Engineering the electronic structure of TiO2 by transition-metal doping: A first-principles DFT study

By means of first-principles density-functional theory (DFT) calculations, we perform a comparative analysis of the electronic and magnetic properties of transition-metal-doped TiO2. The electronic bandgaps of TixM1−xO2, where M represents 3d-transition metals such as Sc, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, have been determined using the Perdew–Burke–Ernzerhof functional within the generalized-gradient approximation scheme and hybrid HSE06 functional. In the context of pure TiO2, the partial density of states reveals that the electronic bandgap emerges between the O-2p and Ti-3d orbitals. It is suggested that the Ti-3d (t2g) states play a more prominent role in bonding compared to the Ti-3d (eg) states. We performed DFT calculations to investigate the impact of doping with other 3d transition-metal atoms, leading to the emergence of impurity states within the bandgap. The hybridization between the oxygen 2p orbitals and the titanium 3d orbitals in TiO2 is altered by the introduction of doping with 3d transition metals because of the change in the oxidation state of titanium, shifting from solely 4+ to a combination of 4+ and 3+ states. The calculation of spin-polarized density demonstrates the emergence of ferromagnetic properties, particularly in titanium dioxide doped with chromium (Cr), manganese (Mn), and iron (Fe) with large magnetic moments. Our work demonstrates the significant impact of doping transition metals on TiO2, allowing for the precise manipulation of electrical and magnetic properties, and thus holds great potential for the development of spin-based memory devices with possible neuromorphic applications.