Structure Low Dimensionality and Lone-Pair Stereochemical Activity: the Key to Low Thermal Conductivity in the Pb-Sn-S System.

Autor: Acharyya P; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Pal K; Dept. of Physics, Indian Institute of Technology Kanpur, Kanpur 208016, India.; Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos 87545, United States., Zhang B; College of Physics and Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing 401331, China.; Analytical and Testing Center of Chongqing University, Chongqing 401331, China., Barbier T; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Prestipino C; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Boullay P; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Raveau B; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Lemoine P; Institut Jean Lamour, UMR 7198 CNRS - Université de Lorraine, 54011 Nancy, France., Malaman B; Institut Jean Lamour, UMR 7198 CNRS - Université de Lorraine, 54011 Nancy, France., Shen X; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Vaillant M; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France., Renaud A; Univ Rennes, ISCR - UMR 6226, CNRS, F-35000 Rennes, France., Uberuaga BP; Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos 87545, United States., Candolfi C; Institut Jean Lamour, UMR 7198 CNRS - Université de Lorraine, 54011 Nancy, France., Zhou X; College of Physics and Institute of Advanced Interdisciplinary Studies, Chongqing University, Chongqing 401331, China.; Analytical and Testing Center of Chongqing University, Chongqing 401331, China., Guilmeau E; CRISMAT, CNRS, Normandie Univ, ENSICAEN, UNICAEN, 14000 Caen, France.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 May 15; Vol. 146 (19), pp. 13477-13487. Date of Electronic Publication: 2024 May 01.
DOI: 10.1021/jacs.4c02893
Abstrakt: Recently, metal sulfides have begun to receive attention as potential cost-effective materials for thermoelectric applications beyond optoelectronic and photovoltaic devices. Herein, based on a comparative analysis of the structural and transport properties of 2D PbSnS 2 and 1D PbSnS 3 , we demonstrate that the intrinsic effects that govern the low lattice thermal conductivity (κ L ) of these sulfides originate from the combination of the low dimensionality of their crystal structures with the stereochemical activity of the lone-pair electrons of cations. The presence of weak bonds in these materials, responsible for phonon scattering, results in inherently low κ L of 1.0 W/m K in 1D PbSnS 3 and 0.6 W/m K in 2D PbSnS 2 at room temperature. However, the nature of the thermal transport is quite distinct. 1D PbSnS 3 exhibits a higher thermal conductivity with a crystalline-like peak at low temperatures, while 2D PbSnS 2 demonstrates glassy thermal conductivity in the entire temperature range investigated. First-principles density functional theory calculations reveal that the presence of antibonding states below the Fermi level, especially in PbSnS 2 , contributes to the very low κ L . In addition, the calculated phonon dispersions exhibit very soft acoustic phonon branches that give rise to soft lattices and very low speeds of sounds.
Databáze: MEDLINE
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