Methods for high-yield synthesis of higher germanes and higher silanes

High-yield synthesis of higher germanes and higher silanes includes the hydrolysis of a germanium- or silicon-containing alloy with chemical formula AxByGe(Si), wherein A=Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, and rare earth metals; B=Al, Si, Sn, Ga, Zn, Fe, Co, Ni, Cu, Ag; x=0-10, y=0-10. The hydrolysis reaction is promoted by an acidic substance such as boron oxide (B2O3), citric acid, hydrochloric acid (HCl), or sulfuric acid (H2SO4). The present invention provides an efficient method of drying higher germanes and higher silanes to prevent their further hydrolysis. Another synthetic process involves the reaction of germanium oxide, borohydride and boron oxide with water. Still another process comprises hydrolyzing the Si1-xGex alloy with a very dilute base solution. The methods enable production of higher germanes from a wide range of germanium-starting materials, including germanium byproducts, impure germanium compounds, and waste products generated in the plasma deposition of thin films containing germanium.