Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study
Abstract
Boron suboxide (B6O) is a boron-rich compound derived from the α-rhombohedral boron lattice with extreme hardness and unusual semiconducting properties. In this work, density functional theory (DFT) was used to show that unit cell volume, mechanical strength, band gaps, and thermodynamic stabilities of B6O were influenced by the interstitial elements and point defects at the icosahedral sites. While the hexagonal unit cell volume (HUCV) varies with interstitial occupancy, it is the icosahedral defect that weakens the intrinsic bulk modulus of B6O. Using the hybrid HSE functional, we confirmed that the perfect B6O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. The formation free energies calculated over a wide range of temperatures (0–2500 K) and pressures (0–80 GPa) predict that formations of interstitial defects become favorable only at higher temperatures (ca. 1800 K) in bulk B6O lattices. The nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barriermore »
- Authors:
-
- Kansas State Univ., Manhattan, KS (United States)
- Publication Date:
- Research Org.:
- Kansas State Univ., Manhattan, KS (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1894427
- Grant/Contract Number:
- SC0021264; AC02-05CH11231; CHE-1726332; CNS-1006860; EPS-1006860; EPS-0919443
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 37; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Chemical structure; Defects; Energy; Lattices; Potential energy
Citation Formats
Liu, Bin, Evans, Dylan, Deng, Hao, and Edgar, James. Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.2c05590.
Liu, Bin, Evans, Dylan, Deng, Hao, & Edgar, James. Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study. United States. https://doi.org/10.1021/acs.jpcc.2c05590
Liu, Bin, Evans, Dylan, Deng, Hao, and Edgar, James. Tue .
"Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study". United States. https://doi.org/10.1021/acs.jpcc.2c05590. https://www.osti.gov/servlets/purl/1894427.
@article{osti_1894427,
title = {Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study},
author = {Liu, Bin and Evans, Dylan and Deng, Hao and Edgar, James},
abstractNote = {Boron suboxide (B6O) is a boron-rich compound derived from the α-rhombohedral boron lattice with extreme hardness and unusual semiconducting properties. In this work, density functional theory (DFT) was used to show that unit cell volume, mechanical strength, band gaps, and thermodynamic stabilities of B6O were influenced by the interstitial elements and point defects at the icosahedral sites. While the hexagonal unit cell volume (HUCV) varies with interstitial occupancy, it is the icosahedral defect that weakens the intrinsic bulk modulus of B6O. Using the hybrid HSE functional, we confirmed that the perfect B6O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. The formation free energies calculated over a wide range of temperatures (0–2500 K) and pressures (0–80 GPa) predict that formations of interstitial defects become favorable only at higher temperatures (ca. 1800 K) in bulk B6O lattices. The nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barrier of 0.16 eV. More complex B diffusion paths involving the reorganization of icosahedral boron atoms incur higher barriers (>1 eV). In contrast, the diffusion of interstitial O atoms is facile with a barrier of 0.4 eV. Lastly, successive O insertions into the α-B lattice were performed using DFT to generate a basic understanding of the oxidation process. Furthermore, these calculations provide fundamental atomistic insights into the growth of B6O crystals and control of their point defects.},
doi = {10.1021/acs.jpcc.2c05590},
journal = {Journal of Physical Chemistry. C},
number = 37,
volume = 126,
place = {United States},
year = {Tue Sep 13 00:00:00 EDT 2022},
month = {Tue Sep 13 00:00:00 EDT 2022}
}
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Melt growth and properties of B6P crystals
journal, January 1983
- Slack, Glen A.; McNelly, T. F.; Taft, E. A.
- Journal of Physics and Chemistry of Solids, Vol. 44, Issue 10
Synthesis and structure of non-stoichiometric B6O
journal, July 1997
- Olofsson, Malin; Lundström, Torsten
- Journal of Alloys and Compounds, Vol. 257, Issue 1-2
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Experimental study and critical review of structural, thermodynamic and mechanical properties of superhard refractory boron suboxide B6O
journal, December 2011
- Kurakevych, O. O.; Solozhenko, V. L.
- Journal of Superhard Materials, Vol. 33, Issue 6
Structure refinement of the boron suboxide B6O by the Rietveld method
conference, January 1991
- Bolmgren, H.; Lundström, T.; Okada, S.
- AIP Conference Proceedings
Absence of defect clusters in electron irradiated boron carbide
journal, January 1985
- Stoto, T.; Zuppiroli, L.; Pelissier, J.
- Radiation Effects, Vol. 90, Issue 3-4
sumo: Command-line tools for plotting and analysis of periodic ab initio calculations
journal, August 2018
- M. Ganose, Alex; J. Jackson, Adam; O. Scanlon, David
- Journal of Open Source Software, Vol. 3, Issue 28
Some crystallography, chemistry, physics, and thermodynamics of B12O2, B12P2, B12As2, and related alpha-boron type crystals
journal, September 2014
- Slack, Glen A.; Morgan, Kenneth E.
- Journal of Physics and Chemistry of Solids, Vol. 75, Issue 9
Boron suboxide: As hard as cubic boron nitride
journal, July 2002
- He, Duanwei; Zhao, Yusheng; Daemen, L.
- Applied Physics Letters, Vol. 81, Issue 4
Growth of boron suboxide crystals in the B–B2O3 system at high pressure and high temperature
journal, February 2002
- He, Duanwei; Akaishi, Minoru; Scott, Brian L.
