High-resolution neutron diffraction study of possible charge ordering in Na0.5CoO2

The structure of Na0.5CoO2, the low-temperature insulator that separates the antiferromagnetic and normal metals in the NaxCoO2 phase diagram, is studied by high-resolution powder neutron diffraction at temperatures between 10 and 300 K. Profile analysis confirms that it has an orthorhombic symmetry structure, space group Pnmm, consisting of layers of edge-sharing CoO6 octahedra in a triangular lattice, with Na ions occupying ordered positions in the interleaving planes. The oxygen content is found to be stoichiometric within 1%, indicating that the Na concentration accurately determines the electronic doping. The Na ordering creates two distinct Co sites, in parallel chains running along one crystallographic direction. The differences in their Co-O bond distances and the derived bond valence sums, reflections of the degree of charge ordering in this phase, are very small.