Abstract
Materials with intrinsically low thermal conductivity are of fundamental interests. Here we report a new sort of simple one-dimensional (1D) crystal structured bismuth selenohalides (BiSeX, X = Br, I) with extremely low thermal conductivity of ∼0.27 W m−1 K−1 at 573 K. The mechanism of the extremely low thermal conductivity in 1D BiSeX is elucidated systematically using the first-principles calculations, neutron powder-diffraction measurements and temperature tunable aberration-corrected scanning transmission electron microscopy (STEM). Results reveal that the 1D structure of BiSeX possesses unique soft bonding character, low phonon velocity, strong anharmonicity of both acoustic and optical phonon modes, and large off-center displacement of Bi and halogen atoms. Cooperatively, all these features contribute to the minimal phonon transport. These findings provide a novel selection rule to search low thermal conductivity materials with potential applications in thermoelectrics and thermal barrier coatings.
摘要
本征低热导率材料的研究具有重要的科学意义, 已引起广泛关注. 本工作报道了一类具有简单一维晶体结构的超低热导率材料: 铋硒卤族化合物(BiSeX, X = Br, I). 研究发现, BiSeI的热导率在573 K仅为∼0.27 W m−1 K−1, 达到了最低本征热导率的理论极限值. 本研究采用第一性原理计算结合粉末中子衍射和变温球差扫描透射电子显微镜表征, 深入探究了其超低热导率的机制. 研究表明, BiSeX的一维结构赋予了材料低热导特性: 弱的成键特性、 低的声子速度、 声学支和光学支的强非简谐性以及Bi和卤族元素较大的偏移效应, 从而有效阻碍了声子输运, 使得BiSeX具有超低的热导率. 本研究提出了在具有一维结构的材料中寻找低传导特性的新思路, 该研究思路在热电材料和热障涂层材料等低热传导需求领域中具有广阔的应用前景.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Li S, Zheng Q, Lv Y, et al. High thermal conductivity in cubic boron arsenide crystals. Science, 2018, 361: 579–581
Wan C, Qu Z, He Y, et al. Ultralow thermal conductivity in highly anion-defective aluminates. Phys Rev Lett, 2008, 101: 085901
Padture NP, Gell M, Jordan EH. Thermal barrier coatings for gasturbine engine applications. Science, 2002, 296: 280–284
Zhao LD, Pei YL, Liu Y, et al. InFeZnO4 as promising thermal barrier coatings. J Am Ceramic Soc, 2011, 94: 1664–1666
Zhao LD, Lo SH, Zhang Y, et al. Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals. Nature, 2014, 508: 373–377
He J, Tritt TM. Advances in thermoelectric materials research: Looking back and moving forward. Science, 2017, 357: eaak9997
Tan G, Zhao LD, Kanatzidis MG. Rationally designing highperformance bulk thermoelectric materials. Chem Rev, 2016, 116: 12123–12149
Ying P, Li X, Wang Y, et al. Hierarchical chemical bonds contributing to the intrinsically low thermal conductivity in α-MgAgSb thermoelectric materials. Adv Funct Mater, 2017, 27: 1604145
Xiao Y, Zhao LD. Seeking new, highly effective thermoelectrics. Science, 2020, 367: 1196–1197
Lindsay L, Broido DA, Reinecke TL. First-principles determination of ultrahigh thermal conductivity of boron arsenide: A competitor for diamond? Phys Rev Lett, 2013, 111: 025901
Kang JS, Li M, Wu H, et al. Experimental observation of high thermal conductivity in boron arsenide. Science, 2018, 361: 575–578
Tian F, Song B, Chen X, et al. Unusual high thermal conductivity in boron arsenide bulk crystals. Science, 2018, 361: 582–585
Chen K, Song B, Ravichandran NK, et al. Ultrahigh thermal conductivity in isotope-enriched cubic boron nitride. Science, 2020, 367: 555–559
Brown SR, Kauzlarich SM, Gascoin F, et al. Yb14MnSb11: New high efficiency thermoelectric material for power generation. Chem Mater, 2006, 18: 1873–1877
Zhao J, Hao S, Islam SM, et al. Six quaternary chalcogenides of the pavonite homologous series with ultralow lattice thermal conductivity. Chem Mater, 2019, 31: 3430–3439
Miller SA, Gorai P, Ortiz BR, et al. Capturing anharmonicity in a lattice thermal conductivity model for high-throughput predictions. Chem Mater, 2017, 29: 2494–2501
Chang C, Zhao LD. Anharmoncity and low thermal conductivity in thermoelectrics. Mater Today Phys, 2018, 4: 50–57
Mukhopadhyay S, Parker DS, Sales BC, et al. Two-channel model for ultralow thermal conductivity of crystalline Tl3VSe4. Science, 2018, 360: 1455–1458