- Journal of Materials Research, Vol. 17, Issue 2
Self-healing in B 12 P 2 through Mediated Defect Recombination
journal, November 2016
- Huber, S. P.; Gullikson, E.; Frye, C. D.
- Chemistry of Materials, Vol. 28, Issue 22
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Bonding and doping of simple icosahedral-boride semiconductors
journal, April 2004
- Emin, David
- Journal of Solid State Chemistry, Vol. 177, Issue 4-5
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Non-stoichiometry of boron suboxide (B6O)
journal, March 1976
- Bills, (Mrs.)P. M.; Lewis, D.
- Journal of the Less Common Metals, Vol. 45, Issue 2
Electronic structure and defect properties of from hybrid functional and many-body perturbation theory calculations: A possible ambipolar transparent conductor
journal, July 2014
- Varley, J. B.; Lordi, V.; Miglio, A.
- Physical Review B, Vol. 90, Issue 4
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Identification and design principles of low hole effective mass p-type transparent conducting oxides
journal, August 2013
- Hautier, Geoffroy; Miglio, Anna; Ceder, Gerbrand
- Nature Communications, Vol. 4, Issue 1
Thermoelectric Properties of Hot-pressed Boron Suboxide (B6O)
journal, January 2002
- Akashi, Takaya; Itoh, Tsuyoshi; Gunjishima, Itaru
- MATERIALS TRANSACTIONS, Vol. 43, Issue 7
Production of α-Rhombohedral Boron by Amorphous Boron Crystallization
journal, October 2000
- Shalamberidze, S. O.; Kalandadze, G. I.; Khulelidze, D. E.
- Journal of Solid State Chemistry, Vol. 154, Issue 1
B6O-Based Composite to Rival Polycrystalline Cubic Boron Nitride
journal, December 2007
- Chen, C.; He, D.; Kou, Z.
- Advanced Materials, Vol. 19, Issue 23
The Existence and Formation of the Solid B[sub 6]O
journal, January 1962
- Rizzo, H. F.; Simmons, W. C.; Bielstein, H. O.
- Journal of The Electrochemical Society, Vol. 109, Issue 11
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Hot pressing of boron suboxide B12O2
journal, March 1986
- Brodhag, C.; Thevenot, F.
- Journal of the Less Common Metals, Vol. 117, Issue 1-2
Unusual properties of icosahedral boron-rich solids
journal, September 2006
- Emin, David
- Journal of Solid State Chemistry, Vol. 179, Issue 9
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
Defect clustering and self-healing of electron-irradiated boron-rich solids
journal, May 1995
- Carrard, M.; Emin, D.; Zuppiroli, L.
- Physical Review B, Vol. 51, Issue 17
Hard boron–suboxide-based films deposited in a sputter-sourced, high-density plasma deposition system
journal, September 1997
- Doughty, C.; Gorbatkin, S. M.; Tsui, T. Y.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 15, Issue 5
Boron suboxide ultrahard materials
journal, July 2013
- Herrmann, M.; Sigalas, I.; Thiele, M.
- International Journal of Refractory Metals and Hard Materials, Vol. 39
Thermodynamics of impurities in semiconductors
journal, September 2004
- Estreicher, S. K.; Sanati, M.; West, D.
- Physical Review B, Vol. 70, Issue 12
Thermodynamic Stability of Boron: The Role of Defects and Zero Point Motion
journal, March 2007
- van Setten, Michiel J.; Uijttewaal, Matthé A.; de Wijs, Gilles A.
- Journal of the American Chemical Society, Vol. 129, Issue 9
Superhard boron suboxide (B6O): Crystal structure, synthesis, properties, applications, and materials based thereon
journal, March 2022
- Perevislov, Sergey N.
- Mendeleev Communications, Vol. 32, Issue 2
Electronic structure and optical properties of theB 12 O 2 crystal
journal, July 1996
- Li, Dong; Ching, W. Y.
- Physical Review B, Vol. 54, Issue 3
Improved tetrahedron method for Brillouin-zone integrations
journal, June 1994
- Blöchl, Peter E.; Jepsen, O.; Andersen, O. K.
- Physical Review B, Vol. 49, Issue 23
Thermal Conductivity of Boron and Some Boron Compounds
journal, September 1971
- Slack, Glen A.; Oliver, D. W.; Horn, F. H.
- Physical Review B, Vol. 4, Issue 6
Icosahedral packing of B12 icosahedra in boron suboxide (B6O)
journal, January 1998
- Hubert, Hervé; Devouard, Bertrand; Garvie, Laurence A. J.
- Nature, Vol. 391, Issue 6665
Crystal structure of B6O
conference, January 1991
- Higashi, Iwami; Kobayashi, Masayoshi; Bernhard, Jonte
- AIP Conference Proceedings
Isotope dependencies of Raman spectra of and Bonding of intericosahedral chains
journal, August 1997
- Aselage, T. L.; Tallant, D. R.; Emin, D.
- Physical Review B, Vol. 56, Issue 6
High-Pressure, High-Temperature Synthesis and Characterization of Boron Suboxide (B6O)
journal, May 1998
- Hubert, Hervé; Garvie, Laurence A. J.; Devouard, Bertrand
- Chemistry of Materials, Vol. 10, Issue 6