Computational study of GaAs1-xNx and GaN1-yAsy alloys and arsenic impurities in GaN

We have studied the structural and electronic properties of As-rich GaAs1-xNx and N-rich GaN1-yAsy alloys in a large composition range using first-principles methods. We have systematically investigated the effect of the impurity atom configuration near both GaAs and GaN sides of the concentration range on the total energies, lattice constants and bandgaps. The N ( As) atoms, replacing substitutionally As (N) atoms in GaAs (GaN), cause the surrounding Ga atoms to relax inwards (outwards), making the Ga-N (Ga-As) bond length about 15% shorter (longer) than the corresponding Ga-As (Ga-N) bond length in GaAs (GaN). The total energies of the relaxed alloy supercells and the bandgaps experience large fluctuations within different configurations and these fluctuations grow stronger if the impurity concentration is increased. Substituting As atoms with N in GaAs induces modifications near the conduction band minimum, while substituting N atoms with As in GaN modifies the states near the valence band maximum. Both lead to bandgap reduction, which is at first rapid but later slows down. The relative size of the fluctuations is much larger in the case of GaAs1-xNx alloys. We have also looked into the question of which substitutional site (Ga or N) As occupies in GaN. We find that under Ga-rich conditions arsenic prefers the substitutional N site over the Ga site within a large range of Fermi level values.