Phase Transitions in Quasi-one-dimensional Selenide BaNbSe3and Superconductivity in BaNb2Se5

Samples with various compositions around BaNbSe3were prepared. X-ray analysis revealed that the compound is stable at the composition of BaNb0.80Se3, which formally requires Nb5+ions (d0). The single-phase region extends to the composition BaNb0.95Se3. A semiconductor-to-metal transition was observed at ∼140 K in BaNb0.95Se3. Seebeck measurements showed that the dominant carriers were electrons, which are considered to originate from Nb4+ions (d1) coexisting with Nb5+ions. On the basis of detailed phase study, the transition was revealed to be intrinsic to BaNb0.95Se3with a very slight Ba deficiency. BaNb0.95Se3with a slight Ba excess shows a semiconductor-to-semiconductor transition at 200-300 K. Seebeck measurements showed that the dominant carriers are electrons above the transition and are holes below the transition. A new compound, BaNb2Se5with a BaTa2S5-type structure, was found to show superconductivity at 2.5 K.