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Alteration of Ti 2p XPS spectra for TiO 2 single crystal was measured during Ar ion sputtering. The acceleration voltage of Ar ion bombardment ranged from 10 V to 2 kV. Components of Ti 2+ and Ti 3+ as reduced states have appeared, in addition to the Ti 4+ state, after ion bombardment at 2 kV. However, although a small amount of Ti 3+ has been observed in the case of 10 V bombardment, the Ti 2+ component has not appeared. The intensities of the reduced states (Ti 2+ and/or Ti 3+ ) that have appeared at each acceleration voltage reach constant values after a long sputtering time. This saturation shows that the surface reaches an equilibrium state between the sputtered atoms and implanted ions. Moreover, the intensities of the reduced states increase with increasing accelerating voltage of the primary ions. The alteration by 10 V ion bombardment suggests that there is a critical energy for reduction to the Ti 2+ state.
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Hashimoto et al. (2002) studied this question.
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