Achieving Superior Thermoelectric Performance in Ge₄Se₃Te via Symmetry Manipulation with I–V–VI₂ Alloying

Abstract Although orthorhombic GeSe is predicted to have an ultrahigh figure of merit, ZT ≈ 2.5, up to now, the highest experimental value is ≈0.2 due to the low carrier concentration (n_H ≈ 10¹⁸ cm⁻³). Improving symmetry is an effective approach for enhancing the ZT of GeSe‐based materials. With Te‐alloying, Ge₄Se₃Te displays the two‐dimensional hexagonal structure and high n_H ≈ 1.23 × 10²¹ cm⁻³. Interestingly, Ge₄Se₃Te transformed from the hexagonal into the rhombohedral phase with only ≈2% I–V–VI₂‐alloying (I = Li, Na, K, Cu, Ag; V = Sb, Bi; VI = Se, Te). According to the calculated results of Ge_0.82Ag_0.09Bi_0.09Se_0.614Te_0.386 single‐crystal grown via AgBiTe₂‐alloying, it exhibits a higher valley degeneracy than the hexagonal Ge₄Se₃Te. For instance, AgBiTe₂‐alloying induces a strong band convergence and band inversion effect, resulting in a significantly enhanced Seebeck coefficient and power factor with a similar n_H from 17 µV K⁻¹ and 0.63 µW cm⁻¹ K⁻² for pristine Ge₄Se₃Te to 124 µV K⁻¹ and 5.97 µW cm⁻¹ K⁻² for 12%AgBiTe₂‐alloyed sample, respectively. Moreover, the sharply reduced phonon velocity, nano‐domain wall structure, and strong anharmonicity lead to low lattice thermal conductivity. As a result, a record‐high average ZT ≈0.95 over 323–773 K with an excellent ZT ≈ 1.30 is achieved at 723 K.