Sodium ordering and the control of magnetism in sodium cobaltate

Abstract The long-range three-dimensional ordering of Na + ions was studied in a sample of composition Na 0.75 CoO 2 using single-crystal neutron diffraction. Large-scale numerical simulations reveal the ordering principle for this system, the formation of multi-vacancy charged droplets then order long range, and the structure factors from these defect clusters are in good agreement with the observed neutron diffraction intensities. The electrostatic potential is found to be the dominant factor in determining the sodium ordering and its associated distortion field. The superstructures induce a periodic potential in the CoO 2 , giving potential wells that are larger than the single-particle hopping frequency and so able to localize holes. The results readily explain many of the observed electrical and magnetic properties, including the three dimensionality of the magnetic excitations.