Fast oxygen exchange and diffusion kinetics of grain boundaries in Sr-doped LaMnO3 thin films.

In this study, the contribution of grain boundaries to the oxygen reduction and diffusion kinetics of La0.8Sr0.2MnO3 (LSM) thin films is investigated. Polycrystalline LSM thin films with columnar grains of different grain sizes as well as epitaxial thin films were prepared by pulsed laser deposition. (18)O tracer exchange experiments were performed at temperatures from 570 °C to 810 °C and subsequently analyzed by secondary ion mass spectrometry (SIMS). The isotope concentration depth profiles of polycrystalline films clearly indicate contributions from diffusion and surface exchange in grains as well as in grain boundaries. Measured depth profiles were analyzed by finite element modeling and revealed the diffusion coefficients D and oxygen exchange coefficients k of both the grain bulk and grain boundaries. Values obtained for grain boundaries (Dgb and kgb) are almost three orders of magnitude higher than those of the grains (Dg and kg). Hence, grain boundaries may not only facilitate fast oxygen diffusion but also fast oxygen exchange kinetics. Variation of the A-site stoichiometry ((La0.8Sr0.2)0.95MnO3) did not lead to large changes of the kinetic parameters. Properties found for epitaxial layers without grain boundaries (Db and kb) are close to those of the grains in polycrystalline layers.

Electrochemical properties of La0.6Sr0.4CoO3 - δ thin films investigated by complementary impedance spectroscopy and isotope exchange depth profiling.

The oxygen exchange and diffusion properties of La0.6Sr0.4CoO3 - Î´ thin films on yttria stabilized zirconia were analyzed by impedance spectroscopy and 18O tracer experiments. The investigations were performed on the same thin film samples and at the same temperature (400 °C) in order to get complementary information by the two methods. Electrochemical impedance spectroscopy can reveal resistive and capacitive contributions of such systems, but an exact interpretation of the spectra of complex oxide electrodes is often difficult from impedance data alone. It is shown that additional isotope exchange depth profiling can significantly help interpreting impedance spectra by giving reliable information on the individual contribution and exact location of resistances (surface, electrode bulk, interface). The measurements also allowed quantitative comparison of electrode polarization resistances obtained by different methods.

How UV light lowers the conductivity of SrTiO3 by photochemical water splitting at elevated temperature.

Nominally undoped SrTiO3 single crystals were illuminated by UV light at 350 °C in oxidizing as well as reducing atmospheres. In N2/O2 atmospheres, UV irradiation enhances the conductivity of SrTiO3 by several orders of magnitude. In dry H2 atmosphere UV exposure leads to the opposite conductivity effect, i.e., above band gap energy illumination surprisingly lowers the conductivity. This is discussed in the framework of a defect chemical model. We show that a shift in defect concentrations due to UV-driven oxygen incorporation from the gas phase into the oxide is the main cause of the measured conductivity changes. A model is introduced to illustrate the thermodynamic and kinetic drivers of the processes under UV irradiation. Noteably, in reducing H2/H2O atmospheres, the incorporation of oxygen into the investigated oxide under UV light takes place via water splitting. Owing to the predominant electron conduction of SrTiO3 in equilibrium with H2, oxygen incorporation upon UV and thus an increase of the oxygen chemical potential leads to a decrease of the majority electronic charge carrier, here electrons, which lowers the conductivity under UV irradiation.

Dislocations Accelerate Oxygen Ion Diffusion in La0.8Sr0.2MnO3 Epitaxial Thin Films.

Revealing whether dislocations accelerate oxygen ion transport is important for providing abilities in tuning the ionic conductivity of ceramic materials. In this study, we report how dislocations affect oxygen ion diffusion in Sr-doped LaMnO3 (LSM), a model perovskite oxide that serves in energy conversion technologies. LSM epitaxial thin films with thicknesses ranging from 10 nm to more than 100 nm were prepared by pulsed laser deposition on single-crystal LaAlO3 and SrTiO3 substrates. The lattice mismatch between the film and substrates induces compressive or tensile in-plane strain in the LSM layers. This lattice strain is partially reduced by dislocations, especially in the LSM films on LaAlO3. Oxygen isotope exchange measured by secondary ion mass spectrometry revealed the existence of at least two very different diffusion coefficients in the LSM films on LaAlO3. The diffusion profiles can be quantitatively explained by the existence of fast oxygen ion diffusion along threading dislocations that is faster by up to 3 orders of magnitude compared to that in LSM bulk.

Operando X-ray Investigation of Electrode/Electrolyte Interfaces in Model Solid Oxide Fuel Cells.

We employed operando anomalous surface X-ray diffraction to investigate the buried interface between the cathode and the electrolyte of a model solid oxide fuel cell with atomic resolution. The cell was studied under different oxygen pressures at elevated temperatures and polarizations by external potential control. Making use of anomalous X-ray diffraction effects at the Y and Zr K-edges allowed us to resolve the interfacial structure and chemical composition of a (100)-oriented, 9.5 mol % yttria-stabilized zirconia (YSZ) single crystal electrolyte below a La0.6Sr0.4CoO3-δ (LSC) electrode. We observe yttrium segregation toward the YSZ/LSC electrolyte/electrode interface under reducing conditions. Under oxidizing conditions, the interface becomes Y depleted. The yttrium segregation is corroborated by an enhanced outward relaxation of the YSZ interfacial metal ion layer. At the same time, an increase in point defect concentration in the electrolyte at the interface was observed, as evidenced by reduced YSZ crystallographic site occupancies for the cations as well as the oxygen ions. Such changes in composition are expected to strongly influence the oxygen ion transport through this interface which plays an important role for the performance of solid oxide fuel cells. The structure of the interface is compared to the bare YSZ(100) surface structure near the microelectrode under identical conditions and to the structure of the YSZ(100) surface prepared under ultrahigh vacuum conditions.

Apparent Oxygen Uphill Diffusion in La0.8Sr0.2MnO3 Thin Films upon Cathodic Polarization.

The impact of cathodic bias on oxygen transport in La0.8Sr0.2MnO3 (LSM) thin films was investigated. Columnar-grown LSM thin films with different microstructures were deposited by pulsed laser deposition. 18O tracer experiments were performed on thin film microelectrodes with an applied cathodic bias of -300 or -450 mV, and the microelectrodes were subsequently analyzed by time-of-flight secondary ion mass spectrometry. The 18O concentration in the cathodically polarized LSM microelectrodes was strongly increased relative to that in the thermally annealed film (without bias). Most remarkable, however, was the appearance of a pronounced 18O fraction maximum in the center of the films. This strongly depended on the applied bias and on the microstructure of the LSM thin layers. The unusual shape of the 18O depth profiles was caused by a combination of Wagner-Hebb-type stoichiometry polarization of the LSM bulk, fast grain boundary transport and voltage-induced modification of the oxygen incorporation kinetics.