Electronic conduction in La-based perovskite-type oxides

Abstract

A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo_0.5Ni_0.5O_3±δ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo_0.5Ni_0.5O_3±δ exhibits a high conductivity of 1.9 × 10³ S cm^?1 at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 10²² cm^?3 and a small effective mass m? of 0.10 m_e. Notably, LaCo_0.5Ni_0.5O_3±δ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo_0.5Ni_0.5O_3±δ is the most suitable for the fabrication of oxide electrodes and wiring, though La_1?xSr_xCoO_3±δ and La_1?xSr_xMnO_3±δ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 10³ S cm^?1 for La_0.5Sr_0.5CoO_3±δ and 1.5 × 10³ S cm^?1 for La_0.6Sr_0.4MnO_3±δ because oxygen release occurs in La_1?xSr_xCoO_3±δ as elevating temperature and the electrical conductivity of La_0.6Sr_0.4MnO_3±δ slightly decreases at temperatures above 400 K.     

Structures and properties of La1−x,Sr x CoO3−y,prepared by freeze drying

Several samples of La_1–x Sr _x CoO_3–y (x = 1, 0.8, 0.5, 0.2) were prepared by calcining freezedried, stoichiometric mixtures of nitrates at different temperatures and for different lengths of time. Selected samples were characterized by powder X-ray diffraction, conductivity measurements, Brunauer-Emmett-Teller surface area measurement, and by electrochemical cyclic voltammetry in alkaline solutions and alkaline solutions containing methanol. The structures of each composition were complex and varied with composition and preparation conditions. There is evidence for non-stoichiometry caused by oxygen anion vacancies. For La_0.5Sr_0.5CoO_3–y the electrochemical activity towards the oxidation of methanol is a maximum at the fully formed cubic perovskite. The oxidation currents at La_0.8Sr_0.2CoO_3–y and La_0.2Sr_0.8CoO_3–y go through maxima at more distorted structures.     

A new route to synthesize La1?xSrxMnO3

Self-Propagating High-temperature Synthesis (SHS) was used to producecomplex oxides (La_1–x Sr _x MnO₃ with x = 0, 0.1 and 0.2), which are used as the cathode in solid oxide fuel cells (SOFCs). Thermodynamic predications and experiments show that La_1–x Sr _x MnO₃ can be prepared via SHS under moderate conditions from a mixture of La₂O₃ + SrO₂ + Mn, using either gaseous oxygen or solid NaClO₄ as the oxidant. Partial melting at the high combustion temperature increased product homogeneity. The electrical conductivity of the product was 180 S·cm^–1 at 1000°C in air, matching that of sample made by other synthesis processes. SHS enables a more economical production of La_1–x Sr _x MnO₃ than existing commercial processes.     

Combined platinum/perovskite catalyst for an efficient nanostructured air electrode

This work shows the stepwise improvement of air electrodes by the right combination of catalysts. In all electrodes carbon nanotubes serve as carbon support. The electrodes are produced by ultrasonic mixing of the carbon nanotubes and the catalysts. Their catalytic activity towards oxygen reduction in alkaline solution is evaluated by polarisation curves and electrochemical impedance spectroscopy. In a first step La_1?xSr_xMnO₃ perovskites are investigated, as well as La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ are compared. It is found that La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ have a positive impact on different parts of the current–potential curve. In a second step the influence of small amounts of platinum as an additional catalyst besides the perovskite is analyzed with the result that platinum lowers significantly the activation polarisation. Finally, the optimum composition of the electrode is found by using the synergetic effect of platinum, La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃.     

