Crystal Field Splitting is Limiting the Stability and Strength of Ultra-incompressible Orthorhombic Transition Metal Tetraborides

Zhang, R. F.; Wen, X. D.; Legut, D.; Fu, Z. H.; Veprek, S.; Zurek, E.; Mao, H. K.

doi:10.1038/srep23088

Title: Crystal Field Splitting is Limiting the Stability and Strength of Ultra-incompressible Orthorhombic Transition Metal Tetraborides

Journal Article · Tue Mar 01 00:00:00 EST 2016 · Scientific Reports

DOI:https://doi.org/10.1038/srep23088· OSTI ID:1624825

Zhang, R. F. ^[1]; Wen, X. D. ^[2]; Legut, D. ^[3]; Fu, Z. H. ^[4]; Veprek, S. ^[5]; Zurek, E. ^[6]; Mao, H. K. ^[7]

Beihang Univ., Beijing (China). International Research Inst. for Multidisciplinary Science. School of Materials Science and Engineering; Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division; Chinese Academy of Sciences (CAS), Shanxi (China). Inst. of Coal Chemistry. State Key Lab. of Coal Conversion
VSB-Technical Univ. of Ostrava (Czech Republic). IT4 Innovations Center
Beihang Univ., Beijing (China). International Research Inst. for Multidisciplinary Science. School of Materials Science and Engineering
Technical Univ. of Munich (Germany). Dept. of Chemistry
State Univ. of New York (SUNY), Buffalo, NY (United States). Dept. of Chemistry
Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.; Center for High Pressure Science and Technology Advanced Research, Shanghai (China)

The lattice stability and mechanical strengths of the supposedly superhard transition metal tetraborides (TmB4, Tm= Cr, Mn and Fe) evoked recently much attention from the scientific community due to the potential applications of these materials, as well as because of general scientific interests. In the present study, we show that the surprising stabilization of these compounds from a high symmetry to a low symmetry structure is accomplished by an in-plane rotation of the boron network, which maximizes the in-plane hybridization by crystal field splitting between d orbitals of Tm and p orbitals of B. Studies of mechanical and electronic properties of TmB4 suggest that these tetraborides cannot be intrinsically superhard. The mechanical instability is facilitated by a unique in-plane or out-of-plane weakening of the three-dimensional covalent bond network of boron along different shear deformation paths. These results shed a novel view on the origin of the stability and strength of orthorhombic TmB4, highlighting the importance of combinational analysis of a variety of parameters related to plastic deformation of the crystalline materials when attempting to design new ultra-incompressible, and potentially strong and hard solids.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1624825

Journal Information:: Scientific Reports, Vol. 6, Issue 1; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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