Observations of Co^{4+} in a Higher Spin State and the Increase in the Seebeck Coefficient of Thermoelectric Ca_{3}Co_{4}O_{9}

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 Co4þ-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.