First principles investigations in the carbon silicon system of novel tetragonal C8 (diamond) and Si8 allotropes and binary Si4C4 phase

TL;DR

This paper uses density functional theory to propose and analyze novel tetragonal allotropes of carbon, silicon, and silicon carbide, revealing their structures, stability, and electronic properties.

Contribution

It introduces new tetragonal C8, Si8, and Si4C4 phases with detailed structural, stability, and electronic analyses, expanding the understanding of these materials.

Findings

C8 is an ultra-hard allotrope similar to diamond.

Si8 is softer with a Vickers hardness of 13 GPa.

Si4C4 is a stable silicon carbide phase with 33 GPa hardness.

Abstract

Novel extended networks of C8, Si8 and silicon carbide Si4C4 are proposed based on crystal chemistry rationale and optimized structures to ground state energies and derived physical properties within the density functional theory (DFT). The two carbon and silicon allotropes and the silicon carbide belong to primitive tetragonal space group P-4m2 Number 115. C8 allotrope structure made of corner sharing C4 and Si4 tetrahedra is illustrated by charge density projections exhibiting sp3 like carbon hybridization. From careful symmetry analysis, Symmetry analysis of C8 indicated that it is another representation of cubic diamond, space group F-d3m Number 227. C8 is identified as ultra-hard with a similar magnitude of Vickers hardness. The interest in C8 is to serve as template to study Si8 and Si-C binary. Si8 allotrope is found soft with HV =13 GPa alike cubic Si, and Si4C4 is identified with HV =33 GPa close to experimental SiC. All three new phases are mechanically (elastic constants) and dynamically (phonons) stable, and their electronic band structures are characteristic of insulating C8 (diamond) with large band gaps of about 5 eV, and semi-conducting Si8 and Si4C4 with band gaps of about 1 eV.