Ion-impact chemistry in the system titanium-oxygen (studies on bombardment-enhanced conductivity—III)

The bombardment of TiO₂, whether poly- or single crystalline, with Kr ions leads to an altered surface layer having the following characteristics. It exhibits a high electrical conductivity, has the diffraction pattern of finely polycrystalline Ti₂O₃, is on the average 110 ± 20 Å thick (for 30 keV Kr), and is indefinitely stable in air at room temperature. The formation of the layer is favored by increasing the target temperature. Formation is half complete at (6 ± 2) × 10¹⁶ ions/cm², hence at a dose substantially greater than that for the half completion of sputter equilibrium (7 ± 2] × 10¹⁵ ions/cm²). One model which could lead to Ti₂O₃ can be excluded fairly readily: this is thermal-spike stimulated vaporization, as the relevant vapor pressures are too low. More satisfactory is a model in which, due to either preferential oxygen sputtering or internal precipitation of oxygen, Ti₂O₃ nuclei are formed and grow. The reason that the stoichiometry is precisely Ti₂O₃ can be rationalized by an argument based on surface binding energies (E_b), in the sense that E_b for TiO₂ to sputter congruently is 6.4 eV, to yield nuclei of Ti₃O₅ is 5.7, to yield nuclei of Ti₂O₃ is 5.1, and to yield TiO is 6.4. A similar rationalization holds also for impact-induced chemical changes observed or inferred with AgBr, CuO, Fe₂O₃, MoO₃, U₃O₈ and V₂O₅, except that here thermal-spike stimulated vaporization cannot be excluded.