Direct observation of oxygen superstructures in manganites

We report the observation of superstructures associated with the oxygen 2p states in two prototypical manganites using x-ray diffraction at the oxygen K edge. In the stripe order system Bi0.31Ca0.69MnO3, hole-doped O states are orbitally ordered, at the same propagation vector as the Mn orbital ordering, but no oxygen charge stripes are found at this periodicity. In La7/8Sr1/8MnO3, we observe a 2p charge ordering described by alternating hole-poor and hole-rich MnO planes that is consistent with some of the recent predictions.     

The effects of vacancies in oxygen sites on physical properties of the lanthanum manganites

Abstract

The non-stoichiometric solution Ln_1?xSr_xMnO_3-δ□_δ was prepared by the classic ceramic method. The physical properties as crystallographic, magnetic and electrical properties were studied. A structural phase transition from rhombohedral to orthorhombic was observed at a concentration of Mn⁴⁺ between 10% and 15% per Mn atom in the unit formula. The magnetic properties are very sensitive to the presence of vacancies at the oxygen sites. The non-stoichiometric, samples change from metallic to insulating behaviour depending on their vacancy concentration. In the semiconductor phase, the activation energy value changes with the structural phase, increasing in the rhombohedral phase and decreasing in the orthorhombic phase.     

Structure, oxygen stoichiometry and electrical conductivity in the system Sr-Ce-Co-O

Mixed oxides in the system S-Ce-Co-O were prepared by solid state reaction and by freeze-drying of precursor compounds followed by thermal treatment. Two types of perovskite oxides exist in the system: Solid solutions of the type Sr_{1 − y}Ce_yCoO_{3 − x} and mixed oxides of the type (1 − y)SrCeO₃ − ySrCoO_{3 − x}. Microstructures and phase compositions were determined by electron microscopy and X-ray diffraction. SrCoO_{3 − x} forms a solid solution of ceria on the A-site in the strontium cobaltite lattice up to 0.15 mol Ce. This solid solution corresponds to the high-temperature structure of pure SrCoO_{3 − x} and is characterized by high oxygen exchange and electrical conductivity. The oxygen deficiency x was measured by solid electrolyte coulometry. The oxygen deficiency of solid solutions Sr_{1 − y}Ce_yCoO_{3 − x} increases with temperature and decreases with pO₂ in the ambient atmosphere and with increasing Ce dopant concentration. The pO₂-T-x diagram of the solid solution was determined. The T, pO₂ and dopant concentration dependencies of electrical conductivity were measured by a four-point d.c. technique. By Ce doping strontium cobaltite becomes a stabilized high-conductive material (maximum conductivity: 500 S cm⁻¹ at 400 °C, E_a = 0.025 eV, p-type). Above this temperature the T-coefficient of the conductivity changes from positive (semiconducting) to negative values.     

Determination of the magnetic symmetry of hexagonal manganites by second harmonic generation

Optical second harmonic spectroscopy is introduced as a powerful supplement for the determination of complex magnetic structures. Experimental efforts are simplified and new degrees of freedom are opened. Thereby, some principal or technical restrictions of neutron or magnetic x-ray diffraction experiments are overcome. High spatial resolution leads to additional information about magnetically ordered matter. As an example, the noncollinear magnetic structure of the hexagonal manganites RMnO3 ( R = Sc, Y, Ho, Er, Tm, Yb, Lu) is analyzed. The results show that some earlier conclusions on their magnetic symmetry and properties should be revised.     

Influence of lattice oxygen stoichiometry on the mechanism of methane oxidation in SOFC anodes

There is growing interest in developing oxide materials for direct hydrocarbon solid oxide fuel cell anodes. In addition to electronic and ionic conductivities, the electrocatalytic activity of these materials is a critical requirement for a high performance anode. In this paper, we present evidence for the important role of variable lattice oxygen stoichiometry and anode geometry in dictating the activity and reaction mechanism of La_0.75Sr_0.25Cr_1 − xMn_xO_3 − δ-based anodes for CH₄ oxidation. Total oxidation of CH₄ is favored by low oxygen vacancy concentration and availability of reducible B-site cations. The non-linear dependence of electrode polarization resistance with current density is attributed to dynamic changes in lattice oxygen vacancy concentration. The relatively high open circuit potential of porous anodes compared with thin films is attributed to an increase in secondary reactions of the fuel within the porous anode.     