Dutta M, Matteppanavar S, Prasad MVD, et al. Ultralow thermal conductivity in chain-like TlSe due to inherent Tl+ rattling. J Am Chem Soc, 2019, 141: 20293–20299
Samanta M, Pal K, Pal P, et al. Localized vibrations of Bi bilayer leading to ultralow lattice thermal conductivity and high thermoelectric performance in weak topological insulator n-type BiSe. J Am Chem Soc, 2018, 140: 5866–5872
Jana MK, Biswas K. Crystalline solids with intrinsically low lattice thermal conductivity for thermoelectric energy conversion. ACS Energy Lett, 2018, 3: 1315–1324
Peng B, Xu K, Zhang H, et al. 1D SbSeI, SbSI, and SbSBr with high stability and novel properties for microelectronic, optoelectronic, and thermoelectric applications. Adv Theor Simul, 2018, 1: 1700005
Pele V, Barreteau C, Berardan D, et al. Direct synthesis of BiCuChO-type oxychalcogenides by mechanical alloying. J Solid State Chem, 2013, 203: 187–191
Xiao Y, Chang C, Pei Y, et al. Origin of low thermal conductivity in SnSe. Phys Rev B, 2016, 94: 125203
He W, Wang D, Dong JF, et al. Remarkable electron and phonon band structures lead to a high thermoelectric performance ZT>1 in earth-abundant and eco-friendly SnS crystals. J Mater Chem A, 2018, 6: 10048–10056
Chen Y, Wang D, Zhou Y, et al. Enhancing the thermoelectric performance of Bi2S3: A promising earth-abundant thermoelectric material. Front Phys, 2018, 14: 13601
Lai W, Wang Y, Morelli DT, et al. From bonding asymmetry to anharmonic rattling in Cu12Sb4S13 tetrahedrites: When lone-pair electrons are not so lonely. Adv Funct Mater, 2015, 25: 3648–3657
Wölfing B, Kloc C, Teubner J, et al. High performance thermoelectric Tl9BiTe6 with an extremely low thermal conductivity. Phys Rev Lett, 2001, 86: 4350–4353
Tan G, Hao S, Zhao J, et al. High thermoelectric performance in electron-doped AgBi3S5 with ultralow thermal conductivity. J Am Chem Soc, 2017, 139: 6467–6473
Kurosaki K, Yamanaka S. Low-thermal-conductivity group 13 chalcogenides as high-efficiency thermoelectric materials. Phys Status Solidi A, 2013, 210: 82–88
He W, Wang D, Wu H, et al. High thermoelectric performance in low-cost SnS0.91Se0.09 crystals. Science, 2019, 365: 1418–1424
Qin B, Wang D, He W, et al. Realizing high thermoelectric performance in p-type SnSe through crystal structure modification. J Am Chem Soc, 2019, 141: 1141–1149
Savin A, Jepsen O, Flad J, et al. Electron localization in solid-state structures of the elements: The diamond structure. Angew Chem Int Ed Engl, 1992, 31: 187–188
Shi X, Chen L, Uher C. Recent advances in high-performance bulk thermoelectric materials. Int Mater Rev, 2016, 61: 379–415
Morelli DT, Jovovic V, Heremans JP. Intrinsically minimal thermal conductivity in cubic I-V-VI2 semiconductors. Phys Rev Lett, 2008, 101: 035901
Slack GA. Nonmetallic crystals with high thermal conductivity. J Phys Chem Solids, 1973, 34: 321–335
Pei Y, Chang C, Wang Z, et al. Multiple converged conduction bands in K2Bi8Se13: A promising thermoelectric material with extremely low thermal conductivity. J Am Chem Soc, 2016, 138: 16364–16371
Ding J, Xu B, Lin Y, et al. Lattice vibration modes of the layered material BiCuSeO and first principles study of its thermoelectric properties. New J Phys, 2015, 17: 083012
Nielsen MD, Ozolins V, Heremans JP. Lone pair electrons minimize lattice thermal conductivity. Energy Environ Sci, 2013, 6: 570–578
Barreteau C, Berardan D, Dragoe N. Studies on the thermal stability of BiCuSeO. J Solid State Chem, 2015, 222: 53–59
Zhang Y, Ozoliņš V, Morelli D, et al. Prediction of new stable compounds and promising thermoelectrics in the Cu-Sb-Se system. Chem Mater, 2014, 26: 3427–3435
Hao S, Shi F, Dravid VP, et al. Computational prediction of high thermoelectric performance in hole doped layered GeSe. Chem Mater, 2016, 28: 3218–3226
