Ge monoxide [GeO(II)] and dioxide [GeO2(IV)], which are selectively formed on Ge substrate by controlling pH and redox potential in pretreatment solution, are confirmed by XPS. ΔEC in GeO(II)/Ge and GeO2(IV)/Ge are almost the same, whereas ΔEV in GeO(II)/Ge is smaller than that in GeO2(IV)/Ge, resulting in smaller Eg of GeO(II). GeO(g) desorption is suppressed in LaAlO3/Ge gate stack, whereas GeO(g) desorbs through LaAlO3 layer when there is an intentional interfacial GeO(II) layer, leading to a large increase in Jg. GeO(g) desorption temperature in Ge oxide/Ge gate stacks decreases with the increase in the ratio of GeO(II) in Ge oxide and is independent of the oxidation techniques. Since GeO(g) desorption is accompanied by H2O(g) desorption, a new model to explain the GeO(g) desorption phenomena is proposed, in which Ge(OH)2 decomposes into GeO(g) and H2O(g). Highly effective etching methods of Ge oxide, using HCl solution and HCl vapor at higher temperature than boiling point of Ge (hydro-)chloride are demonstrated.