Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs

Abstract

Contemporary theories of defects and impurities in semiconductors rely to a large extent on supercell calculations within density-functional theory using the approximate local-density approximation (LDA) or generalized gradient approximation (GGA) functionals. Such calculations are, however, affected by considerable uncertainties associated with: (i) the ``band-gap problem,'' which occurs not only in the Kohn-Sham single-particle energies but also in the quasiparticle gap (LDA or GGA) calculated from total-energy differences, and (ii) supercell finite-size effects. In the case of the oxygen vacancy in ZnO, uncertainties (i) and (ii) have led to a large spread in the theoretical predictions, with some calculations suggesting negligible vacancy concentrations, even under Zn-rich conditions, and others predicting high concentrations. Here, we critically assess (i) the different methodologies to correct the band-gap problem. We discuss approaches based on the extrapolation of perturbations which open the band gap, and the self-consistent band-gap correction employing the $\text{LDA}+U$ method for $d$ and $s$ states simultaneously. From the comparison of the results of different gap-correction, including also recent results from other literature, we conclude that to date there is no universal scheme for band gap correction in general defect systems. Therefore, we turn instead to classification of different types of defect behavior to provide guidelines on how the physically correct situation in an LDA defect calculation can be recovered. (ii) Supercell finite-size effects: We performed test calculations in large supercells of up to 1728 atoms, resolving a long-standing debate pertaining to image charge corrections for charged defects. We show that once finite-size effects not related to electrostatic interactions are eliminated, the analytic form of the image charge correction as proposed by Makov and Payne leads to size-independent defect formation energies, thus allowing the calculation of well-converged energies in fairly small supercells. We find that the delocalized contribution to the defect charge (i.e., the defect-induced change of the charge distribution) is dominated by the dielectric screening response of the host, which leads to an unexpected effective $1/L$ scaling of the image charge energy, despite the nominal $1/{L}^{3}$ scaling of the third-order term. Based on this analysis, we suggest that a simple scaling of the first order term by a constant factor (approximately 2/3) yields a simple but accurate image-charge correction for common supercell geometries. Finally, we discuss the theoretical controversy pertaining to the formation energy of the O vacancy in ZnO in light of the assessment of different methodologies in the present work, and we review the present experimental situation on the topic.