Band Engineering Of Gasbn Alloy For Solar Fuel Applications

III-nitride nanostructures possess ideal attributes for harvesting solar energy and generating solar fuel through natural water splitting. The most basic requirement of the latter is to engineer the band gap of the semiconductor to straddle the redox potential of water molecules. To this end, using first principles method we predict that GaN engineered with Sb doping at the dilute limit of 0.3% and/or slightly less is suitable for photochemical water splitting applications. The valence band edge is very significantly enhanced by dilute Sb doping while the conduction band edge is not. The microscopic physics behind the strong band bowing by such a small impurity concentration, not seen in other III-V semiconductors, is revealed by investigating the quantum interaction between Sb impurity states and the host GaN states. The dilute doping limit dictates very large systems to be calculated at the hybrid exchange-correlation level which is made possible by our newly developed first principles approach.