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High frequency atomic tunneling yields ultralow and glass-like thermal conductivity in chalcogenide single crystals

Sun, Bo and Niu, Shanyuan and Hermann, Raphaël P. and Moon, Jaeyun and Shulumba, Nina and Page, Katharine and Zhao, Boyang and Thind, Arashdeep S. and Mahalingam, Krishnamurthy and Milam-Guerrero, JoAnna and Haiges, Ralf and Mecklenburg, Matthew and Melot, Brent C. and Jho, Young-Dahl and Howe, Brandon M. and Mishra, Rohan and Alatas, Ahmet and Winn, Barry and Manley, Michael E. and Ravichandran, Jayakanth and Minnich, Austin J. (2020) High frequency atomic tunneling yields ultralow and glass-like thermal conductivity in chalcogenide single crystals. Nature Communications, 11 (1). Art. No. 6039. ISSN 2041-1723. PMCID PMC7699621. https://resolver.caltech.edu/CaltechAUTHORS:20201202-091711333

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Abstract

Crystalline solids exhibiting glass-like thermal conductivity have attracted substantial attention both for fundamental interest and applications such as thermoelectrics. In most crystals, the competition of phonon scattering by anharmonic interactions and crystalline imperfections leads to a non-monotonic trend of thermal conductivity with temperature. Defect-free crystals that exhibit the glassy trend of low thermal conductivity with a monotonic increase with temperature are desirable because they are intrinsically thermally insulating while retaining useful properties of perfect crystals. However, this behavior is rare, and its microscopic origin remains unclear. Here, we report the observation of ultralow and glass-like thermal conductivity in a hexagonal perovskite chalcogenide single crystal, BaTiS₃, despite its highly symmetric and simple primitive cell. Elastic and inelastic scattering measurements reveal the quantum mechanical origin of this unusual trend. A two-level atomic tunneling system exists in a shallow double-well potential of the Ti atom and is of sufficiently high frequency to scatter heat-carrying phonons up to room temperature. While atomic tunneling has been invoked to explain the low-temperature thermal conductivity of solids for decades, our study establishes the presence of sub-THz frequency tunneling systems even in high-quality, electrically insulating single crystals, leading to anomalous transport properties well above cryogenic temperatures.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1038/s41467-020-19872-wDOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc7699621PubMed CentralArticle
ORCID:
AuthorORCID
Sun, Bo0000-0002-2122-6637
Hermann, Raphaël P.0000-0002-6138-5624
Moon, Jaeyun0000-0003-0128-4108
Shulumba, Nina0000-0002-2374-7487
Page, Katharine0000-0002-9071-3383
Milam-Guerrero, JoAnna0000-0002-1533-0251
Haiges, Ralf0000-0003-4151-3593
Melot, Brent C.0000-0002-7078-8206
Mishra, Rohan0000-0003-1261-0087
Alatas, Ahmet0000-0001-6521-856X
Manley, Michael E.0000-0003-4053-9986
Ravichandran, Jayakanth0000-0001-5030-9143
Minnich, Austin J.0000-0002-9671-9540
Additional Information:© The Author(s) 2020. This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. Received 28 June 2020; Accepted 25 October 2020; Published 27 November 2020. N.S. and A.J.M. acknowledge the support of the DARPA MATRIX program under Grant No. HR0011-15-2-0039. B.S., Y.J., and A.J.M. acknowledge the support of the GIST-Caltech Research Collaboration in 2018. J.R. and S.N. acknowledge the support from the Air Force Office of Scientific Research under award no. FA9550-16-1-0335 and Army Research Office under award no. W911NF-19-1-0137. Neutron and X-ray scattering research (R.P.H. and M.E.M.) and STEM characterization (A.S.T. and R.M.) are sponsored by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Materials Sciences and Engineering Division. J.M.-G. and B.C.M. gratefully acknowledge support from the Office of Naval Research Grant No. N00014-15-1-2411. A.S.T. and R.M. acknowledge support through the National Science Foundation grant DMR-1806147. S.N. acknowledges Link Foundation Energy Fellowship. This research used resources at the Spallation Neutron Source and the Center for Nanophase Materials Sciences, DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, and resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. We thank Dr. Rakesh Singh and Cameron Kopas for performing the RBS experiments. M.E.M. and R.P.H. acknowledge encouraging discussions with Brian Sales. Data availability: The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files. Author Contributions: These authors contributed equally: Bo Sun, Shanyuan Niu, Raphael P. Hermann. A.J.M. and J.R. conceived the project and supervised the research. B.S. performed TDTR measurements with help from Y.-D.J. on thin film deposition. S.N. grew the crystals and performed structural characterizations and electrical measurements with B.Z. N.S. contributed to the first-principle calculations. K.L.P. and M.E.M. conducted the neutron diffraction measurements. A.S.T., R.M., K.M., B.M.H., and M.M. performed STEM imaging studies. R.H. contributed to single-crystal XRD measurements. J.M.-G. and B.C.M. contributed to heat capacity studies. R.P.H., J.M., A.A., and M.E.M. conducted the inelastic X-ray scattering measurements and analysis. M.E.M. and B.W. conducted the inelastic neutron scattering measurements to identify the tunneling mechanism proposed by R.P.H. All authors discussed the results. B.S., A.J.M., and M.E.M. wrote the manuscript with contributions from all authors. The authors declare no competing interests. Peer review information: Nature Communications thanks Jie Ma, Nuo Yang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Funders:
Funding AgencyGrant Number
Defense Advanced Research Projects Agency (DARPA)HR0011-15-2-0039
GIST-Caltech Research CollaborationUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)FA9550-16-1-0335
Army Research Office (ARO)W911NF-19-1-0137
Department of Energy (DOE)DE-AC02-06CH11357
Office of Naval Research (ONR)N00014-15-1-2411
NSFDMR-1806147
Link FoundationUNSPECIFIED
Subject Keywords:Materials for energy and catalysis; Quantum mechanics; Structure of solids and liquids
Issue or Number:1
PubMed Central ID:PMC7699621
Record Number:CaltechAUTHORS:20201202-091711333
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20201202-091711333
Official Citation:Sun, B., Niu, S., Hermann, R.P. et al. High frequency atomic tunneling yields ultralow and glass-like thermal conductivity in chalcogenide single crystals. Nat Commun 11, 6039 (2020). https://doi.org/10.1038/s41467-020-19872-w
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:106874
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:02 Dec 2020 17:39
Last Modified:07 Dec 2020 17:30

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