Quasiparticle electronic structure of charged oxygen vacancies in TiO2

Physics – Condensed Matter – Strongly Correlated Electrons

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Scientific paper

We studied the oxygen vacancies($V_{O}$) in rutile TiO2 by using $G_0W_0$ approximation on top of GGA+$U$ as a method of choice to improve the gap. Since there is no extensive agreement regarding the characteristic of electron localization for $ TiO_2$, we examine combined $G_0W_0$@GGA+$U$ scheme in which both are conceptually one step toward better enumeration of the non locality of exchange-correlation potential . Our $G_0W_0$@GGA+$U$ results realize and confirm the weak nature of electron correlation in rutile $TiO_2$ and shows that the $U$-dependence of the energy gap in perfect bulk is slightly stronger than in defected sample. In addition, we studied the $U$- dependency of $V_O$ defect states and found that different charged vacancies shows different $U$-dependence . While the application of $G_0W_0$ correction would improve the quasiparticle gap and formation energies, however the $V_O$ states, in contrast to experiment, remains entangled with the conduction band. Finally, we used PBE0 and HSE06 hybrid functionals and found that these exchange-correlation functional particularly HSE06 that reproduced the real gap and provide desire description of the screening, properly disentangle the neutral and singly ionized $V_O$ from the conduction band . According to hybrid functional calculations, all vacancies are stabilized and $V_O$ with 2+ charge state is the most stable vacancy in the whole Fermi-level range inside the gap and hence $V_O$ acts as a shallow donor.

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