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First-principles study of novel icosahedral-based B12CN and B13CN structures

基于二十面体的新型B12CN和B13CN结构的第一性原理研究

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Abstract

Boron-rich compounds with icosahedral-based structures possess rich, fascinating electronic and mechanical properties. Herein, the first comprehensive and systematic study of the crystal structures and properties of ternary B12CN and B13CN compounds with icosahedral structures has been performed by using particle swarm optimized structure prediction methods in combination with first-principles calculations. Compared with the widely studied variant structure of α-boron, the newly discovered Cmc21 structures are thermodynamically more stable for B12CN and B13CN. For structures with the same space group, B13CN possesses superior thermodynamic stability and mechanical properties than B12CN. Electronic structure calculations indicate that the boron-rich B-C-N system has abundant and tunable electronic properties, i.e., B13CN is a semiconductor, and B12CN possesses a hole-type conducting characteristic. The systematic study of structural ideal tensile strength indicates successive damage to icosahedra and successive bond breaks between icosahedra during tensile processes, leading to interesting deformation mechanisms, such as stress re-enhancement, structural multistep damage, and creep-like deformation.

摘要

以二十面体为基元的富硼化合物具有复杂多样的电子和机械性能. 在本工作中, 我们采用粒子群优化结构预测方法结合第一性原理计算, 首次对二十面体基元的三元B12CN和B13CN化合物的晶体结构和性质进行了全面系统的研究. 我们搜索得到了B13CN和B12CN化合物的新结构, 其空间群均为Cmc21, 与α-B的变体结构相比, 新结构具有更优异的热力学稳定性. B12CN的热力学稳定性和机械性能均稍逊于B13CN. 此外, B含量的微小差异造成了B12CN与B13CN两种三元化合物迥异的电学特性, 即B13CN具有半导体特性, 而B12CN具有空穴型导电特性. 此外, 在B12CN与B13CN系列新结构的拉伸过程中, 由于二十面体的连续破坏和二十面体之间的连续断键造成的应力再增强、 结构多级破坏和类蠕变变形等特殊变形机制也同样被揭示.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2018YFA0703400), the National Natural Science Foundation of China (52073245, 52002118, 52202071, and 52202049), Macao Youth Scholars Program (AM2021015), and the Postdoctoral Science Preferential Funding of Hebei Province (B2022003021 and B2021005001).

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Center for High Pressure Science (CHiPS), State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, China

    Li Zhu  (朱莉), Mengdong Ma  (马梦冬), Qi Gao  (高琦), Yingju Wu  (武英举), Pan Ying  (应盼), Xudong Wei  (魏旭东), Zhisheng Zhao  (赵智胜), Julong He  (何巨龙) & Yongjun Tian  (田永君)

  2. Macao Institute of Materials Science and Engineering, Macau University of Science and Technology, Taipa, Macao SAR, 999078, China

    Mengdong Ma  (马梦冬)

  3. National-Local Joint Engineering Laboratory of Intelligent Manufacturing Oriented Automobile Die & Mould, Tianjin University of Technology and Education, Tianjin, 300222, China

    Mei Xiong  (熊美)

  4. Key Laboratory for Microstructural Material Physics of Hebei Province, School of Science, Yanshan University, Qinhuangdao, 066004, China

    Yingju Wu  (武英举)

  5. Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, China

    Shengwei Xin  (辛圣炜)

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  1. Li Zhu  (朱莉)
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  2. Mengdong Ma  (马梦冬)
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  5. Yingju Wu  (武英举)
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  7. Xudong Wei  (魏旭东)
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  8. Zhisheng Zhao  (赵智胜)
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  9. Shengwei Xin  (辛圣炜)
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  10. Julong He  (何巨龙)
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  11. Yongjun Tian  (田永君)
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Contributions

Author contributions The original idea was conceived by Zhu L, Ma M, Xin S, and He J. The manuscript was drafted by Zhu L, Ma M, Xiong M, Gao Q, Wu Y, Ying P, Wei X, Zhao Z, Xin S, He J, and Tian Y. All authors discussed and commented on the manuscript.

Corresponding authors

Correspondence to Mengdong Ma  (马梦冬), Shengwei Xin  (辛圣炜) or Julong He  (何巨龙).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Li Zhu is a PhD candidate at the Center for High Pressure Science (CHiPS), State Key Laboratory of Metastable Materials Science and Technology, Yanshan University. Her research interest focuses on the theoretical design and experimental synthesis of novel metastable materials under high pressure and high temperature.

Mengdong Ma received his PhD degree from the CHiPS, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University in 2019. Then, he worked as a postdoctoral fellow at the South China University of Technology and Macau University of Science and Technology supported by Macao Young Scholars Program. His research interests include the design and synthesis of hard and superhard ceramics.

Shengwei Xin received his PhD degree in materials science from Yanshan University in 2011. Currently, he works as an associate professor at the Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University. His research focuses on the fabrication, microstructure, physical and mechanical properties of high-entropy and/or nanocrystalline metallic and ceramic materials.

Julong He is a professor at the CHiPS, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University. He obtained his PhD degree in engineering from Yanshan University in 2004. His research interests include the design and synthesis of superhard materials and novel metastable materials.

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Zhu, L., Ma, M., Xiong, M. et al. First-principles study of novel icosahedral-based B12CN and B13CN structures. Sci. China Mater. 66, 4480–4488 (2023). https://doi.org/10.1007/s40843-023-2593-3

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