Thermodynamic Study on Hydrogen Reduction of Germanium Tetrachloride to Germanium

This study elucidates the thermodynamic reaction mechanism of the GeCl4 hydrogen reduction process for Ge preparation. Five independent reactions in the Ge-Cl-H ternary system were identified, utilizing the phase law, mass conservation principles, and thermodynamic data, with H2 as the reducing agent. Additionally, the effects of the temperature, feed ratio, and pressure on the germanium deposition rate during the GeCl4 hydrogen reduction process were investigated, guided by these five reactions. The results indicate that, with fixed temperature and pressure, a higher feed ratio (nH2/nGeCl4) leads to an increased germanium deposition rate. Conversely, with a constant feed ratio, increased pressure results in a lower deposition rate at low temperatures. The optimal operating conditions for germanium preparation via the hydrogen reduction of GeCl4 were determined: the temperature was 450 °C, the feed ratio was 20, the pressure was 0.1 MPa, and the deposition rate of the germanium was 36.12% under this condition.