The simultaneous effect of 3d impurities of transition metals and oxygen vacancy defect on TiO2 anatase and rutile

In this work, the formation of oxygen-vacancy defect in 3d metals-doped TiO2 anatase and rutile structures is first investigated. The systematic calculations of formation energy, crystalline stability, band structure and density of state (DOS) of TiO2 samples of anatase and rutile doped with 3d transition metals with and without oxygen defect is done using FHI-aims as a software package based on the density functional theory. The results of this research show that 3d impurities can influence the formation energy of O-vacancy defect noticeably, where all studied dopants except Mn and Zn diminish the formation energy of O-vacancy, leading to a higher activity. Also, among 3d transition matals, only Fe impurity in the presence of O-vacancy shows an inhibitor effect for the transition phase of anatase to rutile. The results of the band structure and DOS also show that the presence of O-vacancy defect in both anatase and rutile phases, in addition to creating occupied defect states under the conduction band, can lead to the appearance of a semiconductor of type n, as well as increasing the original band gap. Also, with O-vacancy, the presence of 3d impurities create defect states shifted to a lower energy from the conduction band to the valance band by increasing the atomic number of impurities. Here, with Fe, Ni, Co and Cu impurities, defect states appear inside the band gap, extending the exciting range of TiO2 photocatalyst to the visible region. The analysis of partial DOS also shows that the 3d orbital of impurities has the main contribution to the defect states.