Electronic texture of the thermoelectric oxide Na0.75CoO2

From Co-59 and Na-23 NMR, we demonstrate the impact of the Na+ vacancy ordering on the cobalt electronic states in Na0.75CoO2: at long time scales, there is neither a disproportionation into 75% Co3+ and 25% Co4+ states, nor a mixed-valence metal with a uniform Co3.25+ state. Instead, the system adopts an intermediate configuration in which 30% of the lattice sites form an ordered pattern of localized Co3+ states. Above 180 K, an anomalous mobility of specific Na+ sites is found to coexist with this electronic texture, suggesting that the formation of the latter may contribute to stabilizing the Na+ ordering. Control of the ion doping in these materials thus appears to be crucial for fine-tuning of their thermoelectric properties.