料的太阳吸收率从0.78降低至0.27,提高了热致变色材料的实用性。     

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.