Structural Heterogeneity in Medium-Entropy AgMnSbPbTe 4 for Glassy Thermal Transport and High Thermoelectric Performance

Liu, Yukun [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000180881407); Li, Zhi [Northwestern Univ., Evanston, IL (United States)] (ORCID:000000030451567X); Sarkar, Debattam [Northwestern Univ., Evanston, IL (United States)] (ORCID:0009000103934058); Ribet, Stephanie M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]; Zhao, Hengdi [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000346066323); Xie, Hongyao [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000224723866); Yanda, Premakumar [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)] (ORCID:0000000197981236); Li, Juncen [Northwestern Univ., Evanston, IL (United States)]; Dong, Jinfeng [Nanyang Technological Univ. (Singapore)] (ORCID:0000000230268054); Yan, Alfred [Northwestern Univ., Evanston, IL (United States)]; Shekhar, Chandra [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)]; Yan, Qingyu [Nanyang Technological Univ. (Singapore)] (ORCID:0000000303173225); Snyder, G. Jeffrey [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000314148682); Grayson, Matthew A. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000349145043); Felser, Claudia [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)]; dos Reis, Roberto [Northwestern Univ., Evanston, IL (United States)]; Wolverton, Christopher [Northwestern Univ., Evanston, IL (United States)] (ORCID:000000032248474X); Kanatzidis, Mercouri G. [Northwestern Univ., Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000320374168); Dravid, Vinayak P. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000260073063)

doi:10.1021/jacs.5c17198

DOE OSTI · 3364121

Structural Heterogeneity in Medium-Entropy AgMnSbPbTe 4 for Glassy Thermal Transport and High Thermoelectric Performance

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Abstract

Medium-entropy semiconductors represent a unique category of entropy-engineered materials. They possess a considerable level of randomness in atomic mixing, although this is not sufficient to conclusively achieve single-phase structure stabilization, in contrast to high-entropy materials. This introduces strong competition between the formation of different phases, which can potentially lead to structural heterogeneity. Here, in this work, we uncover endotaxial nanoprecipitates in the microscopically identified homogeneous medium-entropy semiconductor AgMnSbPbTe 4 . These nanoprecipitates initially crystallize in a cubic phase $(Fm\bar{3}m)$ within kinetically stabilized AgMnSbPbTe 4 , subsequently evolving into a thermodynamically stable monoclinic phase $(P2_1/c)$ during thermal annealing while maintaining an endotaxial relationship with the matrix lattice. This nanophase segregation and the resultant lattice mismatch at interfaces introduce strain fluctuations up to 5% at intervals of 20 nm across the entire microstructure. Within the matrix phase, atomic displacement of up to 23 pm was observed. This structural heterogeneity results in glass-like thermal transport behavior, achieving an ultralow lattice thermal conductivity κ L = 0.312 Wm –1 K –1 at 800 K, which is in accordance with the amorphous limit predicted by the Cahill model. The synergy of band convergence effect and well-maintained carrier mobility leads to a maximum ZT of 1.72 at 800 K and an average ZT avg of 1.02 over the temperature range of 300–825 K. This study highlights that the underexplored structural heterogeneity in medium-entropy semiconductors can potentially yield beneficial phenomena, such as the phonon-glass electron-crystal transport behavior in this case, which holds promise for advancing thermoelectric applications.

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Liu, Yukun [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000180881407), Li, Zhi [Northwestern Univ., Evanston, IL (United States)] (ORCID:000000030451567X), Sarkar, Debattam [Northwestern Univ., Evanston, IL (United States)] (ORCID:0009000103934058), Ribet, Stephanie M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Zhao, Hengdi [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000346066323), Xie, Hongyao [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000224723866), Yanda, Premakumar [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)] (ORCID:0000000197981236), Li, Juncen [Northwestern Univ., Evanston, IL (United States)], Dong, Jinfeng [Nanyang Technological Univ. (Singapore)] (ORCID:0000000230268054), Yan, Alfred [Northwestern Univ., Evanston, IL (United States)], Shekhar, Chandra [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)], Yan, Qingyu [Nanyang Technological Univ. (Singapore)] (ORCID:0000000303173225), Snyder, G. Jeffrey [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000314148682), Grayson, Matthew A. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000349145043), Felser, Claudia [Max Planck Institute for Chemical Physics of Solids, Dresden (Germany)], dos Reis, Roberto [Northwestern Univ., Evanston, IL (United States)], Wolverton, Christopher [Northwestern Univ., Evanston, IL (United States)] (ORCID:000000032248474X), Kanatzidis, Mercouri G. [Northwestern Univ., Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000320374168), Dravid, Vinayak P. [Northwestern Univ., Evanston, IL (United States)] (ORCID:0000000260073063). 2026-01-06. Structural Heterogeneity in Medium-Entropy AgMnSbPbTe 4 for Glassy Thermal Transport and High Thermoelectric Performance. https://doi.org/10.1021/jacs.5c17198

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