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Register a new userEntanglement of charge transfer, hole doping, exchange interaction and octahedron tilting angle and their influence on the conductivity of La1-xSrxFe0.75Ni0.25O3-{delta}: A combination of x-ray spectroscopy and diffraction
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Substitution of La by Sr in the 25% Ni doped charge transfer insulator LaFeO3 creates structural changes that inflect the electrical conductivity caused by small polaron hopping via exchange interactions and charge transfer. The substitution forms electron holes and a structural crossover from orthorhombic to rhombohedral symmetry, and then to cubic symmetry. The structural crossover is accompanied by a crossover from Fe3+-O2--Fe3+ superexchange interaction to Fe3+-O2--Fe4+ double exchange interaction, as evidenced by a considerable increase of conductivity. These interactions and charge transfer mechanism depend on superexchange angle, which approaches 180{deg} upon increasing Sr concentration, leading an increased overlap between the O (2p) and Fe/Ni (3d) orbitals.
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Iron resonant valance band photoemission spectra of Sr substituted LaFe0.75Ni0.25 O3-{delta} have been recorded across the Fe 2p - 3d absorption threshold to obtain Fe specific spectral information on the 3d projected partial density of states. Comparison with La1-xSrxFeO3 resonant VB PES literature data suggests that substitution of Fe by Ni forms electron holes which are mainly O 2p character. Substitution of La by Sr increases the hole concentration to an extent that the eg structure vanishes. The variation of the eg and t2g structures is paralleled by the changes in the electrical conductivity.
In this work we report a structural, electrical and magnetic characterization of the La1-xNaxMn1-yRuyO3+d (LNMRO) system with x = 0.05, 0.15 and y = 0, 0.05, 0.15, also comprising an investigation of the role of the oxygen content on the related redox properties. The experimental investigation has been realized with the aid of X-ray powder diffraction, electron microprobe analysis, thermogravimetry, electrical resistivity and magnetization measurements, and electron paramagnetic resonance. We demonstrate that the effect of ruthenium doping on the studied LNMRO compounds is not only directly related to the Ru/Mn substitution and to the Ru oxidation state but also indirectly connected to the oxygen content in the sample. Our data show that ruthenium addition can improve electrical and magnetic properties of non-optimally (low) cation doped manganites, causing an increase of the TC value and the insurgence of MR effect, as observed for the x = 0.05 and y = 0.05 sample.
We report the doping dependence of the order of the ferromagnetic metal to paramagnetic insulator phase transition in La1-xCaxMnO3. At x = 0.33, magnetization and specific heat data show a first order transition, with an entropy change (2.3 J/molK) accounted for by both volume expansion and the discontinuity of M ~ 1.7 Bohr magnetons via the Clausius-Clapeyron equation. At x = 0.4, the data show a continuous transition with tricritical point exponents alpha = 0.48+/- 0.06, beta = 0.25+/- 0.03, gamma = 1.03+/- 0.05, and delta = 5.0 +/- 0.8. This tricritical point separates first order (x<0.4) from second order (x>0.4) transitions.
Recent experimental discoveries have brought a diverse set of broken symmetry states to the center stage of research on cuprate superconductors. Here, we focus on a thematic understanding of the diverse phenomenology by exploring a strong-coupling mechanism of symmetry breaking driven by frustration of antiferromagnetic order. We achieve this through a variational study of a three-band model of the CuO$_2$ plane with Kondo-type exchange couplings between doped oxygen holes and classical copper spins. Two main findings from this strong-coupling multi-band perspective are 1) that the symmetry hierarchy of spin stripe, charge stripe, intra-unit-cell nematic order and isotropic phases are all accessible microscopically within the model, 2) many symmetry-breaking patterns compete with energy differences within a few meV per Cu atom to produce a rich phase diagram. These results indicate that the diverse phenomenology of broken-symmetry states in hole-doped antiferromagnetic charge-transfer insulators may indeed arise from hole-doped frustration of antiferromagnetism.
We have explored spin, charge and orbitally ordered states in La1-xSrxMnO3 (0 < x < 1/2) using model Hartree-Fock calculations on d-p-type lattice models. At x=1/8, several charge and orbitally modulated states are found to be stable and almost degenerate in energy with a homogeneous ferromagnetic state. The present calculation indicates that a ferromagnetic state with a charge modulation along the c-axis which is consistent with the experiment by Yamada et al. might be responsible for the anomalous behavior around x = 1/8.
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