Surface potentials of acceptor- and donor-doped CeO2 thin films and their relation to oxygen surface exchange.

Surface Fermi level positions, ionisation potentials, and work functions of acceptor-, donor-, and nominally undoped CeO2 have been determined by means of in situ photoelectron spectroscopy on films grown with different surface orientation and preparation conditions. The Fermi energy varies in accordance with the doping and oxygen activity. The ionisation potentials are largely unaffected by the preparation conditions and surface orientation. They are comparable for nominally undoped, 1% donor-doped, and 1% acceptor-doped films. The majority of the 10% Gd-doped films exhibit a 0.5 eV lower ionisation potential, which might be related to the presence of a surface space-charge region. The lower ionisation potential of the 10% Gd-doped films compensates for their lower Fermi energies and eventually results in work functions being largely independent on doping. Oxygen surface exchange coefficients determined using secondary ion mass spectrometry and conductivity relaxation experiments reveal similar magnitudes and are not strongly affected by doping type, concentration, and surface orientation. The results indicate that surface space-charge regions are crucial for oxygen surface exchange but do not allow to finally identify the rate determining step for oxygen incorporation into CeO2-based materials.

Oxygen Surface Exchange and Tracer Diffusion in Differently Oriented Thin Films of Gd-Doped CeO2.

The exchange of 18O between gaseous molecular oxygen and thin-film samples of Ce0.99Gd0.01O1.995 with two different, nominal surface orientations [(111) and (110)] was studied. Oxygen isotope exchange experiments were conducted in the temperature range of 573 ≤ T/K ≤ 673 at an oxygen activity of aO2 = 0.2. Subsequently, secondary ion mass spectrometry (SIMS) measurements were performed on the thin-film samples to obtain 18O isotope depth profiles. All 18O diffusion profiles showed two features, suggesting spatially nonuniform oxygen tracer diffusion coefficients in the samples. A numerical solution to the diffusion equation was used to describe the experimental profiles and yielded oxygen tracer diffusion coefficients D* and oxygen surface exchange coefficients k*. Values of D* obtained were found, surprisingly, to be different for the two orientations and also orders of magnitude lower than values for ceramic samples in this temperature range. As possible explanations, we examine quantitatively the effect of halide anion impurities and the effect of ultrasmall columnar grains on oxygen tracer diffusion. Surface exchange coefficients for the (111) oriented surface were found to be roughly 1 order of magnitude higher than those for (110). We discuss two possible explanations for the observed behavior: the enrichment of anion impurities at the surface and the interaction between the surface and vapor water in the gas phase.

Computational Study of Oxygen Diffusion along a[100] Dislocations in the Perovskite Oxide SrTiO3.

We used classical molecular-dynamics simulations to study the atomistic structure of, and the diffusion of oxygen ions along, the periodic array of edge dislocations comprising a symmetrical 6.0° [100] tilt grain boundary in SrTiO3. The results indicate that, at elevated temperatures, the two types of dislocation core (TiO2-type and SrO-type) that make up the boundary are stable and that oxygen-deficient cores maintain their dissociated structures. They also confirm that oxygen vacancies prefer to reside at the cores rather than in the bulk. Tracer diffusion coefficients of oxygen were obtained for oxygen-deficient bulk and grain-boundary simulation cells at temperatures in the range of 1000 ≤ T/K ≤ 2300. Calculated values of the oxygen-vacancy diffusion coefficient for the bulk phase agree extremely well with published experimental data. Tracer diffusion coefficients obtained for the grain-boundary cell are, in comparison to those for the bulk, lower in magnitude and have a higher activation enthalpy, indicating that, relative to the bulk, the migration of oxygen ions along a[100] dislocation cores in SrTiO3 is hindered. These results provide further support for the decoupled model of filament formation in resistively switching SrTiO3.