ABSTRACT
From 59Co and 23Na 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.
ABSTRACT
A 59Co NMR study of CoO2, the x=0 end member of AxCoO2 (A=Na,Li,...) cobaltates, reveals a metallic ground state, though with clear signs of strong electron correlations: low-energy spin fluctuations develop at wave vectors q not equal to 0 and a crossover to a Fermi-liquid regime occurs below a characteristic temperature T* approximately 7 K. Despite some uncertainty over the exact cobalt oxidation state in this material, the results show that electronic correlations are revealed as x is reduced below 0.3. The data are consistent with NaxCoO2 being close to the Mott transition in the x-->0 limit.
ABSTRACT
Crystallographic, magnetic, and NMR properties of a Na1CoO2 single crystal with x approximately = 1 are presented. We identify the stoichiometric Na1CoO2 phase, which is shown to be a nonmagnetic insulator, as expected for homogeneous planes of Co3+ ions with S = 0. In addition, we present evidence that, because of slight average Na deficiency, chemical and electronic phase separation leads to a segregation of Na vacancies into the well-defined, magnetic, Na0.8CoO2 phase. The importance of phase separation is discussed in the context of magnetic order for x approximately = 0.8 and the occurrence of a metal-insulator transition for x --> 1.
