Band-edge problem in the theoretical determination of defect energy levels: the O vacancy in ZnO as a benchmark case

TL;DR

This paper examines the impact of different computational methods on defect energy level calculations in ZnO, emphasizing the importance of proper band edge alignment for accurate defect level predictions.

Contribution

It demonstrates a procedure for aligning band structures to improve defect level accuracy across various DFT-based methods.

Findings

Different methods yield varying defect levels without proper alignment.

Alignment via external potential ensures consistency across methods.

Accurate defect levels require correct band edge positioning.

Abstract

Calculations of formation energies and charge transition levels of defects routinely rely on density functional theory (DFT) for describing the electronic structure. Since bulk band gaps of semiconductors and insulators are not well described in semilocal approximations to DFT, band-gap correction schemes or advanced theoretical models which properly describe band gaps need to be employed. However, it has become apparent that different methods that reproduce the experimental band gap can yield substantially different results regarding charge transition levels of point defects. We investigate this problem in the case of the (+2/0) charge transition level of the O vacancy in ZnO, which has attracted considerable attention as a benchmark case. For this purpose, we first perform calculations based on non-screened hybrid density functionals, and then compare our results with those of other methods. While our results agree very well with those obtained with screened hybrid functionals, they are strikingly different compared to those obtained with other band-gap corrected schemes. Nevertheless, we show that all the different methods agree well with each other and with our calculations when a suitable alignment procedure is adopted. The proposed procedure consists in aligning the electron band structure through an external potential, such as the vacuum level. When the electron densities are well reproduced, this procedure is equivalent to an alignment through the average electrostatic potential in a calculation subject to periodic boundary conditions. We stress that, in order to give accurate defect levels, a theoretical scheme is required to yield not only band gaps in agreement with experiment, but also band edges correctly positioned with respect to such a reference potential.