Combining electrochemical and quantitative elemental analysis to investigate the sulfur poisoning process of ceria thin film fuel electrodes.

This work deals with the effect of sulfur incorporation into model-type GDC thin films on their in-plane ionic conductivity. By means of impedance measurements, a strongly deteriorating effect on the grain boundary conductivity was confirmed, which additionally depends on the applied electrochemical polarisation. To quantify the total amount of sulfur incorporated into GDC thin films, online-laser ablation of solids in liquid (online-LASIL) was used as a novel solid sampling strategy. Online-LASIL combines several advantages of conventional sample introduction systems and enables the detection of S as a minor component in a very limited sample system (in the present case 35 µg total sample mass). To reach the requested sensitivity for S detection using an inductively coupled plasma-mass spectrometer (ICP-MS), the reaction cell of the quadrupole instrument was used and the parameters for the mass shift reaction with O2 were optimised. The combination of electrical and quantitative analytical results allows the identification of a potential sulfur incorporation pathway, which very likely proceeds along GDC grain boundaries with oxysulfide formation as the main driver of ion transport degradation. Depending on the applied cathodic bias, the measured amount of sulfur would be equivalent to 1-4 lattice constants of GDC transformed into an oxysulfide phase at the material's grain boundaries.

Measurement of the across-plane conductivity of YSZ thin films on silicon.

Across-plane conductivity measurements on ion conducting thin films of a few ten nanometers thickness are challenging due to frequently occurring short-circuits through pinholes in the layer. In this contribution, a method is proposed which allowed across-plane conductivity measurements on yttria stabilized zirconia (YSZ) layers with thicknesses as low as 20 nm. YSZ layers were prepared onto silicon substrates with a thin native silica interlayer and the across-plane conductivity was measured on circular microelectrodes by impedance spectroscopy. The silica interlayer exhibits strongly blocking behavior, which helps to avoid short-circuits through pinholes. Different relaxation frequencies of YSZ and silica make separation of these layers possible. An equivalent circuit is suggested, which allows extraction of YSZ properties, and its validity is proven by varying microelectrodes size and layer thickness. All parameters yield the expected behavior.

The grain and grain boundary impedance of sol-gel prepared thin layers of yttria stabilized zirconia (YSZ).

Separating grain and grain boundary impedance contributions of ion conducting thin films is a highly non-trivial task. Recently, it could be shown that long, thin, closely spaced, and interdigitally arranged electrodes enabled such a separation on pulsed laser deposited yttria stabilized zirconia (YSZ) thin films. In this contribution, the same approach was used to investigate YSZ layers prepared by the sol-gel route on sapphire substrates. Grain and grain boundary properties were quantified for layers between 28 and 168 nm thickness. Only for the thinnest of the investigated layers, a deviation from macroscopic bulk properties was found, which could be correlated to interfacial strain in the epitaxial layer. A dependence of the preferential orientation on the film thickness was found.

Measurement of 18O tracer diffusion coefficients in thin yttria stabilized zirconia films.

In this paper we present a method to measure oxygen tracer diffusion coefficients in thin ion conducting films without being limited by slow oxygen incorporation kinetics. The method is based on a two step process. In the first step a substantial amount of 18O tracer is locally incorporated for example into an yttria stabilized zirconia (YSZ) layer at low temperatures with the aid of an electric current, thus overcoming slow thermal oxygen exchange while still limiting lateral diffusion to a minimum. In the second step controlled diffusion takes place at elevated temperatures in ultra high vacuum (UHV) to impede loss of tracer due to oxygen exchange at the film surface. In this second step the surface of the thin film may additionally be modified compared to the oxygen incorporation step. This allows to easily investigate effects of interfaces on ion transport. The achieved in-plane concentration profiles are then measured by secondary ion mass spectrometry (SIMS). Comparison with electrical measurements on YSZ thin films proves the applicability of the method.

The separation of grain and grain boundary impedance in thin yttria stabilized zirconia (YSZ) layers.

An improved electrode geometry is proposed to study thin ion conducting films by impedance spectroscopy. It is shown that long, thin, and closely spaced electrodes arranged interdigitally allow a separation of grain and grain boundary effects also in very thin films. This separation is shown to be successful for yttria stabilized zirconia (YSZ) layers thinner than 20 nm. In a series of experiments it is demonstrated that the extracted parameters correspond to the YSZ grain boundary and grain bulk resistances or to grain boundary and substrate capacitances. Results also show that our YSZ films produced by pulsed-laser deposition (PLD) on sapphire substrates exhibit a bulk conductivity which is very close to that of macroscopic YSZ samples.