Emergent charge ordering in near half doped Na$_{0.46}$CoO$_{2}$


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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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