Lattice distortion in mixed-valent materials

Using a simple model, we calculate rigorously the distribution function of displacements of anions in mixed-valent rare-earth compounds, and find that the anions always adopt dynamically distorted positions corresponding to the valence fluctuations in the rare-earth ions contrary to the previous study.     

Magnetorefractive effect in manganites

The magnetotrans mittance and magnetoreflectance of manganite films and one-dimensional magnetophotonic crystals containing a manganite film as a defect are calculated. The calculations demonstrate that the magnetotransmittance and magnetoreflectance of manganites with a colossal magnetoresistance can be treated as a manifestation of the magnetorefractive effect. The magnitude of the magnetorefractive effect in transmission can reach 20–40% at low temperatures. The effect in reflection amounts to 1–2% for a 300-nm-thick film and can be substantially amplified through multibeam interference in the symmetric and antisymmetric structures of magnetophotonic crystals with a built-in defect.     

Cooperative jahn-teller coupling in the manganites

The cooperative Jahn-Teller coupling between the Mn e(g) electrons and the oxygen octahedral distortions in LaMnO3 is studied using ab initio density-functional calculations and tight-binding models. The linear and quadratic vibronic coupling parameters are calculated using density-functional methods. It is shown that the cooperative Jahn-Teller coupling, primarily due to the interoctahedral electron hopping (band structure term), leads to the ordering of the octahedral distortion and simultaneously to orbital ordering. The coupling results in a two-minima adiabatic potential surface in the solid, instead of the three-minima "Mexican-hat" surface for the isolated octahedron.     

Electronic correlations in manganites

The influence of local electronic correlations on the properties of colossal magnetoresistive manganites is investigated. To this end, a ferromagnetic two-band Kondo lattice model is supplemented with the local Coulomb repulsion missing in this model and is analyzed within dynamical mean-field theory. Results for the spectral function, optical conductivity, and the paramagnetic-to-ferromagnetic phase transition show that electronic correlations have drastic effects and may explain some experimental observations.     

Magnetocaloric effect in manganites

The magnetocaloric effect (MCE) in La_{1 ? x} Sr _x MnO₃, Sm_0.55Sr_0.45MnO₃, and PrBaMn₂O₆ compounds is studied. The maximum values of MCE (??T _max) determined by a direct method in the second and third compositions and in La_0.9Sr_0.1MnO₃ are found to be much lower than those calculated from the change of the magnetic part of entropy in the Curie temperature (T _C) and the Néel temperature (T _N) range. The negative contribution of the antiferromagnetic (AFM) part of a sample in the La_{1 ? x} Sr _x MnO₃ system at 0.1 ?? x ?? 0.3 decreases ??T _max and changes the ??T(T) curve shape, shifting its maximum 20?C40 K above T _C. Lower values of ??T _max are detected in the range T _C = 130?142 K in polycrystalline and single-crystal Sm_0.55Sr_0.45MnO₃ samples cooled in air. If such samples were cooled in an oxygen atmosphere (which restores broken Mn-O-Mn bonds and, thus, increases the volume of CE-type AFM clusters), the maximum in the temperature dependence of MCE is located at T _N (243 K) for CE-type AFM clusters. A magnetic field applied to a sample during the MCE measurements transforms these clusters into a ferromagnetic (FM) state, and both types of clusters decompose at T = T _N. The PrBaMn₂O₆ composition undergoes an AFM-FM transition at 231 K, and the temperature dependence of its MCE has a sharp minimum at T = 234 K, where MCE is negative, and a broad maximum covering T _C. The absolute values of MCE at both extrema are several times lower than those calculated from the change in the magnetic entropy. These phenomena are explained by the presence of a magnetically heterogeneous FM-AFM state in these manganites.     

