Structural modifications of GeO₂ glass under high pressure and high temperature

Vitreous GeO$_2$ has been compressed at high temperature, to investigate the effect of thermal activation on the structural reorganization during compression. The measurements were performed in-situ using micro Raman spectroscopy under pressure up to 6 GPa and temperature up to 400$^\circ$C. The evolution of the Raman shift of the main band (400-500 cm$^{-1}$) with temperature during compression evidences a pressure window around 3 GPa within which temperature has a remarkable influence on the structure, in particular the intermediate range order. We find that this change is well correlated with previous ex-situ density measurements from high pressure-high temperature densifications. Moreover, coordination changes from tetrahedrally (GeO$_4$) to octahedrally (GeO$_6$) coordinated GeO$_2$ are accelerated with the heating during the compression.