First-Principles Study on Structural Properties of GeO$_2$ and SiO$_2$ under Compression and Expansion Pressure

TL;DR

This study uses first-principles calculations to analyze how different polymorphs of GeO₂ and SiO₂ structurally respond to pressure changes, revealing stability preferences and bond flexibility differences.

Contribution

It provides a comparative first-principles analysis of structural variations and stability of GeO₂ and SiO₂ polymorphs under pressure, highlighting bond flexibility effects.

Findings

Rutile is the most stable GeO₂ phase.

Quartz is the preferred SiO₂ phase.

GeO₂ tetrahedra are more distorted under volume change.

Abstract

The detailed analysis of the structural variations of three GeO$_2$ and SiO$_2$ polymorphs ($\alpha$-quartz, $\alpha$-cristobalite, and rutile) under compression and expansion pressure is reported. First-principles total-energy calculations reveal that the rutile structure is the most stable phase among the phases of GeO$_2$, while SiO$_2$ preferentially forms quartz. GeO$_4$ tetrahedras of quartz and cristobalite GeO$_2$ phases at the equilibrium volume are more significantly distorted than those of SiO$_2$. Moreover, in the case of quartz GeO$_2$ and cristobalite GeO$_2$, all O-Ge-O bond angles vary when the volume of the GeO$_2$ bulk changes from the equilibrium point, which causes further deformation of tetrahedra. In contrast, the tilt angle formed by Si-O-Si in SiO$_2$ markedly changes. This flexibility of the O-Ge-O bonds reduces the stress at the Ge/GeO$_2$ interface due to the lattice-constant mismatch and results in the low defective interface observed in the experiments [Matsubara \textit{et al.}: Appl. Phys. Lett. \textbf{93} (2008) 032104; Hosoi \textit{et al.}: Appl. Phys. Lett. \textbf{94} (2009) 202112].