Journal of the American Chemical Society, Vol.131, No.24, 8660-8668, 2009
Ordered Rock-Salt Related Nanoclusters in CaMnO2
Oxygen engineering techniques performed under adequate controlled atmosphere show that the CaMnO3-CaMnO2 topotactic reduction-oxidation process proceeds via oxygen diffusion while the cationic sublattice remains almost unaltered. Extra superlattice reflections in selected area electron diffraction patterns indicate doubling of the CaMnO2 rock-salt cell along the cubic directions of a distorted rhombohedral cell originated by ordering of Ca2+ and Mn2+ ions distributed in nanoclusters into a NaCl-type matrix, as evidenced by dark field electron microscope images. The local nature of the information provided by the transmission electron microscopy techniques used to characterize the rock-salt type Ca1-xMnxO2 solid solution clearly hints at the existence of subtle extra ordering in other upper oxides of the Ca-Mn-O system. The combination of local characterization techniques like electron microscopy with more average ones like powder X-ray and neutron diffraction allows a very complete characterization of the system.