Ge$_{136}$ type-II clathrate as precursor for the synthesis of metastable germanium polymorphs: a computational study

TL;DR

This computational study investigates how pressure and temperature influence the formation of metastable germanium phases from Ge$_{136}$ clathrate, revealing pathways for synthesizing novel polymorphs via amorphous intermediates.

Contribution

It introduces a detailed ab initio metadynamics approach to understand phase transitions and metastable polymorph formation in germanium under compression.

Findings

Metastable bct-5 phase competes with $eta$-Sn Ge at 2.5 GPa.

Amorphous intermediates facilitate formation of denser phases.

Structural landscape history influences polymorph selectivity.

Abstract

The response to compression of the clathrate type-II structure Ge(cF136) is investigated by means of \textit{ab initio} small-cell metadynamics at different temperatures and pressures. At lower pressure $p$=2.5 GPa the metastable metallic bct-5 phase competes against $\beta$-Sn Ge(tI4), which forms at higher pressures. On lowering temperature, the presence of amorphous intermediates obtained from Ge$_{136}$ is more pronounced and is instrumental to the formation of denser structural motifs, from which metallic bct-5 can form. Therein, anisotropic box fluctuations promote phase formation. The metadynamics runs are analysed in depth using a set of topological descriptors, including coordination sequence and ring statistics. Differences in the structural landscape history and amorphous intermediates are critical for the selective formation of particular metastable polymorphs, towards turning crystal structure predictions into actual materials.