Ab initio study of band gap properties in novel metastable BC8/ST12 Si\(_x\)Ge\(_{1-x}\) alloys

The cubic \(Ia\bar{3}\) (BC8) and tetragonal \(P4_32_12\) (ST12) high pressure modifications of Si and Ge are attractive candidates for applications in optoelectronic, thermoelectric or plasmonic devices. Si\(_x\)Ge\(_{1-x}\) alloys in BC8/ST12 modifications could help overcome the indirect and narrow band gaps of the pure phases and enable tailoring for specific use-cases. Such alloys have experimentally been found to be stable at ambient conditions after release from high pressure synthesis, however their fundamental properties are not known. In this work, we employ {\it ab initio} calculations based on density functional theory (DFT) to investigate the electronic properties of these compounds as a function of composition \(x\). We obtain the effective band structures of intermediate alloys by constructing special quasi random structures (SQS) and unfolding their band structure to the corresponding primitive cell. Furthermore, we show that the indirect band gap of the ST12 Ge end-member can be tuned to become direct at \(x_\text{Si} \approx 0.16\). Finally, our investigations also demonstrate that the BC8 modification, on the other hand, is insensitive to compositional changes and is a narrow direct band gap semiconductor only in the case of pure Si.