Low-energy tetrahedral polymorphs of carbon, silicon, and germanium

TL;DR

This study uses density functional theory and ab initio random structure searching to identify low-energy tetrahedral polymorphs of carbon, silicon, and germanium, revealing promising candidates with unique structures and potential applications.

Contribution

The paper introduces new low-energy tetrahedral polymorphs of group 14 elements, including a metastable Pbam phase and a chiral P41 21 2 structure, expanding the known structural landscape.

Findings

Pbam structure is a low-energy, low-density metastable phase in C, Si, and Ge.

Silicon Pbam has a direct band gap of about 1.4 eV, suitable for photovoltaics.

P41 21 2 structure features a Cairo-type pentagonal tiling, likely candidate for silicon phase XIII.

Abstract

Searches for low-energy tetrahedral polymorphs of carbon and silicon have been performed using density functional theory computations and the ab initio random structure searching (AIRSS) ap- proach. Several of the hypothetical phases obtained in our searches have enthalpies that are lower or comparable to those of other polymorphs of group 14 elements that have either been experimentally synthesized or recently proposed as the structure of unknown phases obtained in experiments, and should thus be considered as particularly interesting candidates. A structure of P bam symmetry with 24 atoms in the unit cell was found to be a low energy, low-density metastable polymorph in carbon, silicon, and germanium. In silicon, Pbam is found to have a direct band gap at the zone center with an estimated value of 1.4 eV, which suggests applications as a photovoltaic material. We have also found a low-energy chiral framework structure of P 41 21 2 symmetry with 20 atoms per cell containing fivefold spirals of atoms, whose projected topology is that of the so-called Cairo-type two- dimensional pentagonal tiling. We suggest that P41 21 2 is a likely candidate for the structure of the unknown phase XIII of silicon. We discuss Pbam and P41 21 2 in detail, contrasting their energetics and structures with those of other group 14 elements, particularly the recently proposed P42 /ncm structure, for which we also provide a detailed interpretation as a network of tilted diamond-like tetrahedra.