Structural and electronic properties of the Nb$_4$-cluster compound Ga$_{1.33}$Nb$_4$X$_8$ (X = S, Se)

Abstract

We report resistivity, thermopower and magnetic susceptibility measurements on the Nb$_4$-cluster compounds Ga$_{1.33}$Nb$_4$X$_{8}$ (X = S, Se), derived from vacancy ordered spinels A$_x$T$_4$X$_8$. The cubic selenide phase is insulating and its resistivity crosses over from $\lnρ \sim T^{-1}$ to $\sim T^{-1/2}$ on cooling below 150 K, indicating variable range hopping (VRH) conduction at low temperatures. This is similar to that previously reported for V$_4$ and Mo$_4$ cluster compounds. The rhombohedrally distorted sulfide is metallic and shows a minimum in resistance at $\sim $ 56 K below which the resistivity varies as $ρ(T) \sim T^{-1/2}$. The thermopower of the selenide becomes temperature independent below the crossover temperature. These Nb$_4$ compounds exhibit enhanced Pauli-paramagnetic magnetic susceptibility ($χ$) irrespective of their transport properties and both undergo a similar transition in $χ(T) \sim 30$ K. We discuss these properties in the model of hopping conduction under long-range Coulomb repulsion effects and derive consistency between some of the transport and magnetic parameters.