We have used neutrons to better understand its properties. Neutron diffraction from Na_xCoO₂ reveals a kaleidoscope of sodium ordering patterns as a function of concentration. Electrostatic forces stabilize sodium vacancies into clusters (shown in red in the figure) and these order long range at simple fractional fillings. The sodium superstructures strongly affect the electronic behaviour of Na_xCoO₂. They cause some of the charge carriers in the Co layers to be trapped, and in this way the sodium ordering can be used to control the electronic properties. The Coulomb landscape in the figure shows how the mobile charge carriers are confined to restricted regions of the plane, enhancing their interactions and explaining their anomalous properties. The vacancy clusters form cages in which sodium ions can rattle, disrupting phonon propagation without affecting the electrical conductivity and resulting in Na_xCoO₂’s thermoelectric properties.

DJP Morris, JP Goff (University of Liverpool), DA Tennant (HMI Berlin, Germany), M Roger (CEA Saclay, France), D Prabhakaran (University of Oxford), MJ Gutmann (ISIS)

Research date: December 2007

Further Information

M Roger et al., Nature 445 (2007) 631​