Probing of Bi doped GeTe thermoelectrics leads to revelation of resonant states

Quest for lead free high performance mid temperature thermoelectric materials has led to extensive research on SnTe and GeTe based materials. Among various strategies implemented to improve the transport properties of GeTe, electronic structure engineering holds a prominent place. Herein, we reinvestigate the impact of substitutional doping of Bi in GeTe on its electronic structure in both rhombohedral and cubic phase. We uncover that Bi introduces resonance levels in GeTe acting as a first n-type resonant dopant in both rhombohedral and cubic phases. We also report for the first time that Bi resonance states undergo Rashba splitting in low temperature rhombohedral phase. Bi doping acts in a multifunctional way by tuning the carrier concentration, causing conduction band convergence and phonon scattering in addition to improving the band effective mass by distorting the density of states near the Fermi level to enhance the thermoelectric performance of the material. The convergence of L, Z and Sigma valence bands in rhombohedral phase due to Bi doping leads to manifestation of Rashba effect in p-type material which was not reported till date. Thus, we propose that the chemical potential tuning can result in p-type as well as n-type Bi doped GeTe for thermoelectric application. (c) 2022 Published by Elsevier B.V.

Automated summary

The substitutional doping of Bi in GeTe is investigated, revealing the introduction of resonance levels and Rashba splitting in the low-temperature rhombohedral phase. Bi doping acts multifunctionally by tuning carrier concentration, causing conduction band convergence, and enhancing the thermoelectric performance of the material through distortion of the density of states near the Fermi level. The convergence of valence bands leads to the manifestation of the Rashba effect in p-type GeTe.