Structural studies of a mixed-valence state in the incommensurate composite crystal Sr1.261CoO3

The incommensurate modulated crystal structure of the hexagonal cobalt oxide Sr_1.261CoO₃ has been studied using a four-dimensional (4D) superspace profile analysis of neutron powder diffraction data. Sr_1.261CoO₃ is a composite crystal that consists of the [CoO₃] and [2Sr] subsystems. The [CoO₃] subsystem forms 1D chains that run parallel to the c-axis and consist of face-sharing CoO₆ polyhedra with octahedral (Oh) and trigonal prismatic (TP) coordinations. The structure analysis reveals that the [CoO₃] chains contain 73.9% Oh and 26.1% TP sites, and that the TP sites have longer Co–O bonds than the Oh sites: d_av. =2.039(4) Å (TP) and 1.895(3) Å (Oh). The averaged Co bond valences are Co^3.56(3)+ in the Oh sites and Co^2.45(3)+ in the TP sites, suggesting that a considerable amount of Co³⁺ ions are mixed with Co⁴⁺ions in the Oh sites and with Co²⁺ ions in the TP sites. The observed magnetic susceptibility can be well explained assuming that the compound has the Co mixed-valence state with the spin configurations of S=0 low-spin state for Co³⁺(dε⁶), S=1/2 low-spin state for Co⁴⁺(dε⁵) and S=3/2 high-spin state for Co²⁺(dε⁵dγ²). The Weiss temperature, approximately 0.8 K, implies that Sr_1.261CoO₃ naturally assumes a Curie paramagnetic state, probably owing to the obstruction of the intrachain magnetic interaction by the nonmagnetic Co³⁺ ions. These results suggest that the nonmagnetic Co³⁺ ions play an essential role in the magnetism of Sr_2γCoO₃ systems.     

High-temperature oxygen non-stoichiometry, conductivity and structure in strontium-rich nickelates La2−xSrxNiO4−δ (x = 1 and 1.4)

Oxygen non-stoichiometry, electrical conductivity and thermal expansion of La_2−xSr_xNiO_4−δ phases with high levels of strontium-substitution (1 ≤ x ≤ 1.4) have been investigated in air and oxygen atmosphere in the temperature range 20–1050 °C. These phases retain the K₂NiF₄-type structure of La₂NiO₄ (tetragonal, space group I4/mmm). The oxygen vacancy fraction was determined independently from thermogravimetric and neutron diffraction experiments, and is found to increase considerably on heating. The electrical resistivity, thermal expansion and cell parameters with temperature show peculiar variations with temperature, and differ notably from La₂NiO_4±δ in this respect. These variations are tentatively correlated with the evolution of nickel oxidation state, which crosses from a Ni³⁺/Ni⁴⁺ to a Ni²⁺/Ni³⁺ equilibrium on heating.     

Influence of Ag-doping in La0.5Sr0.5CoO3 on Its Structural and Magnetic Properties

The structural and magnetic properties of the mixed valent cobaltites La_0.5Sr_0.5?x Ag _x CoO₃ (0≤x≤0.15) with perovskite structure have been investigated. X-ray diffraction (XRD) analysis using Rietveld refinement shows that all our samples crystallize in the orthorhombic structure with $R\overline{3}c$ space group. Although the unit cell volume remains almost constant, the Co–O bond length and the Co–O–Co bond angle are sensitive to the Ag addition. All our studied samples undergo a paramagnetic-ferromagnetic transition with decreasing temperature. The zero field cooled (ZFC) and field cooled (FC) magnetization curves at 50 mT of La_0.5Sr_0.5CoO₃ (x=0) sample exhibits thermomagnetic irreversibility indicating frustration and competition of both antiferromagnetic and ferromagnetic interactions. It is suggested that Co³⁺ ions are in the intermediate spin state but Co⁴⁺ ions stay in a mixture of intermediate and high spin states. Ag addition leads to dramatic changes in magnetic properties. An interesting result has been obtained for La_0.5Sr_0.4Ag_0.1CoO₃, where the ZFC and FC curves coincide. For La_0.5Sr_0.35Ag_0.15CoO₃ (x=0.15) sample, the observed thermomagnetic irreversibility is much higher than that observed in x=0 sample. Hysteresis loops were recorded for x=0, 0.05, 0.1, and 0.15. The coercitive field is found to increase with Ag content reaching 0.26 T for x=0.15 whereas the remanent magnetization decreases.     

Itinerant electron behaviour and long-range ordering in La1−x Sr x CoO3

Electrical resistivity of La_1?x Sr _x CoO₃ is reduced significantly by the substitution of Ni³⁺ ions in place of the cobalt ions. In the La_1?x Sr _x Co_1?y Ni _y O₃ system, for small values ofx(x=0·05) superparamagnetic clusters seem to be formed at lower temperatures (<300 K). The formation of such clusters is not affected by the presence of nickel ions. Whenx is large, the occurrence of long-range ordering seems to depend on the itinerancy of charge carriers.     

