SCIENCE CHINA Materials, Volume 63 , Issue 9 : 1759-1768(2020) https://doi.org/10.1007/s40843-020-1407-x

Extremely low thermal conductivity from bismuth selenohalides with 1D soft crystal structure

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  • ReceivedMay 13, 2020
  • AcceptedMay 20, 2020
  • PublishedJun 11, 2020


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.

Funded by

the National Key Research and Development Program of China(2018YFA0702100,2018YFB0703600)

the National Natural Science Foundation of China(51772012,51632005)

Shenzhen Peacock Plan team(KQTD2016022619565991)

Beijing Natural Science Foundation(JQ18004)

China Postdoctoral Science Foundation Grant(2019M650429)

111 Project(B17002)

the National Science Foundation for Distinguished Young Scholars(51925101)

Singapore Ministry of Education Tier 1 grant(R-284-000-212-114)


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.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

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.

Author 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

Supporting data are available in the online version.


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  • Figure 1

    Experimental thermal conductivities as a function of temperature. (a) The thermal conductivities of IV-VI compounds show a decreasing trend as the crystal structure dimension decreases from 3D, 2D to 1D, and the thermal conductivity of BiSeBr and BiSeI are further reduced due to the 1D soft crystal structures from halogen atoms. (b) Comparison of the thermal conductivity of the present bismuth selenohalides with various compounds exhibiting intrinsically low thermal conductivity. The dashed line refers to the theoretical minimal thermal conductivity of BiSeI.

  • Figure 2

    Schematic crystal structures and electronic localization functions (ELFs) of 2D, 1D, and soft 1D Bi2Se3, Sb2Se3 and BiSeI, respectively. Schematic diagrams and the corresponding crystal structures of (a, d) 2D slabs in Bi2Se3, (b, e) 1D chain in Sb2Se3 and (c, f) 1D chain with migration of halogens in BiSeI. The crystal structures of Bi2Se3, Sb2Se3 and BiSeI viewed along the c direction are given in (g–i), respectively. (j–l) The projected ELF along the chain. The isosurface level of ELF is 0.9.

  • Figure 3

    The morphology of BiSeI. (a) Wires shape and (b) parallel chains in soft 1D BiSeI.

  • Figure 4

    Crystal structures and bond lengths of 2D Bi2Se3, 1D Sb2Se3, and soft 1D BiSeI/BiSeBr. (a1, b1, c1) Atomically-resolved STEM HAADF images of BiSeI along [001], [010], [100] zone axes, respectively. The inset in (a1) is an enlarged STEM HAADF image of BiSeBr along the [001] zone axis. The insets in (b1, c1) are electron diffraction patterns. (a2, b2, c2) Enlarged STEM HAADF images from (a1, b1, c1), respectively, where different atoms are marked. (a3, b3, c3) Structural models along [001], [010], [100] zone axes, which are consistent with (a2, b2, c2). (d1, e1) Atomically-resolved STEM HAADF images of Sb2Se3 along [001] and [100] zone axes, respectively, with electron diffraction patterns insets. (d2, e2) Enlarged STEM HAADF images from (d1) and (e1), respectively, where different atoms are marked. (d3, e3) Structural models along [001] and [100] zone axes, which are consistent with (d2) and (e2). (f1) Atomically-resolved STEM HAADF image of Bi2Se3 along the [101] zone axis, with electron diffraction pattern inset. (f2) Enlarged STEM HAADF image from (f1), where different atoms are marked. (f3) Structural model along the [101] zone axeis, which is consistent with (f2).

  • Figure 5

    Temperature-dependent atom displacement. STEM HAADF images of (a1–a3) BiSeI and (b1–b3) Bi2Se3 acquired during in-situ heating at 298, 373 and 448 K, respectively. (c) Temperature-dependent Bi–Bi and Bi–Se bond length changes in BiSeI and Bi2Se3 with respect to those at 298 K.

  • Figure 6

    Comparison of the averaged maximum acoustic phonon frequency and phonon group velocity along three crystallographic axes, and Grüneisen dispersions. Averaged (a) maximum acoustic phonon frequency and (b) phonon velocity of transverse (TA, TA') and longitudinal (LA) acoustic modes along three crystalline axes. Calculated Grüneisen dispersions of (c) 2D Bi2Se3, (d) 1D Sb2Se3, (e) 1D BiSeBr, and (f) 1D BiSeI along high symmetry lines. Insets show the corresponding first Brillouin zone and high symmetry points, elucidating that the thermal transport properties of the materials with 1D soft structure are favorable.

  • Figure 7

    Frozen phonon potentials and displacement patterns of the optical mode calculated by the First-principles. Anharmonic frozen-phonon potentials of (a) Eg mode in 2D Bi2Se3, (b) Ag mode in 1D Sb2Se3, (c) Ag mode in 1D BiSeBr and (d) Ag mode in 1D BiSeI. The insets are the displacement patterns of the corresponding modes at the Γ point.

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