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Phase boundary between rutile-type and CaCl₂-type germanium dioxide determined by in situ X-ray observations

¹ Institute for Solid State Physics, University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
² Institute for Frontier Research on Earth Evolution, Japan Marine Science & Technology Center, 2-15 Natsushima-cho, Yokosuka-shi, Kanagawa 237-0061, Japan
³ Department of Earth and Planetary Sciences, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro, Tokyo 152-8551, Japan
⁴ Japan Synchrotron Radiation Research Institute, Mikazuki-cho, Sayo-gun, Hyogo 679-5198, Japan

In situ synchrotron X-ray experiments of the GeO₂ system were made at pressures of 28–45 GPa and temperatures of 300–2300 K, using a diamond anvil cell combined with a laser heating and a 6–8 type multianvil high-pressure apparatus. We observed a second-order phase transition between tetragonal rutile-type (P4₂/mnm) and orthorhombic CaCl₂-type (Pnnm) phases under high pressure and temperature. The transition kinetics seem to have little effect on the second-order phase transition because the cell constants exhibit no discontinuities between the phases. Therefore, the phase transitions could be observed at low temperature conditions in this study. The phase boundary was determined to be P (GPa) = (34.9 ± 1.2) + (0.0086 ± 0.0024) x (T – 1300) (K).

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