Localized to Itinerant Electronic Transition in Perovskite Oxides

Interest in the transition metal oxides with perovskite related structures goes back to the 1950s when the sodium tungsten bronzes NaxWO3 were shown to be metallic [1 ], the system LalxSr~MnO3 was found to contain a ferromagnetic conductive phase [2], and La0.sSr0.sCoO3 was reported to be a ferromagnetic metal, but with a peculiar magnetization of 1.5 #a/Co atom [3]. Stoichiometric oxide perovskites have the generic formula AMO3 in which the A site is at the center of a simple cubic array of M sites; the oxide ions form (180 4)) M O M bridges to give an MO3 array of corner shared MO6/2 octahedra and the larger A cations have twelvefold oxygen coordination. Mismatch between the A O and M O equilibrium bond lengths introduces internal stresses. A compressive stress on the MO3 array is accommodated by a lowering of the M O M bond angle from 180 to (180 4)); a tensile stress on the M O M bonds is accommodated by the formation of hexagonal polytypes [4].