The realization of n‐type Ge chalcogenides is elusive owing to intrinsic Ge vacancies that make them p‐type semiconductors. GeSe crystallizes into a layered orthorhombic structure similar to SnSe at ambient conditions. The high‐symmetry cubic phase of GeSe is predicted to be stabilized by applying 7 GPa external pressure or by enhancing the entropy by increasing to temperature to 920 K. Stabilization of the n‐type cubic phase of GeSe at ambient conditions was achieved by alloying with AgBiSe₂ (30–50 mol %), enhancing the entropy through solid solution mixing. The interplay of positive and negative chemical pressure anomalously changes the band gap of GeSe with increasing the AgBiSe₂ concentration. The band gap of n‐type cubic (GeSe)_1−x(AgBiSe₂)_x (0.30≤x≤0.50) has a value in the 0.3–0.4 eV range, which is significantly lower than orthorhombic GeSe (1.1 eV). Cubic (GeSe)_1−x(AgBiSe₂)_x exhibits an ultralow lattice thermal conductivity (κ_L≈0.43 W m⁻¹ K⁻¹) in the 300–723 K range. The low κ_L is attributed to significant phonon scattering by entropy‐driven enhanced solid‐solution point defects.

中文翻译：

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通过AgBiSe2的熵驱动合金稳定n型立方GeSe：超低导热率和有希望的热电性能

由于固有的Ge空位使它们成为p型半导体，因此难以实现n型Ge硫族化物。在环境条件下，GeSe结晶成类似于SnSe的层状正交晶体结构。预计通过施加7 GPa外部压力或通过将温度升高至920 K来增强熵，可以稳定GeSe的高对称立方相。在室温下，通过与Ge合金化，可以实现GeSe的n型立方相的稳定化。 AgBiSe ₂（30–50 mol％），通过固溶体混合增强了熵。随着AgBiSe ₂浓度的增加，正负化学压力的相互作用异常地改变了GeSe的带隙。n型立方（GeSe）_1-x（AgBiSe ₂）_x（0.30≤x≤0.50）的值在0.3–0.4 eV的范围内，大大低于正交晶体GeSe（1.1 eV）。立方（GESE）_1-x（AgBiSe ₂）_X表现出超低晶格热导率（κ_大号≈0.43脉冲W M ^-1  ķ ^-1在300-723 K范围之外）。低κ_大号由熵驱动的增强固溶点缺陷归因于显著声子散射。