Observations of Co4+ in a higher spin state and the increase in the Seebeck coefficient of thermoelectric Ca3Co4O9.

Ca3Co4O9 has a unique structure that leads to exceptionally high thermoelectric transport. Here we report the achievement of a 27% increase in the room-temperature in-plane Seebeck coefficient of Ca3Co4O9 thin films. We combine aberration-corrected Z-contrast imaging, atomic-column resolved electron energy-loss spectroscopy, and density-functional calculations to show that the increase is caused by stacking faults with Co4+-ions in a higher spin state compared to that of bulk Ca3Co4O9. The higher Seebeck coefficient makes the Ca3Co4O9 system suitable for many high temperature waste-heat-recovery applications.

Atomic structure of highly strained BiFeO3 thin films.

We determine the atomic structure of the pseudotetragonal T phase and the pseudorhombohedral R phase in highly strained multiferroic BiFeO(3) thin films by using a combination of atomic-resolution scanning transmission electron microscopy and electron energy-loss spectroscopy. The coordination of the Fe atoms and their displacement relative to the O and Bi positions are assessed by direct imaging. These observations allow us to interpret the electronic structure data derived from electron energy-loss spectroscopy and provide evidence for the giant spontaneous polarization in strained BiFeO(3) thin films.

Simulation of spatially resolved electron energy loss near-edge structure for scanning transmission electron microscopy.

Aberration-corrected scanning transmission electron microscopy yields probe-position-dependent energy-loss near-edge structure (ELNES) measurements, potentially providing spatial mapping of the underlying electronic states. ELNES calculations, however, typically describe excitations by a plane wave traveling in vacuum, neglecting the interaction of the electron probe with the local electronic environment as it propagates through the specimen. Here, we report a methodology that combines a full electronic-structure calculation with propagation of a focused beam in a thin film. The results demonstrate that only a detailed calculation using this approach can provide quantitative agreement with observed variations in probe-position-dependent ELNES.