Hybrid functional calculations on the Na and K impurities in substitutional and interstitial positions in Cu2ZnSnSe4

We studied the energetics, atomic and electronic structure of Na and K extrinsic defects in Cu₂ZnSnSe₄ by ab initio calculations using the HSE06 hybrid functional. Our results show that (i) among all substitutional positions, the Cu-site is the most favorable position for both Na and K. (ii) The tetrahedrally coordinated interstitial site has a lower formation energy than the octahedrally coordinated interstitial site. (iii) Based on the band structure calculations we can conclude, Se-related defects lead to the formation of defect states within the band gap.