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通过AgBiSe的熵驱动合金化稳定n型立方GeSe:超低热导率和有前景的热电性能。

Stabilizing n-Type Cubic GeSe by Entropy-Driven Alloying of AgBiSe : Ultralow Thermal Conductivity and Promising Thermoelectric Performance.

作者信息

Roychowdhury Subhajit, Ghosh Tanmoy, Arora Raagya, Waghmare Umesh V, Biswas Kanishka

机构信息

New Chemistry Unit and School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore, India.

Theoretical Science Unit and School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore, India.

出版信息

Angew Chem Int Ed Engl. 2018 Nov 12;57(46):15167-15171. doi: 10.1002/anie.201809841. Epub 2018 Oct 15.

Abstract

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 AgBiSe (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 AgBiSe concentration. The band gap of n-type cubic (GeSe) (AgBiSe ) (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) (AgBiSe ) exhibits an ultralow lattice thermal conductivity (κ ≈0.43 W m  K ) in the 300-723 K range. The low κ is attributed to significant phonon scattering by entropy-driven enhanced solid-solution point defects.

摘要

由于存在本征锗空位使其成为p型半导体,n型锗硫族化合物的实现一直难以捉摸。在环境条件下,GeSe结晶为类似于SnSe的层状正交结构。据预测,通过施加7 GPa的外部压力或通过将温度升高至920 K来增加熵,可以使GeSe的高对称立方相稳定。通过与AgBiSe(30 - 50 mol%)合金化,在环境条件下实现了GeSe的n型立方相的稳定,通过固溶混合增加了熵。随着AgBiSe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)(AgBiSe)(0.30≤x≤0.50)的带隙在0.3 - 0.4 eV范围内,明显低于正交晶系的GeSe(1.1 eV)。立方(GeSe)(AgBiSe)在300 - 723 K范围内表现出超低的晶格热导率(κ≈0.43 W·m⁻¹·K⁻¹)。低κ归因于熵驱动的增强固溶体点缺陷引起的显著声子散射。

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