Anomalous Thermopower and High ZT in GeMnTe2 Driven by Spin's Thermodynamic Entropy

NaxCoO2 was known 20 years ago as a unique example in which spin entropy dominates the thermoelectric behavior. Hitherto, however, little has been learned about how to manipulate the spin degree of freedom in thermoelectrics. Here, we report the enhanced thermoelectric performance of GeMnTe2 by controlling the spin's thermodynamic entropy. The anomalously large thermopower of GeMnTe2 is demonstrated to originate from the disordering of spin orientation under finite temperature. Based on the careful analysis of Heisenberg model, it is indicated that the spin-system entropy can be tuned by modifying the hybridization between Te-p and Mn-d orbitals. As a consequent strategy, Se doping enlarges the thermopower effectively, while neither carrier concentration nor band gap is affected. The measurement of magnetic susceptibility provides a solid evidence for the inherent relationship between the spin's thermodynamic entropy and thermopower. By further introducing Bi doing, the maximum ZT in Ge0.94Bi0.06MnTe1.94Se0.06 reaches 1.4 at 840 K, which is 45% higher than the previous report of Bi-doped GeMnTe2. This work reveals the high thermoelectric performance of GeMnTe2 and also provides an insightful understanding of the spin degree of freedom in thermoelectrics.

Automated summary

By controlling the spin's thermodynamic entropy, the enhanced thermoelectric performance of GeMnTe2 has been demonstrated in this study, with the anomalously large thermopower originating from the disordering of spin orientation under finite temperature. The manipulation of spin-system entropy by modifying the hybridization between Te-p and Mn-d orbitals has been shown to be an effective strategy, with Se doping effectively enlarging the thermopower without affecting carrier concentration or band gap.