Solitonic phase in manganites

Orbital order present in several transition metal compounds could give rise to topological defects. Here we argue that the topological defects in orbital ordered half doped manganites are orbital solitons that carry a charge of +/-e/2. When extra charge is added to the system an array of solitons is formed and an incommensurate solitonic phase occurs. The striking experimental asymmetry in the phase diagram as electrons or holes are added to half doped manganites is explained by the energy difference between positive and negative charged solitons. The presence of nanoscale inhomogeneities in manganites is naturally explained by the existence of solitonic phases.     

Comparative evaluation of methods for precise determination of oxygen stoichiometry in highT c oxides

A comparative study of the methods for oxygen stoichiometry—direct inert gas fusion method and two indirect iodometric methods—has been carried out. The indirect iodometric method in which Cu(III) is directly estimated, has been found to be more precise. Several samples of YBa₂Cu₃O _x of varyingx, their fluorine-substituted counterparts and also Bi₂Sr₂Ca₁Cu₂O _x and Tl₂Ba₂Ca₁Cu₂O _x have been analysed.     

Effect of oxygen stoichiometry and microstructure on superconducting properties of YBaCuO films

Microstructure and oxygen stoichiometry of YBaCuO films manufactured by laser ablation are investigated. Dependence of the specific electrical resistivity and superconducting parameters of films on microstructure and oxygen stoichiometry is demonstrated. Conditions of deposition are determined, under which films with minimum microstructure defects and good conducting properties are formed. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 41–45, February, 2007.     

Ferromagnetism and electron-phonon coupling in the manganites

The physics of ferromagnetic doped manganites, such as La 1-x Ca x MnO 3 with x ≈ 0.2-0.4, is reviewed. The concept of double exchange is discussed within the general framework of itinerant electron magnetism. The new feature in this context is the coupling of electrons to local phonon modes. Emphasis is placed on the quantum nature of the phonons and the link with polaron physics. However it is stressed that the manganites fall into an intermediate coupling regime where standard small-polaron theory does not apply. The recently-developed many-body coherent potential approximation is able to deal with this situation and Green's recent application to the Holstein double-exchange model is described. Issues addressed include the nature of the basic electronic structure, the metal-insulator transition, a unification of colossal magnetoresistance, pressure effects and the isotope effect, pseudogaps in spectroscopy and the effect of electron-phonon coupling on spin waves.     

Orbital correlations in doped manganites

We review our recent X-ray scattering studies of charge and orbital order in doped manganites, with specific emphasis on the role of orbital correlations in Pr_1-xCa_xMnO₃. For x=0.25, we find an orbital structure indistinguishable from the undoped structure and long-range orbital order at low temperatures. For dopings 0.3≤x≤0.5, we find scattering consistent with a charge and orbitally ordered CE-type structure. While in each case the charge order peaks are resolution limited, the orbital order exhibits only short-range correlations. We report the doping dependence of the correlation length and discuss the connection between the orbital correlations and the finite magnetic correlation length observed on the Mn³⁺ sublattice with neutron-scattering techniques. The physical origin of these domains, which appear to be isotropic, remains unclear. We find that weak orbital correlations persist well above the phase transition, with a correlation length of 1–2 lattice constants at high temperatures. Significantly, we observe similar correlations at high temperatures in La_0.7Ca_0.3MnO₃, which does not have an orbitally ordered ground state, and we conclude that such correlations are robust to variations in the relative strength of the electron–phonon coupling. Received: 22 May 2001 / Accepted: 4 July 2001 / Published online: 5 October 2001     

Weak amplification of the magnetocaloric effect in manganites

The magnetocaloric effect (MCE) has been measured by direct method in La_0.8Ag_0.15MnO₃ and La_0.85Ag_0.15MnO₃ before and after coating of Fe–Co layer on the surfaces of manganites. An evaporated film thickness has been 500 nm. The measurements have shown the MCE to be increased by 7%–8% under 26 kOe after Fe–Co coating on the flat surfaces.