• Accepted Paper

First-principles finite-size correction schemes for point defects of Cu3N

Abdul M. Reyes, Sebastian E. Reyes-Lillo, and Eduardo Menéndez-Proupin

Phys. Rev. B - Accepted 9 November, 2026

DOI: https://doi.org/10.1103/dp4r-xs56

Abstract

Point defects play a key role in determining semiconductor properties, such as electrical conductivity and photoluminescence, and often enable functional behavior. Accurate first-principles supercell simulations of point defects require reliable finite-size corrections. In this study, we combine PBE+U structural relaxations with HSE hybrid-functional calculations to determine defect formation energies and thermodynamic transition levels of Cu3N. Finite-size trends are quantified using Γ-point calculations in supercells containing 256, 864, and 2048 atoms. We assess and extend the Makov-Payne and Lany-Zunger correction schemes by introducing additional 1/Ln terms, together with core-level potential alignment and defect-specific scaling models. Using Cu3N as a case study, we show that charged vacancies are accurately described by the Makov-Payne-type scaling (1/L+1/L3), whereas interstitial defects with shallow or weakly localized electronic character are better captured by a hydrogenic impurity model that accounts for defect-band dispersion. Residual trends for neutral or weakly localized defects are described by higher-order polynomial fits in 1/L3 and 1/L4. Hybrid-functional energetics corrected using PBE+U-based finite-size trends confirm the intrinsic p−n doping character of Cu3N under the conditions considered and demonstrate that no single finite-size correction can be transferred across all defect types.

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