Spin singlet pairing of bismuth in titania

Abstract

The formation of electron and hole traps in semiconductors via atomistic defects is the fundamental microscopic mechanism for tuning the electronic and photonic properties of these materials. Here we find in experiments that bismuth atoms doped into anatase TiO2 as substituents can appear as paired diatomic defects. Through first-principles density functional theory calculations, we reveal that the observed bismuth pair is separated by a medium distance of 6.37 Å through a delicate balance of Pauli repulsion and effective attractive interaction. We further clarify that the effective attractive interaction is related to the exchange coupling between the two bismuth defect states, which also leads to the formation of a spin singlet electronic state of the two unpaired electrons. Our study brings up a new type of defect state in TiO2, and motivates further experimental and theoretical studies of multi-electronic states in materials.