Edvinas Navickas

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

Abstract 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,

Water-Induced Decoupling of Tracer and Electrochemical Oxygen Exchange Kinetics on Mixed Conducting Electrodes.

Isotope exchange depth profiling and electrochemical impedance spectroscopy are usually regarded as complementary tools for measuring the surface oxygen exchange activity of mixed conducting oxides, for example used in solid oxide fuel cell (SOFC) electrodes. Only very few studies compared electrical (kq) and tracer (k*) exchange coefficients of solid–gas interfaces measured under identical conditions. The 1:1 correlation between kq and k* often made is thus more an assumption than experimentally verified. In this study it is shown that the measured rates of electrical and tracer exchange of oxygen may strongly differ. Simultaneous acquisition of kq and k* on La0.6Sr0.4FeO3-δ and SrTi0.3Fe0.7O3-δ thin film electrodes revealed that k* > 100 kq in humid oxidizing (16O2 + H218O) and humid reducing (H2 + H218O) atmospheres. These results are explained by fast water adsorption and dissociation on surface oxygen vacancies, forming two surface hydroxyl groups. Hence, interpreting experimentally determined k* values in terms of electrochemically relevant oxygen exchange is not straightforward.

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.

The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT)

The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La3+ donor-doped, Fe3+ acceptor-doped and La3+/Fe3+-co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

Consequences of the CMR effect on EELS in TEM

Double perovskite oxides have gained in importance and exhibit negative magnetoresistance, which is known as colossal magnetoresistance (CMR) effect. Using a La2CoMnO6 (LCM) thin film layer, we proved that the physical consequences of the CMR effect do also influence the electron energy loss spectrometry (EELS) signal. We observed a change of the band gap at low energy losses and were able to study the magnetisation with chemical sensitivity by employing energy loss magnetic chiral dichroism (EMCD) below the Curie temperature TC, where the CMR effect becomes significant.