Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Investigation of activated transport in hole doped rare earth manganites in the high temperature paramagnetic regime

Electronic transport in the high temperature paramagnetic regime of the colossal magnetoresistive oxides, La(1-x)A(x)MnO(3), A=Ca, Sr, Ba, x similar or equal to 0.1-0.3, has been investigated using resistivity measurements. The main motivation for this work is to relook into the actual magnitude of the activation energy for transport in a number of manganites and study its variation as a function of hole doping (x), average A-site cation radius (< r(A)>), cationic disorder (sigma(2)) and strain (epsilon(zz)). We show that contrary to current practice, the description of a single activation energy in this phase is not entirely accurate. Our results clearly reveal a strong dependence of the activation energy on the hole doping as well as disorder. Comparing the results across different substituent species with different < r(A)> reveals the importance of sigma(2) as a metric to qualify any analysis based on (r(A)). (c) 2006 Elsevier Ltd. All rights reserved.

Structure, dielectric, and magnetic properties of Sr2TiMnO6 ceramics

Sr2TiMnO6, a double perovskite associated with high degree of B-site cation disorder was investigated in detail for its structural, magnetic, and dielectric properties. Though x-ray powder diffraction analysis confirms its cubic structure, first order Raman scattering and infrared reflectivity spectra indicate a breaking of the local cubic symmetry. The magnetization study reveals an anomaly at 14 K owing to a ferrimagnetic/canted antiferromagneticlike ordering arising from local Mn-O-Mn clusters. Saturated M-H hysteresis loops obtained at 5 K also reflect the weak ferromagnetic exchange interactions present in the system and an approximate estimation of Mn3+/Mn4+ was done using the magnetization data for the samples sintered at different temperatures. The conductivity and dielectric behavior of this system has been investigated in a broad temperature range of 10 to 300 K. Intrinsic permittivity was obtained only below 100 K whereas giant permittivity due to conductivity and Maxwell-Wagner polarization was observed at higher temperatures. X-ray photoemission studies further confirmed the presence of mixed oxidation states of Mn and the valence band spectra analysis was carried out in detail. (C) 2010 American Institute of Physics. doi: 10.1063/1.3500369]

Thermal expansion of doped lanthanum gallates

Thermal expansion of several compositions of Sr and Mg-doped LaGaO3 including an A-site deficient composition (La0.9Sr0.1)(0.98)(Ga0.8Mg0.2)O-2.821 were measured in the temperature range from 298 to 1273 K. The effect of doping on thermal expansion was studied by varying the composition at one site of the perovskite structure (either A or B), while keeping the composition at the other site invariant. Thermal expansion varied nonlinearly with temperature and exhibited an inflexion between 550 and 620 K, probably related to the change in crystal structure from orthorhombic to rhombohedral. The dependence of average thermal expansion coefficient (alpha (av)) on the dopant concentration on either A or B site of the perovskite structure was found to be linear, when the composition at the other site was kept constant. Mg doping on the B-site had a greater effect on the average thermal expansion coefficient than Sr doping on the A-site. Cation deficiency at the A-site decreases thermal expansion when compositions at both sites are held constant.

High-temperature reactions of alkali and plagioclase feldspars with alkali and alkaline-earth chlorides-formation of celsian

High-temperature reactions (Ca 900-degrees-C) involving albite, K-feldspar or plagioclase and K, Ba-or K, Sr chlorides were experimentally studied. These experiments reveal that the reaction between K-exchanged albite, potash feldspar, or plagioclase and Ba-chloride/Ba-K chloride results in the formation of celsian by the breakdown of the starting feldspar structure above 800-degrees-C. Sr-feldspar does not form under similar conditions. A size-effect of the large M-site cation appears to be responsible for the formation of celsian. The reaction between K-feldspar and barium chloride may be used as a method for synthesizing celsian.

Growth and Characterization Studies of ABi2ta2o9 (A = Ba, Sr and Ca) Ferroelectric Thin Films

Thin films of ferroelectric ABi2Ta2O9 bismuth-layered structure, where A = Ba, Sr and Ca, were prepared by pulsed laser deposition technique on Pt/TiO2/SiO2/Si(100) substrates. The influence of substrate temperature between 500 to 750°C, and oxygen partial pressure 100-300 mTorr, on the structural and electrical properties of the films was investigated. The films deposited above 650°C substrate temperature showed complete Aurivillius layered structure. Films annealed at 750°C for 1h in oxygen atmosphere have exhibited better electrical properties. Atomic force microscopy study of surface topography shows that the films grown at lower temperature has smaller grains and higher surface roughness. This paper discusses the pronounced influence of A-site cation substitution on the structural and ferroelectric properties with the aid of Raman spectroscopy, X-ray diffraction and electrical properties. The degradation of ferroelectric properties with Ba and Ca substitution at A-sites is attributed to the higher structural distortion caused by changing tolerance factor. A systematic proportionate variation of coercive field is attributed to electronegativity difference of A-site cations.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.

Electronic, structural, and optical properties of the host and Cr-doped cadmium thioindate

The cadmium thioindate spinel CdIn2S4 semiconductor has potential applications for optoelectronic devices. We present a theoretical study of the structural and optoelectronic properties of the host and of the Cr-doped ternary spinel. For the host spinel, we analyze the direct or indirect character of the energy bandgap, the change of the energy bandgap with the anion displacement parameter and with the site cation distribution, and the optical properties. The main effect of the Cr doping is the creation of an intermediate band within the energy bandgap. The character and the occupation of this band are analyzed for two substitutions: Cr by In and Cr by Cd. This band permits more channels for the photon absorption. The optical properties are obtained and analyzed. The absorption coefficients are decomposed into contributions from the different absorption channels and from the inter-and intra-atomic components.

From ab initio quantum mechanics to molecular neurobiology: A cation–π binding site in the nicotinic receptor

The nicotinic acetylcholine receptor is the prototype ligand-gated ion channel. A number of aromatic amino acids have been identified as contributing to the agonist binding site, suggesting that cation–π interactions may be involved in binding the quaternary ammonium group of the agonist, acetylcholine. Here we show a compelling correlation between: (i) ab initio quantum mechanical predictions of cation–π binding abilities and (ii) EC50 values for acetylcholine at the receptor for a series of tryptophan derivatives that were incorporated into the receptor by using the in vivo nonsense-suppression method for unnatural amino acid incorporation. Such a correlation is seen at one, and only one, of the aromatic residues—tryptophan-149 of the α subunit. This finding indicates that, on binding, the cationic, quaternary ammonium group of acetylcholine makes van der Waals contact with the indole side chain of α tryptophan-149, providing the most precise structural information to date on this receptor. Consistent with this model, a tethered quaternary ammonium group emanating from position α149 produces a constitutively active receptor.