New Antiferromagnetic Perovskite CaCo 3 V 4 O 12 Prepared at High-Pressure and High-Temperature Conditions (original) (raw)

A new perovskite, CaCo 2+ 3 V 4+ 4 O 12 , has been synthesized at high-pressure and high-temperature (HP-HT) conditions. The properties of this perovskite were examined by a range of techniques. CaCo 3 V 4 O 12 was found to adopt a double-perovskite cubic lattice [a = 7.3428(6) Å] with Im3̅ symmetry. We have established that this new perovskite is stable at ambient conditions, and its oxidation and/or decomposition at ambient pressure begins above 500°C. It undergoes an abrupt antiferromagnetic transition around 98 K. Electrical resistivity data suggest semimetallic conductivity in the temperature range of 1.6−370 K. We have established that the Co 2+ ions in CaCo 3 V 4 O 12 are in the high-spin state with a sizable orbital moment, even though their square-planar oxygen coordination could be more suitable for the low-spin state, which is prone to Jahn−Teller distortion. Electrical resistivity curves also exhibit a distinct steplike feature around 100 K. CaCo 3 V 4 O 12 is a first example of perovskite in which the sites A′ are fully occupied by Co 2+ ions, and hence its synthesis opens the door to a new class of double perovskites, ACo 3 B 4 O 12 , that may be derived by chemical substitution of the A sublattice by lanthanides, sodium, strontium, and bismuth and by other elements and/or of the B sublattice by some other transition metals.