The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.

The mixed ionic-electronic conductor (MIEC) (Ba 0.5 Sr 0.5 )(Co 0.8 Fe 0.2 )O 3-δ (BSCF) is a renowned material with applications in membrane reactors and as cathodes in solid-oxide fuel cells. Despite BSCF's large oxygen permeabilities, long-time phase instability at intermediate temperatures has been reported. However, the mechanism of this decomposition is still unclear. Here, we present a study of the synthesis of BSCF and compare our results with those obtained from long-time decomposition. Rietveld and Le Bail analysis as well as transmission electron microscopy studies were applied to investigate the reaction sequence in BSCF formation. We are now able to draw the following conclusion about the reaction mechanism: the formation as well as decomposition is due to a reversible reordering of the hexagonal AO 3 -layer stacking sequence in the cubic perovskite, which can occur if the cubic BSCF is kept at temperatures below T ) 1173 K for long time periods, thereby leading to the decomposition of BSCF into a three-phase mixture. The driving force for this reaction was identified to occur at the cobalt site because cobalt prefers a low-spin configuration in the 3+ oxidation state. This reaction occurs only at temperatures below T ) 1173 K because of the oxidation of cobalt at low temperatures.

Pulsed Laser Deposition (PLD) was used to prepare thin fi lms with the nominal composition La 0.58 Sr 0.4 Co 0.2 Fe 0.8 O 3− δ (LSCF). The thin fi lm microstructure was investigated as a function of PLD deposition parameters such as: substrate temperature, ambient gas pressure, target-to-substrate distance, laser fl uence and frequency. It was found that the ambient gas pressure and the substrate temperature are the key PLD process parameters determining the thin fi lm micro-and nanostructure. A map of the LSCF fi lm nanostructures is presented as a function of substrate temperature (25-700 ° C) and oxygen background pressure (0.013-0.4 mbar), with fi lm structures ranging from fully dense to highly porous. Fully crystalline, dense, and crack-free LSCF fi lms with a thickness of 300 nm were obtained at an oxygen pressure lower than 0.13 mbar at a temperature of 600 ° C. The obtained knowledge on the structure allows for tailoring of perovskite thin fi lm nanostructure, e.g., for solid oxide fuel cell cathodes. A simple geometrical model is proposed, allowing estimation of the catalytic active surface area of the prepared thin fi lms. It is shown that voids at columnar grain boundaries can result in an increase of the surface area by approximately 25 times, when compared to dense fl at fi lms.

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Single phase and strained LuMnO(3) thin films are discovered to display coexisting ferromagnetic and antiferromagnetic orders. A large moment ferromagnetism (≈1μ(B)), which is absent in bulk samples, is shown to display a magnetic moment distribution that is peaked at the highly strained substrate-film interface. We further show that the strain-induced ferromagnetism and the antiferromagnetic order are coupled via an exchange field, therefore demonstrating strained rare-earth manganite thin films as promising candidate systems for new multifunctional devices.

Partially amorphous La 0.6 Sr 0.4 CoO 3-δ (LSC) thin-fi lm cathodes are fabricated using pulsed laser deposition and are integrated in free-standing micro-solid oxide fuel cells (micro-SOFC) with a 3YSZ electrolyte and a Pt anode. A low degree of crystallinity of the LSC layers is achieved by taking advantage of the miniaturization of the cells, which permits low-temperature operation (300-450 °C). Thermomechanically stable micro-SOFC are obtained with strongly buckled electrolyte membranes. The nanoporous columnar microstructure of the LSC layers provides a large surface area for oxygen incorporation and is also believed to reduce the amount of stress at the cathode/ electrolyte interface. With a high rate of failure-free micro-SOFC membranes, it is possible to avoid gas cross-over and open-circuit voltages of 1.06 V are attained. First power densities as high as 200-262 mW cm −2 at 400-450 °C are achieved. The area-specifi c resistance of the oxygen reduction reaction is lower than 0.3 Ω cm 2 at 400 °C around the peak power density. These outstanding fi ndings demonstrate that partially amorphous oxides are promising electrode candidates for the next-generation of solid oxide fuel cells working at low-temperatures.

The crystallization and microstuctural evolution upon thermal treatment of yttria‐stabilized zirconia (YSZ, Zr0.85Y0.15O1‐δ) thin films deposited by spray pyrolysis at 370 °C are investigated. The as‐deposited YSZ films are mainly amorphous with a few crystallites of 3 nm in diameter and crystallize in the temperature range from 400 °C to 900 °C. Fully crystalline YSZ thin films are obtained after heating to 900 °C or by isothermal dwells for at least 17 h at a temperature as low as 600 °C. Three exothermic heat releasing processes with activation energies are assigned to the crystallization and the oxidation of residuals from the precursor. Microporosity develops during crystallization and mass loss. During crystallization the microstrain decreases from 4% to less than 1%. Simultaneously, the average grain size increases from 3 nm to 10 nm. The tetragonal phase content of the YSZ thin film increases with increasing temperature and isothermal dwell time. Based on these data, gentle processing conditions can be designed for zirconia based thin films, which meet the requirements for Si‐based microfabrication of miniaturized electrochemical devices such as micro‐solid oxide fuel cells or sensors.