New cathode compositions based on La0.84Sr0.16Mn1−xMxO3, where M = Al, Ga for solid oxide fuel cell

In order to identify new cathode compositions for the high temperature solid oxide fuel cell, we have investigated the effect of the trivalent cations Al and Ga at the Mn site of the well-studied cathode composition La_0.84Sr_0.16MnO₃. All the compositions have been prepared by the low temperature citrate-nitrate auto-ignition process and sintered within the temperature range of 1150-1350 °C for 4 h. In order to understand the compatibility of the prepared samples as alternative cathode materials, we compared their electrical conductivity and thermal expansion coefficient with those of La_0.84Sr_0.16MnO₃ and yttria-stabilized zirconia. A 10 mol% Al doped La_0.84Sr_0.16MnO₃ composition exhibited a conductivity of around 122 S cm⁻¹ at 950 °C and a thermal expansion coefficient of 11.04 × 10⁻⁶ K with a minimum reactivity towards yttria-stabilized zirconia. Though the conductivity of the new composition is lower than that of La_0.84Sr_0.16MnO₃ (169 S cm⁻¹ at 950 °C), it is still high enough for use as a cathode material.     

Optical Conductivity of La1.875Ba0.04Sr0.085CuO4

The in-plane optical conductivity and dc resistivity of La_1.875Ba_0.125–YSr _Y CuO₄ with y = 0.085 was measured from 30 to 20,000 cm^–1 and from 295 to 8 K. A strong extra-Drude absorption at finite frequency is detected both in the normal and superconducting state, and remains unchanged when the free carriers condensate. The present results confirm and extend recent infrared data on La_2–xSr_xCuO₄.     

Surface characterization and catalytic properties of La1−x -Sr x CoO3

The surface chemical states of the perovskite-type compounds, strontium doped lanthanum cobalt oxides (La_1?x Sr _x CoO₃), have been investigated using X-ray photoelectron spectroscopy (XPS). Catalytic oxidations of both methane and CO have also been investigated using flow methods. The chemical composition of the surface of La_1?x Sr _x CoO₃ was very different from that in the bulk, which was measured by X-ray fluorescence spectroscopy (XRFS). The catalytic activity of La_1?x Sr _x CoO₃ increased with an increase in the quantity of cobalt atoms on the surface.     

X-ray photoelectron spectroscopy study of perovskite-type mixed oxides (La1−x A x ′ CoO3)

The surface states of the perovskite-type cerium-, thorium- and strontium-doped lanthanum cobalt oxides (La_1–x Ce _x CoO₃), La_1–x Th _x CoO₃, La_1–x Sr _x CoO₃ x = 0 to 0.03) have been investigated using X-ray photoelectron spectroscopy (XPS). The binding energy differences (BE) between Co2p_3/2 and 01s of lattice oxygen have a maximum value atx = 0.02 in both La_1–x Ce _x CoO₃ and La_1–x Th _x CoO₃. From this result, it is expected that the bonding state between the surface cobalt and lattice oxygen is mostly ionic at this point. The valence band (VB) spectra change greatly atx = 0.02 in both cerium- and thorium-doped samples. We speculate that the high spin trivalent cobalt ion is dominant atx = 0.02 on the surface. On the other hand, the ABEs between Co2p_3/2 and 01s of lattice oxygen decrease with increasingx in La_1–x Sr _x CoO₃. It is expected that the bonding states become covalent in proportion tox. The change of the VB spectra for La_1–x Sr _x CoO₃ near the Fermi level (E _F) can be explained by the formation of the impurity level.     

Fabrication of (La1−x Gd x )2/3Sr1/3MnO3 Manganite Perovskite Nanorods by Sonication-Assisted Coprecipation

(La_1?x Gd _x )_2/3Sr_1/3MnO₃ manganite perovskite nanorods were synthesized by sonication-assisted coprecipitation. Lower sintering temperatures were required for all the samples to crystallize. The fully crystallize samples of (La_0.5Gd_0.5)_2/3Sr_1/3MnO₃ and (La_0.4Gd_0.6)_2/3Sr_1/3MnO₃ show the formation of nanorods upon their synthesis with an average length and width of 160 nm and 20 nm, respectively. The structural, electrical, and magnetic transport properties were investigated.     