Vaqueiro P, Al Orabi RAR, Luu SDN, et al. The role of copper in the thermal conductivity of thermoelectric oxychalcogenides: Do lone pairs matter? Phys Chem Chem Phys, 2015, 17: 31735–31740
Bozin ES, Malliakas CD, Souvatzis P, et al. Entropically stabilized local dipole formation in lead chalcogenides. Science, 2010, 330: 1660–1663
Acknowledgements
We appreciate the help from Prof. Shubin Yang and Dr. Yongzheng Shi for ionic conductivity measurement. This work was supported by the National Key Research and Development Program of China (2018YFA0702100 and 2018YFB0703600), the National Natural Science Foundation of China (51772012 and 51632005), Shenzhen Peacock Plan team (KQTD2016022619565991), Beijing Natural Science Foundation (JQ18004), China Postdoctoral Science Foundation Grant (2019M650429), 111 Project (B17002) and the National Science Foundation for Distinguished Young Scholars (51925101). Wu H acknowledges the financial support from Singapore Ministry of Education Tier 1 grant (R-284-000-212-114) for Lee Kuan Yew Postdoctoral Fellowship. Wang G is grateful to the High Performance Computing Center of Henan Normal University. Wang D thanks the high performance computing (HPC) resources at Beihang University.
Author information
Authors and Affiliations
Contributions
Author contributions Wang D and Zhao LD initiated the work, analyzed the results, and wrote the paper. Wang D and Wang G performed the DFT calculations. Huang Z and Zhao LD synthesized the samples and carried out the thermal and electrical properties measurements. Zhang Y, Wang H and Pennycook SJ carried out the STEM measurements. He L, Wang H, Deng S, Chen J and He L carried out the high temperature neutron powder-diffraction (NPD) measurements and Rietveld refinements. All authors conceived the experiments, analyzed the results, and coedited the manuscript.
Corresponding authors
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Dongyang Wang obtained his BSc and MSc degrees in physics from Henan Normal University, China in 2014 and 2017, respectively. He obtained his PhD degree in materials science from Beihang University in 2020. His current research focuses on the exploration and design of low thermal conductivity materials.
Zhiwei Huang has been a post-doctoral fellow in Prof. Li-Dong Zhao’s group at Beihang University since 2018. He got the BE degree in applied chemistry from Jilin University and PhD degree in physical chemistry from Dalian Institute of Chemical Physics, Chinese Academy of Sciences in 2018. His research interests are metal chalcogenides-based thermoelectric materials.
Haijun Wu is a Lee Kuan Yew Postdoctoral fellow at the Department of Materials Science and Engineering, National University of Singapore (NUS), Singapore. He obtained his BSc and MSc degrees from Xi’an Jiaotong University, China in 2009 and 2012, respectively. He obtained his PhD degree from NUS in 2019. His research interests are STEM and EELS, and structure-property correlation in energy materials, e.g., thermoelectrics, piezoelectrics/ferroelectrics, and functional oxide interfaces.
Li-Dong Zhao is a full professor of materials science and engineering at Beihang University, China. He received his PhD degree from the University of Science and Technology Beijing, China, in 2009. He was a postdoctoral research associate at the Université Paris-Sud and Northwestern University from 2009 to 2014. His research interests include electrical and thermal transport behaviors in the compounds with layered structures. Group website: http://shi.buaa.edu.cn/zhaolidong/zh_CN/index.htm
Supplementary Information
Rights and permissions
About this article
Cite this article
Wang, D., Huang, Z., Zhang, Y. et al. Extremely low thermal conductivity from bismuth selenohalides with 1D soft crystal structure. Sci. China Mater. 63, 1759–1768 (2020). https://doi.org/10.1007/s40843-020-1407-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1407-x