Enhanced Thermoelectric Performance through Site-Specific Doping in Tetragonal Cu$_{2}$S: A First-Principles Study

Abstract

This work investigates how site-specific doping can enhance the thermoelectric performance of tetragonal Cu$_{2}$S using Density functional Theory and Projected Atomic Orbital Framework for Electronic Transport. We address the gap in current research, where most doping studies focus on the high-temperature cubic polymorph, leaving the tetragonal structure underexplored. By substituting Cu with Li, Na, or Mg, as well as partially replacing S with Se or Te, we systematically examine changes in electronic structure and transport properties. Our results reveal that cation-site doping can strongly shift the Fermi level. In particular, Li doping enhances the power factor ($\sigma S^2$) by optimizing carrier concentrations and band-edge alignments, whereas Mg, due to its divalent nature, offers a higher carrier density but requires careful balancing to maintain a large Seebeck coefficient. On the anion side, substituting heavier chalcogens (Se or Te) reshapes the valence bands and subtly shifts the Fermi level, yielding moderate improvements in both electrical conductivity and Seebeck coefficient. These doping-induced alterations, captured through transport calculations, demonstrate a clear route for tailoring the interplay between conductivity and thermal transport toward potentially high figure-of-merit values. Overall, the findings highlight the importance of site specificity in doping strategies for tetragonal Cu$_{2}$S, showing that judicious choice of dopant elements and concentrations can significantly improve key thermoelectric metrics. Such insights provide a foundation for experimental validation and further development of Cu$_{2}$S-based materials for mid- to high-temperature thermoelectric applications.