The role of electronic correlation effects for a realistic description of the electronic properties of [Formula: see text]/[Formula: see text] heterostructures as covered by the on-site Coulomb repulsion within the GGA+U approach is investigated. Performing a systematic variation of the values of the Coulomb parameters applied to the Ti 3d and La 4f orbitals we put previous suggestions to include a large value for the La 4f states into perspective. Furthermore, our calculations provide deeper insight into the band gap landscape in the space spanned by these Coulomb parameters and the resulting complex interference effects. In addition, we identify important correlations between the local Coulomb interaction within the La 4f shell, the band gap, and the atomic displacements at the interface. In particular, these on-site Coulomb interactions influence buckling within the LaO interface layer, which via its strong coupling to the electrostatic potential in the LAO overlayer causes considerable shifts of the electronic states at the surface and eventually controls the band gap.

We investigate the effect of oxygen vacancies and hydrogen dopants at the surface and inside slabs of LaAlO3, SrTiO3, and LaAlO3/SrTiO3 heterostructures on the electronic properties by means of electronic structure calculations as based on density functional theory. Depending on the concentration, the presence of these defects in a LaAlO3 slab can suppress the surface conductivity. In contrast, in insulating SrTiO3 slabs already very small concentrations of oxygen vacancies or hydrogen dopant atoms induce a finite occupation of the conduction band. Surface defects in insulating LaAlO3/SrTiO3 heterostructure slabs with three LaAlO3 overlayers lead to the emergence of interface conductivity. Calculated defect formation energies reveal strong preference of hydrogen dopant atoms for surface sites for all structures and concentrations considered. Strong decrease of the defect formation energy of hydrogen adatoms with increasing thickness of the LaAlO3 overlayer and crossover from positive to negative values, taken together with the metallic conductivity induced by hydrogen adatoms, seamlessly explains the semiconductor-metal transition observed for these heterostructures as a function of the overlayer thickness. Moreover, we show that the potential drop and concomitant shift of (layer resolved) band edges is suppressed for the metallic configuration. Finally, magnetism with stable local moments, which form atomically thin magnetic layers at the interface, is generated by oxygen vacancies either at the surface or the interface, or by hydrogen atoms buried at the interface. In particular, oxygen vacancies in the TiO2 interface layer cause drastic downshift of the 3d eg states of the Ti atoms neighboring the vacancies, giving rise to strongly localized magnetic moments, which add to the two-dimensional background magnetization.