Crystal structures of silicon-rich lithium silicides at high pressure

Silicon (Si) is one of the most essential elements, as it is indispensable for modern electronic technology. The standard Si structure at ambient conditions is the cubic diamond structure, and it has an indirect band gap, which prevents it from being considered as a next-generation platform for semiconductor technologies. Therefore, the search for new allotropes of silicon has attracted great attention. Herein, first principles swarm-intelligence structure searches coupled with density-functional theory were performed to explore the stable high-pressure phases of silicon-rich lithium containing compounds, LiSix ( x = 4 – 8 ). The LiSi4 stoichiometry was predicted to be stable, and it was found to assume one of the following space groups, P4/mnc, Cmmm, and C2/m within the pressure range of 0 to 50 GPa. By removing the Li atoms from these compounds, three silicon allotropes were obtained that were metastable at ambient pressures. Our work illustrates how novel silicon allotropes can be predicted using the CALYPSO method.