The interplay of chemical bonding and thermoelectric properties in doped cubic GeTe

GeTe-based alloys hold great promise for thermoelectric applications. Our comprehensive study investigates the intricate interplay between chemical bonding and transport properties in cubic GeTe. We demonstrate a balance between minimizing thermal conductivity and maximizing power factor, guided by the mediating influence of chemical bonding. Our primary findings reveal that Pb-doped GeTe exhibits low lattice thermal conductivity due to weak p-p orbital interactions, whereas In-doping boosts lattice thermal conductivity by reinforcing the chemical bonds, as elucidated by crystal orbital hamilton population (COHP) analysis. Further investigation reveals weak s-p interactions in Bi-, Sb-, and Pb-doped GeTe, and strong s-p interactions in In-doped GeTe compared to the pure GeTe, as probed by projected density of state (PDOS). These dual effects explain the experimentally observed high power factor and enhanced zT in Bi-, Sb-, and Pb- doping in contrast to In-doping. In our study, we find that weak s-p interactions improves electronic performance by modifying DOS whereas weak p-p interactions reduce thermal transport by diminishing the strength of chemical bonding. These findings underscore the correlation between doping-induced modifications in chemical bonding and resulting thermoelectric properties. Utilizing a first-principles framework, we systematically explore the temperature and carrier concentration-dependent transport properties of pure GeTe under relaxation time approximation. Optimization strategies yield a maximum peak power factor times temperature of 2.2 Wm-1 K-1 and a maximum zT value of similar to 0.83 at 800 K, showcasing the potential for tailored thermoelectric performance. Finally, this research presents a systematic approach to improve thermoelectric performance by modifying chemical bonds through doping. Our study elucidates how doping affects transport properties and chemical bonding in GeTe. Weak p-p interactions reduce thermal conductivity by weakening bonds, while favorable s-p interactions boost the power factor.