Thermodynamic Ground States of Multifunctional Metal Dodecaborides

Liang, Yongcheng; Zhang, Yubo; Jiang, Haitao; Wu, Liangcai; Zhang, Wenqing; Heckenberger, Kilian; Hofmann, Kathrin; Reitz, Andreas; Stober, Frederick C.; Albert, Barbara

doi:10.1021/acs.chemmater.8b04776

Thermodynamic Ground States of Multifunctional Metal Dodecaborides

Journal Article · Mon Jan 07 00:00:00 EST 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b04776· OSTI ID:1495449

^[1]; Zhang, Yubo ^[2]; Jiang, Haitao ^[1]; Wu, Liangcai ^[1]; Zhang, Wenqing ^[2]; Heckenberger, Kilian ^[3]; Hofmann, Kathrin ^[3]; Reitz, Andreas ^[3]; Stober, Frederick C. ^[3]; ^[3]

Donghua Univ., Shanghai (China)
Southern Univ. of Science and Technology, Guangdong (China)
Technische Univ. Darmstadt (Germany)

A large class of metal dodecaborides (MB₁₂) is currently raising great expectations as multifunctional materials, but their refined structures are not fully resolved, which severely limits the understanding of structure–property relationships. In this paper, we report that the tetragonal tI26 structure is the thermodynamic ground state of ScB₁₂, and we predict the tetragonal YB₁₂, ZrB₁₂, and HfB₁₂ to be metastable, whereas the cubic cF52 structure is the high-temperature phase of ScB₁₂ and represents the thermodynamic ground state of YB₁₂, ZrB₁₂, and HfB₁₂. Crystal structures based on experimental synchrotron data are reported for tetragonal ScB₁₂ and cubic YB₁₂, and high-temperature X-ray data prove the phase transformation into cubic ScB₁₂. In both types of crystal structures, the most prominent feature is that the boron atoms are linked into a rigid three-dimensional network of interconnected, empty B₁₂-cuboctahedra with metal atoms in large cages in form truncated octahedra consisting of 24 boron atoms. It is the uniqueness of these configurations that causes unusual functionalities, i.e., the coexistence of high hardness, low density, and good electrical conductivity. Furthermore, we elucidate that these physical properties are of electronic origins. These findings not only resolve the longstanding structural puzzle of this family of MB₁₂ but also provide crucial insights into the underlying nature of their remarkable properties.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC)

OSTI ID:: 1495449

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 3 Vol. 31; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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