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


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Authors

Mujica, A 
Pickard, CJ 
Needs, RJ 

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.

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Keywords

cond-mat.mtrl-sci, cond-mat.mtrl-sci, cond-mat.other

Journal Title

Physical Review B - Condensed Matter and Materials Physics

Conference Name

Journal ISSN

1098-0121
1550-235X

Volume Title

91

Publisher

American Physical Society (APS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/J017639/1)
Engineering and Physical Sciences Research Council (EP/K014560/1)
Engineering and Physical Sciences Research Council (EP/F032773/1)
AM acknowledges the financial support of the Ministerio de Educaci´on, Cultura y Deporte (MECD, Spain) through its Programa de Movilidad de Recursos Humanos (Plan Nacional de I+D+i), grant PRX12/00335, and of project MAT2010-21270-C04-03. Access to the MALTA computer cluster (Universidad de Oviedo, Project CSD2007-00045) and the High Performance Computing Service of the University of Cambridge are gratefully acknowledged. RJN and CJP were supported by the Engineering and Physical Sciences Research Council (EPSRC) of the UK.We thank Keith Refson for useful discussions.