Valence State of Ru at the Mn Sites in Pr0.5Sr0.5MnO3: Thermoelectric Power and X-Ray Absorption Near-Edge Structure Spectroscopy

The Ru valence at the Mn sites in Pr_0.5Sr_0.5MnO₃ has been studied using thermoelectric power (TEP) and Ru K- and L _III-edge X-ray absorption near edge structure (XANES) spectroscopy. In comparison with TEP value at 400 K for Pr_1?xSr _x MnO₃ and Pr_0.5Sr_0.5Mn_1?xRu _x O₃, it was found that the Mn-site doped Ru is in the mixed valence state between 4+ and 5+. Ru K- and L _III-edge XANES study of Pr_0.5Sr_0.5Mn_1?xRu _x O₃ (x = 0.04 and 0.1) also confirmed the mixed valence state of Ru from the fact that XANES spectrum of the Mn-site doped Ru is in between those of tetravalent and pentavalent ruthenates. These results indicate that the change of carrier density with Ru doping is not sufficient to understand the drastic enhancement of ferromagnetism observed in Ru-doped Pr_0.5Sr_0.5MnO₃. The prime role of Ru is discussed in terms of Mn valence change and magnetic interactions between Mn and doped Ru ions.     

The tetragonal-orthorhombic transition and the associated changes in the properties of Pr0.5−xNdxSr0.5MnO3

The transition from the tetragonal (I4/mcm) to the orthorhombic (Imma) structure associated with a change in A- to CE-type antiferromagnetism in the Pr_0.5−xNd_xSr_0.5MnO₃ has been investigated by X-ray diffraction as well as magnetization and resistivity measurements. The transition is found to occur between x=0.1 and 0.2.     

Stress relaxation of La1/2Sr1/2MnO3 and La2/3Ca1/3MnO3 at solid oxide fuel cell interfaces

Interfacial stress is thought to have significant effects on electrical and oxygen transport properties in thin films of importance in solid oxide fuel cell applications. We investigate how in-plane biaxial stress modifies the electronic structure of La_2/3Ca_1/3MnO₃ and La_1/2Sr_1/2MnO₃ thin films prepared by pulsed laser deposition on three different substrates to vary the in-plane stress from tensile to compressive. The electronic structure was probed by X-ray absorption spectroscopy of the Mn L_2,3-edge to characterize the interfacial disruption in this region in an element-specific, site-specific manner. The compressive or tensile interfacial strain modifies the relative concentrations of La and Sr in the interfacial region in order to achieve a better lattice match to the contact material. This atomic migration generates an interfacial region dominated by a compound with a single valency for the transition metal ion, resulting in a severe barrier to oxygen and electron transport through this region.     

High-Temperature Thermoelectric Power of The Metal Oxides: La2?xSrxCuO4 and Bi1?xSrxMnO3

We have investigated the high-temperature thermoelectric power (TEP) of La_{2− x} Sr _x CuO₄ (0.05 ≤ x ≤ 0.35) and Bi_{1− x} Sr _x MnO₃ (0.5 ≤ x ≤ 0.8) up to 700 K. Based on the TEP results we have discussed the phase transitions on each case. In the case of high-T _C cuprates, La_{2− x} Sr _x CuO₄ (0.05 ≤ x ≤ 0.35), the TEP shows different temperature dependences in three temperature regions. At low temperature, the positive TEP rises showing a broad peak at temperature T _P, which shifts to lower temperature upon Sr doping. Right above T _P, the TEP decreases linearly as temperature increases. At high temperature, TEP deviates from the linear-T dependence at a certain temperature, T _H, showing a saturation behavior. The systematic change of the TEP behavior is discussed in terms of the two-fluids model, which is an intrinsically inhomogeneous state, consisted of bound pairs and independent carriers in the normal state of the high-T _C superconductors. For Bi_{1− x} Sr _x MnO₃ (0.5 ≤ x ≤ 0.8), the negative TEP is almost temperature-independent in the high temperature regime (T _CO < T < 700 K). Near the charge ordering temperature (T _CO), however, TEP suddenly decreases with decrease of temperature, indicating the suppression of carrier mobility with charge ordering transition. As Bi concentration decreases, T _CO shifts to lower temperature from T _CO ∼ 520 K for x = 0.5 to T _CO ∼ 435 K for x = 0.8, which suggests that charge ordering is related to the local lattice distortion due to highly polarizable 6s² character of Bi³⁺ ion. In comparison with the resistivity data, the TEP results have been discussed in terms of the carrier localization accompanied by local lattice distortion.     

