DFTB Investigations on Transition Metals Doped TiO2 Quantum Dots

Abstract

The structural, optical and electronic properties of different-sized pure as well as transition metals doped TiO2 quantum dots were investigated using density functional tight binding (DFTB) methods. The self-consistent charge density functional tight binding theory (SCC-DFTB) was used to model the TiO2 quantum dots (QDs) of increasing size up to 3.03 nm. The size dependence of density of states, position of molecular orbitals, and gap between highest orbital molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO) of the QDs were studied. It appeared that, when the size of QDs approaches 3.03 nm, the energy gap narrowed down due to quantum confinement effects. The QD Ti27O54 was doped with 3d transition metals to further explore the possibility of tailoring the properties. The dopants introduced 3d impurity gap states which opens the opportunity to modify the band gap or positions of principal bands. The position of a shifted Fermi level was monitored to explore the changes in conductivity and n- or p-type behaviors of the doped QDs. It was observed that TiO2 QDs doped with V and Cr showed the n-type behavior while those doped with Sc, Mn and Fe showed p-type behavior. The findings are helpful to enhance the photocurrent efficiency of dye-sensitized solar cells and use the materials in electronic and optoelectronic properties.