Isostructural phase transition and equation of state of type-I and type-VIII metallic sodium borosilicide clathrates

Abstract: Electronic properties of silicon-based clathrates can be tuned by boron incorporation into the silicon cage network. Sodium borosilicides clathrate outstands with uncommon stoichiometry and expected metallic properties, in contrast to other alcali metal semiconductive Zintl borosilicides. In this study, we report an experimental investigation of the high-pressure behavior of type-I and type-VIII sodium borosilicide clathrates. An isostructural phase transition, marked by an abrupt volume collapse at 13 GPa, is observed exclusively in type-I sodium borosilicide clathrates. This transition is attributed to the pressure-induced diffusion of silicon atoms into cationic sites. This mechanism provides the first experimental validation of a transition predicted theoretically for this class of materials. Isostructural phase transitions were only observed in type-I borosilicide. In contrast, the type-VIII borosilicide phase exhibits conventional elastic compression. The metallic character was established using reflectance spectroscopy over a wide energy range, in good agreement with crystallographic data on the boron content.