Sr and Ba substitution in charge ordered Pr0.5Ca0.5MnO3: Sharp steps in the magnetic and transport properties for a narrow composition range

The magnetic and transport properties of Pr_0.5Ca_0.5−xA_xMnO₃ (A = Sr, Ba) have been investigated in this paper. The substitution of Ca with bigger cations such as Sr and Ba can favour the field-induced ferromagnetism and induce sharp steps in the magnetization versus field and resistivity versus field curves. These properties strongly depend on the thermal history of the samples. All the results have been interpreted by a martensitic-like mechanism based on phase separation induced by A-site size mismatch. The above model can also explain the result that the less efficient ability of Sr substitution than Ba substitution to induce ferromagnetism and sharp steps. Another interesting feature in the system is the existence of an optimum substitution range to induce magnetization steps and reach high field-induced magnetization values for both Sr (x = 0.07–0.10) and Ba (x = 0.01–0.08) substitution. We suggest that the disappearance of the steps beyond the optimum substitution range possibly results from the different nature of phase separation in the optimum substitution range and beyond this range.     

Two Pseudogap Behavior in La2?xSrxCuO4: Thermoelectric Power at High Temperature

Thermoelectric power (TEP) of high-T _C superconductors has been investigated in a wide range of temperature (T _C < T < 700 K) for La_2–x Sr _x CuO₄. TEP of La_2–x Sr _x CuO₄ shows different temperature dependences in three temperature regions. In the low-temperature region, a positive broad TEP peak is observed near T _p, which shifts to lower temperature upon doping. As temperature increases, TEP decreases linearly at intermediate temperature. In the high-temperature region, TEP deviates from the linear temperature dependence at a certain temperature, T _h showing a saturation behavior. As the doping concentration increases, the characteristic temperatures, T _C, T _p, and T _h, show systematic changes. In comparison with pseudogap temperature estimated from other experiments, the large pseudogap behavior in TEP at high temperature has been discussed and distinguished from the small pseudogap observed at lower temperature. A possibility of bound pairs formation in the normal state opening the pseudogap at high temperature is discussed briefly. The coexistence of bound pairs and the normal independent carriers for T _C < T < T_h could be the origin of the intrinsic inhomogeneity.     

Enhanced ferro- and piezoelectric properties in (100)-textured Nb-doped Pb(ZrxTi1 − x)O3 films with compositions at morphotropic phase boundary

To develop high-performance piezoelectric films on conventional Pt(111)/Ti/SiO₂/Si(100) substrates, sol-gel-derived highly [100]-textured Nb-doped Pb(Zr_xTi_1 − x)O₃ (PNZT) thin films with different Zr/Ti ratios ranging from 20/80 to 80/20 were prepared and characterized. The phase structure, ferroelectric and piezoelectric properties of the PZNT films were investigated as a function of Zr/Ti ratios, and it was confirmed that there was distinct phase transition of the PNZT system from tetragonal to rhombohedral when the Zr/Ti ratio varied across the morphotropic phase boundary (MPB). The Nb-doped PZT films showed enhanced remanent polarization but reduced coercive field, whose best values reached 75 μC/cm² and 82 kV/cm, respectively at the composition close to MPB. In addition, the [100]-textured PNZT film at MPB also shows a high piezoelectric coefficient up to 161 pm/V. All these properties are superior to those for undoped PZT films.