Observation of Higher Suppression of Superconducting Transition Temperature in YBa2Cu3O7??? /La0.5Sr0.5CoO3 as?Compared?to?YBa2Cu3O7??? /La0.7Sr0.3MnO3 Bilayers

We report the experimental investigations of the suppression of superconductivity due to the pair breaking effect induced by ferromagnetic layer in YBa₂Cu₃O_7??? /La_0.5Sr_0.5CoO₃ and YBa₂Cu₃O_7??? /La_0.7Sr_0.3MnO₃ bi-layers fabricated by pulsed laser deposition. The current dependent electrical transport studies in the bilayers exhibit a significant reduction in the superconducting transition temperature in accord to I ^2/3 law as compared to single YBa₂Cu₃O_7??? layer, and moreover the superconducting transition temperature in YBa₂Cu₃O_7??? /La_0.7Sr_0.3MnO₃ bilayer is surprisingly found to be much larger than the YBa₂Cu₃O_7??? /La_0.5Sr_0.5CoO₃. It appears that the current driven from a low spin polarization (?11%) material like La_0.5Sr_0.5CoO₃ can also suppress the superconductivity to a larger extent. This indicates that the degree of spin polarization of the ferromagnetic electrode is not the only criteria to determine the suppression of superconductivity by pair breaking effect in superconductor/ferromagnet hybrid structures; rather the transparency of the interface for the spin polarization, the formation of vortex state due to the stray field of ferromagnetic layer and the ferromagnetic domain patterns might play significant roles to determine such effect.     

Structural, magnetic, infrared and Raman studies of La0.8Sr x Ca0.2-x MnO3 (0 ≤ x ≤ 0.2)

We report the results of magnetic, X-ray powder diffraction, infrared and temperature dependent Raman spectra of the La_0.8Sr _x Ca_0.2-x MnO₃ (0 ≤ x ≤ 0.2) manganite. The structure refinement using the Rietveld method indicates that the partial substitution of strontium for calcium (for x ≥ 0.15) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a rhombohedral phase. Magnetic measurement confirms the increase in the Curie temperature from 180 K for La_0.8Ca_0.2MnO₃ to 307 K for La_0.8Sr_0.2MnO₃, respectively. It is argued that the substitution with the larger Sr²⁺ ion strengthens the double-exchange interaction and gives rise to the observed increase of transition temperatures. All manganites show two IR active vibrational modes around 400 and 600 cm^?1. Moreover, when x ≤ 0.1, the absorption band around 400 cm^?1 splits into two peaks. In addition, we have analyzed the frequencies and widths of the observed Raman modes as a function of temperature for all samples with various Sr content. The mode splitting is attributed to both magnetic ordering and large orthorhombic distortion in doped rhombohedral manganites.     

Structure and cation distribution in perovskites with small cations at the A site: the case of ScCoO3

We synthesize ScCoO₃ perovskite and its solid solutions, ScCo_1−xFe_xO₃ and ScCo_1−xCr_xO₃, under high pressure (6 GPa) and high temperature (1570 K) conditions. We find noticeable shifts from the stoichiometric compositions, expressed as (Sc_1−xM_x)MO₃ with x = 0.05–0.11 and M = Co, (Co, Fe) and (Co, Cr). The crystal structure of (Sc_0.95Co_0.05)CoO₃ is refined using synchrotron x-ray powder diffraction data: space group Pnma (No. 62), Z = 4 and lattice parameters a = 5.26766(1) Å, b = 7.14027(2) Å and c = 4.92231(1) Å. (Sc_0.95Co_0.05)CoO₃ crystallizes in the GdFeO₃-type structure similar to other members of the perovskite cobaltite family, ACoO₃ (A³⁺ = Y and Pr-Lu). There is evidence that (Sc_0.95Co_0.05)CoO₃ has non-magnetic low-spin Co³⁺ ions at the B site and paramagnetic high-spin Co³⁺ ions at the A site. In the iron-doped samples (Sc_1−xM_x)MO₃ with M = (Co, Fe), Fe³⁺ ions have a strong preference to occupy the A site of such perovskites at small doping levels.     

