Exploring silicon allotropy and chemistry by high pressure – high temperature conditions

Abstract

Silicon is the second abundant element, after oxygen, in the earth crust. It is essential for today’s electronics because of its ability to show various electronic behaviors that allow covering the numerous fields of cutting-edge applications. Moreover, silicon is not a pollutant and, therefore, is an ideal candidate to replace the actual materials in photovoltaics, like compounds based on the arsenic and heavy metals. It has not replaced them so far because Si is an indirect gap semiconductor and cannot absorb directly the solar photons without thermal agitations of crystal lattice (phonons). This puts it apart from the next-generation applications (light diode, high-performance transistor). That justifies the attempts to create silicon materials with direct gap that can absorb and emit light. Our recent high-pressure studies of the chemical interaction and phase transformations in the Na-Si system, revealed a number of interesting routes to new and known silicon compounds and allotropes. The pressure-temperature range of their formation is suitable for large-volume synthesis and future industrial scaling. The variety of properties observed (e.g. quasi-direct bandgap of open-framework allotrope Si24) allows us to suggest future industrial applications.