Ultralow Thermal Conductivity Approaching the Disordered Limit in Crystalline TlCuZrSe3

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2024-12-16 DOI:10.1021/acs.chemmater.4c03025

Rohit Kumar Rohj, Animesh Bhui, Shaili Sett, Arindam Ghosh, Kanishka Biswas, D. D. Sarma

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Abstract

A comprehensive understanding of thermal transport is crucial for many applications, including heat dissipation systems, thermal barrier coatings, and harnessing potentials of thermoelectric materials. Here, we report an ultralow thermal conductivity, κ, in a p-type layered chalcogenide, TlCuZrSe₃. Our investigation reveals that the anisotropic values of κ in two perpendicular directions in this compound vary between 0.88 and 0.41 Wm^–1K^–1 and 1.15–0.62 Wm^–1K^–1, respectively, over the temperature range of 295–600 K. The low-temperature specific heat data could only be explained by considering Einstein oscillator terms in addition to the conventional Debye model-based contributions, consistent with the presence of localized Tl¹⁺ rattlers. The unique anisotropic crystal structure of TlCuZrSe₃ and the rattling of Tl¹⁺ ions lead to the generation of low-frequency phonons. These relatively flat optical phonon modes hybridize with acoustic phonons, giving rise to strong anharmonicity and phonon scattering channels. Raman spectroscopy confirms that these low-frequency phonon modes have extremely short lifetimes (∼1 ps), explaining the ultralow κ values, approaching the disordered limit, in this highly crystalline material.

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晶体 TlCuZrSe3 接近无序极限的超低导热率

全面了解热传输对于散热系统、隔热涂层和利用热电材料的潜力等许多应用都至关重要。在这里，我们报告了一种 p 型层状钙钛矿 TlCuZrSe3 的超低热导率 κ。我们的研究发现，在 295-600 K 的温度范围内，该化合物在两个垂直方向上的κ各向异性值分别为 0.88 至 0.41 Wm-1K-1 和 1.15 至 0.62 Wm-1K-1。除了传统的基于德拜模型的贡献之外，只有考虑爱因斯坦振荡项才能解释低温比热数据，这与局部 Tl1+ 响子的存在是一致的。TlCuZrSe3 独特的各向异性晶体结构和 Tl1+ 离子的振荡导致了低频声子的产生。这些相对平坦的光学声子模式与声学声子杂化，产生了强烈的非谐波和声子散射通道。拉曼光谱证实，这些低频声子模式的寿命极短（∼1 ps），从而解释了这种高结晶材料中接近无序极限的超低κ值。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.