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Register a new userNa atomic order, Co charge disproportionation and magnetism in Na$_{x}$CoO$_{2}$ for large Na contents
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We have synthesized and characterized four different stable phases of Na ordered Na$_{x}$CoO$_{2}$, for $0.65<x<0.8$. Above 100 K they display similar Curie-Weiss susceptibilities as well as ferromagnetic $q=0$ spin fluctuations in the CoO$_{2}$ planes revealed by $^{23}$Na NMR data. In all phases from $^{59}$Co NMR data we display evidences that the Co disproportionate already above 300 K into non magnetic Co$^{3+}$ and magnetic $approx $Co$^{3.5+}$ sites on which holes delocalize. This allows us to understand that metallic magnetism is favored for these large Na contents. Below 100 K the phases differentiate, and a magnetic order sets in only for $xgtrsim 0.75$ at $T_{N}=$22 K. We suggest that the charge order also governs the low $T$ energy scales and transverse couplings.
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We have synthesized and characterized different stable phases of sodium cobaltates Na$_{x}$CoO$_{2}$ with sodium content $0.65<x<0.80$. We demonstrate that $^{23}$Na NMR allows to determine the difference in the susceptibility of the phases and reveals the presence of Na order in each phase. $^{59}$Co NMR experiments give clear evidence that Co charge disproportionation is a dominant feature of Na cobaltates. Only a small fraction ($approx$ 25%) of cobalts are in a non-magnetic Co$^{3+}$ charge state whereas electrons delocalize on the other cobalts. The magnetic and charge properties of the different Co sites are highly correlated with each other as their magnetic shift $K_{ZZ}$ scales linearly with their quadrupolar frequency $nu_Q$. This reflects the fact that the hole content on the Co orbitals varies from site to site. The unusual charge differentiation found in this system calls for better theoretical understanding of the incidence of the Na atomic order on the electronic structures of these compounds.
$^{59}$Co NMR experiments have been performed on single crystals of the layered cobaltate Na$_{x}$CoO$_{2}$ with x=0.77 which is an antiferromagnet with Neel temperature $T_{N}=22$~K. In this metallic phase six Co sites are resolved in the NMR spectra, with distinct quadrupole frequencies $ u _{Q}$, magnetic shifts $K_{ZZ}$ and nuclear spin lattice relaxation rates $% 1/T_{1}$. Contrary to the $x=1/2$ or $x=2/3$ phases the 3D stacking of the Na planes is not perfect for $x=0.77$ but this does not influence markedly the electronic properties. We evidence that the magnetic and charge properties of the Co sites are highly correlated with each other as $K_{ZZ}$ and $(1/T_{1})^{1/2}$ scale linearly with $ u _{Q}$. The data analysis allows us to separate the contribution $ u_{Q}^{latt}$ of the ionic charges to $ u _{Q}$ from that $ u _{Q}^{el}$ due to the hole orbitals on the Co sites. We could extend coherently this analysis to all the known phases in the Na cobaltate phase diagram. The variation with $x$ of $ u _{Q}^{latt}$ is found to fit rather well numerical computations done in a point charge model. The second term $ u _{Q}^{el}$ allowed us to deduce the hole concentration on the cobalts. These detailed experimental results should stimulate theoretical calculations of the electronic structure involving both the Co orbital configurations and DMFT approaches to take into account the electronic correlations.
We have investigated a set of sodium cobaltates (NaxCoO2) samples with various sodium content (0.67 le x le 0.75) using Nuclear Quadrupole Resonance (NQR). The four different stable phases and an intermediate one have been recognized. The NQR spectra of 59Co allowed us to clearly differentiate the pure phase samples which could be easily distinguished from multi-phase samples. Moreover, we have found that keeping samples at room temperature in contact with humid air leads to destruction of the phase purity and loss of sodium content. The high sodium content sample evolves progressively into a mixture of the detected stable phases until it reaches the x=2/3 composition which appears to be the most stable phase in this part of phase diagram.
We have synthesized and characterized the four different stable phases of Na ordered Na$_{x}$CoO$_{2}$, for $0.65<xlesssim 0.75$. Above 100K they display similar Curie-Weiss spin susceptibilities as well as ferromagnetic $q=0$ spin fluctuations in the CoO$_{2}$ planes revealed respectively by $^{23}$Na NMR shift and spin lattice $T_{1}$ data. The Co disproportionate already above 300K into Co$^{3+}$ and $approx $Co$^{3.5+}$ in all phases, which allows us to understand that magnetism is favoured. Below 100K the paramagnetic properties become quite distinct, and a 3D magnetic order sets in only for $x=0.75$, so that charge order has a subtle incidence on the low $T$ energy scales and transverse magnetic couplings.
We have utilized neutron powder diffraction to probe the crystal structure of layered Na$_{x}$CoO$_{2}$ near the half doping composition of $x=$0.46 over the temperature range of 2 to 600K. Our measurements show evidence of a dynamic transition in the motion of Na-ions at 300K which coincides with the onset of a near zero thermal expansion in the in-plane lattice constants. The effect of the Na-ordering on the CoO$_{2}$ layer is reflected in the octahedral distortion of the two crystallographically inequivalent Co-sites and is evident even at high temperatures. We find evidence of a weak charge separation into stripes of Co$^{+3.5+epsilon}$ and Co$^{+3.5-epsilon}$, $epsilonsim0.06e$ below Tco=150K. We argue that changes in the Na(1)-O bond lengths observed at the magnetic transition at tm=88K reflect changes in the electronic state of the CoO$_{2}$ layer
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