A vibrational study of phase transitions among the GeO2 polymorphs

Infrared and Raman spectra of the quartz, rutile and amorphous forms of GeO₂ have been recorded under pressure and/or temperature, in order to study the crystalline to crystalline — or amorphous — transformations of this compound in the solid state. X-ray diffraction data shown that crystalline quartz-GeO₂ subjected to high pressure amorphizes. Infrared data are consistent with a gradual amorphisation of this compound at static pressures between 6 to 12 GPa at 300 K. With increasing pressure, the Ge-O distance appears to remain constant and amorphization is associated with a progressive change in the coordination of germanium atoms from fourfold to sixfold. This apparent change in coordination is not quenchable at room pressure. On decompression, the Ge in the amorphous form returns to tetrahedral coordination. The anharmonic parameters for the Raman modes of the quartz and rutile forms of GeO₂, have also been estimated from pressure and temperature shifts. These data have been used to calculate heat capacities and entropies of the two polymorphs at different pressures, with the Kieffer vibrational model. The calculated heat capacities at room pressure are within 1% of the experimental values between 20 and 1500 K. The calculated entropies are used to estimate the phase boundary in the (P, T) plane. The slope of the curve at room pressure (17 bar/K) is in good agreement with experimental values.