Photoconductivity in BiFeO3/La0.7Sr0.3MnO3 heterostructure

In this letter, an oxide heterostructure has been fabricated by successively growing La_0.7Sr_0.3MnO₃ (LSMO) and BiFeO₃ (BFO) layers on LaAlO₃ (100) by pulsed laser deposition. Analysis of the leakage current at different temperature demonstrated that the Poole-Frenkel dominated the leakage current mechanism. Additionally, the BiFeO₃/La_0.7Sr_0.3MnO₃ heterostructure exhibits a positive colossal magnetoresistance (MR) effect over a temperature range of 50-320 K. The maximum MR values are determined to be about 45.32% at H = 0.5 T and 28.34% at H = 0.3 T. At last, we report photoconductivity in BiFeO₃/La_0.7Sr_0.3MnO₃ film under illumination from 160 mW/cm² and 200 mW/cm² green-light source, and photoconductivities increase with the intensity of light enhanced.     

Electrical conductivity of LaxSr2−xFe1−yRuyO4±δ

Materials of the K₂NiF₄ structure type have been prepared and the electrical conductivity in air determined for a number of compositions in the La_xSr_2−xFe_1−yRu_yO_4±δ solid solution series including three with Ru substituted for Fe on the B site: La_0.2Sr_1.8Fe_0.6Ru_0.4O_4±δ, La_0.4Sr_1.6Fe_0.7Ru_0.3O_4±δ, and La_0.6Sr_1.4Fe_0.8Ru_0.2O_4±δ. Overall the total conductivity values measured were lower than expected for the Ru-doped materials, with a peak conductivity of ≈2 S cm⁻¹ at 700 °C. In the undoped La_xSr_2−xFeO_4±δ materials, a significant jump in conductivity was observed between the x = 0.7 and 0.8 compositions and was related to the bonding in the materials and the Fe³⁺/Fe⁴⁺ redox behaviour. In all materials, the conduction behaviour was found to follow a semi-conducting trend.     

BiFeO3-doped (Na0.5K0.5)NbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1−x)(Na_0.5K_0.5)NbO₃-xBiFeO₃ (x=0∼0.07) were synthesized by the solid-state reaction. Differential scanning calorimetry (DSC) measurements revealed that an increase in the amount of BiFeO₃ dopant resulted in a decrease in the orthorhombic-tetragonal and tetragonal-cubic phase transition temperature of the material. One percent BiFeO₃ additive suppressed grain growth, which not only benefits the sintering of ceramics but also enhances the piezoelectric and ferroelectric properties, where d₃₃=145pC/N, k_p=0.31, Q_m=80, P_r=11.3 μC cm⁻² and E_c=16.5 kV cm⁻¹. As x_BF>0.01, both piezoelectric and ferroelectric properties decreased rapidly with an increasing amount of dopant.     

Conduction in nanostructured La1?x Sr x FeO3 (0 ≤ x ≤ 1)

We investigated electrical properties of nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) from 300 K?C400 K. The nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was synthesized by citrate gel method requiring no pH control. X-ray diffraction pattern showed that single phase LaFeO₃ with an orthorhombic structure was formed. The structure changed into rhombohedral for x = 0.5 and it became cubic for x = 1.0. For x ?? 0.5, our material showed non-linear current-voltage characteristics and for x > 0.5 it showed linear current-voltage characteristics. Poole Frenkel type conduction mechanism was found to be operative in LaFeO₃ from 300 K?C400 K. The experimental values of field-lowering coefficient were by 2.56?C6.41 times higher than the predicted value and were attributed to the presence of localized fields. The increase in conductance with Sr content was due to formation of Fe⁴⁺ ions in addition to Fe³⁺ with the increase in Sr content. Impedance spectroscopy and ac conductivity analysis of La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was also carried out in the temperature range from 300 K?C400 K and frequency was varied from 20 Hz - 2 MHz. The ac conduction followed the correlated barrier hopping model in La_0.9Sr_0.1FeO₃.