The nature of iron-oxygen vacancy defect centers in PbTiO3

The iron(III) center in ferroelectric PbTiO3 together with an oxygen vacancy forms a charged defect associate, oriented along the crystallographic c-axis. Its microscopic structure has been analyzed in detail comparing results from a semi-empirical Newman superposition model analysis based on finestructure data and from calculations using density functional theory. Both methods give evidence for a substitution of Fe3+ for Ti4+ as an acceptor center. The position of the iron ion in the ferroelectric phase is found to be similar to the B-site in the paraelectric phase. Partial charge compensation is locally provided by a directly coordinated oxygen vacancy. Using high-resolution synchrotron powder diffraction, it was verified that lead titanate remains tetragonal down to 12 K, exhibiting a c/a-ratio of 1.0721.Comment: 11 pages, 5 figures, accepted in Phys. Rev.

Sr Surface Enrichment in Solid Oxide Cells – Approaching the Limits of EDX Analysis by Multivariate Statistical Analysis and Simulations

In solid oxide cells, Sr segregation has been correlated with degradation. Yet, the atomistic mechanism remains unknown. Here we begin to localize the origin of Sr surface nucleation by combining force field based simulations, energy dispersive X-ray spectroscopy (EDX), and multi-variate statistical analysis. We find increased ion mobility in the complexion between yttria-stabilized zirconia and strontium-doped lanthanum manganite. Furthermore, we developed a robust and automated routine to detect localized nucleation seeds of Sr at the complexion surface. This hints at a mechanism originating at the complexion and requires in-depth studies at the atomistic level, where the developed routine can be beneficial for analyzing large hyperspectral EDX datasets