In situ X-ray absorption spectroscopy study of Si 1-xGe xO 2 dissolution and germanium aqueous speciation under hydrothermal conditions

Abstract

The dissolution of Si 1-xGe xO 2 solid solutions under hydrothermal conditions was studied by in situ X-ray absorption spectroscopy. Experiments were performed at the Ge K-edge using a high-pressure cell mounted on the FAME beamline of the European Synchrotron Radiation Facility. Spectra in both transmission and fluorescence mode were collected in isobaric conditions (100 and 150 MPa) up to 475 °C. The local atomic structure around the Ge atom was investigated as a function of the temperature and in pure water and sodium hydroxide solutions. In pure water, the solubility of the cristobalite-type Si 0.8Ge 0.2O 2 increases with the temperature and the Ge atom is in 4-fold coordination. In a sodium hydroxide aqueous solution, a complex between Ge and Na atoms forms and gives rise to precipitation of sodium germanates. Under these conditions, the Ge content in the solution decreases with increasing temperature. These results show that a sodium hydroxide aqueous solution, usually used for quartz crystal growth, is not suitable for Ge-containing crystals. The dissolution kinetics and phase transformation of the solid solution were studied as a function of the atomic fraction of Ge. Ge-rich solid solutions dissolve and transform to stable phases faster than Ge-poorer composition, giving rise to important variations of the Ge content in solution. © 2011 American Chemical Society.