Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Liu, Bin; Evans, Dylan; Deng, Hao; Edgar, James

doi:10.1021/acs.jpcc.2c05590

Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Journal Article · Tue Sep 13 04:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c05590· OSTI ID:1894427

^[1]; Evans, Dylan ^[2]; ^[2]; Edgar, James ^[2]

Kansas State Univ., Manhattan, KS (United States); Kansas State University
Kansas State Univ., Manhattan, KS (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Kansas State Univ., Manhattan, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0021264; AC02-05CH11231

OSTI ID:: 1894427

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 37 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

B6O-Based Composite to Rival Polycrystalline Cubic Boron Nitride Chen, C.; He, D.; Kou, Z. Advanced Materials, Vol. 19, Issue 23 https://doi.org/10.1002/adma.200700836	journal	December 2007
Production of α-Rhombohedral Boron by Amorphous Boron Crystallization Shalamberidze, S. O.; Kalandadze, G. I.; Khulelidze, D. E. Journal of Solid State Chemistry, Vol. 154, Issue 1 https://doi.org/10.1006/jssc.2000.8836	journal	October 2000
Structural Determinants in the Higher Borides Matkovich, V. I.; Economy, J. Boron and Refractory Borides https://doi.org/10.1007/978-3-642-66620-9_7	book	January 1977
Melt growth and properties of B6P crystals Slack, Glen A.; McNelly, T. F.; Taft, E. A. Journal of Physics and Chemistry of Solids, Vol. 44, Issue 10 https://doi.org/10.1016/0022-3697(83)90151-8	journal	January 1983
Non-stoichiometry of boron suboxide (B6O) Bills, (Mrs.)P. M.; Lewis, D. Journal of the Less Common Metals, Vol. 45, Issue 2 https://doi.org/10.1016/0022-5088(76)90284-8	journal	March 1976
Hot pressing of boron suboxide B12O2 Brodhag, C.; Thevenot, F. Journal of the Less Common Metals, Vol. 117, Issue 1-2 https://doi.org/10.1016/0022-5088(86)90003-2	journal	March 1986
Synthesis and structure of non-stoichiometric B6O Olofsson, Malin; Lundström, Torsten Journal of Alloys and Compounds, Vol. 257, Issue 1-2 https://doi.org/10.1016/S0925-8388(97)00008-X	journal	July 1997
Boron suboxide ultrahard materials Herrmann, M.; Sigalas, I.; Thiele, M. International Journal of Refractory Metals and Hard Materials, Vol. 39 https://doi.org/10.1016/j.ijrmhm.2012.02.009	journal	July 2013
Some crystallography, chemistry, physics, and thermodynamics of B12O2, B12P2, B12As2, and related alpha-boron type crystals Slack, Glen A.; Morgan, Kenneth E. Journal of Physics and Chemistry of Solids, Vol. 75, Issue 9 https://doi.org/10.1016/j.jpcs.2013.12.021	journal	September 2014
Bonding and doping of simple icosahedral-boride semiconductors Emin, David Journal of Solid State Chemistry, Vol. 177, Issue 4-5 https://doi.org/10.1016/j.jssc.2003.12.017	journal	April 2004
Unusual properties of icosahedral boron-rich solids Emin, David Journal of Solid State Chemistry, Vol. 179, Issue 9 https://doi.org/10.1016/j.jssc.2006.01.014	journal	September 2006
Superhard boron suboxide (B6O): Crystal structure, synthesis, properties, applications, and materials based thereon Perevislov, Sergey N. Mendeleev Communications, Vol. 32, Issue 2 https://doi.org/10.1016/j.mencom.2022.03.002	journal	March 2022
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Self-healing in B ₁₂ P ₂ through Mediated Defect Recombination Huber, S. P.; Gullikson, E.; Frye, C. D. Chemistry of Materials, Vol. 28, Issue 22 https://doi.org/10.1021/acs.chemmater.6b04075	journal	November 2016
High-Pressure, High-Temperature Synthesis and Characterization of Boron Suboxide (B₆O) Hubert, Hervé; Garvie, Laurence A. J.; Devouard, Bertrand Chemistry of Materials, Vol. 10, Issue 6 https://doi.org/10.1021/cm970433+	journal	May 1998
Thermodynamic Stability of Boron: The Role of Defects and Zero Point Motion van Setten, Michiel J.; Uijttewaal, Matthé A.; de Wijs, Gilles A. Journal of the American Chemical Society, Vol. 129, Issue 9 https://doi.org/10.1021/ja0631246	journal	March 2007
Icosahedral packing of B12 icosahedra in boron suboxide (B6O) Hubert, Hervé; Devouard, Bertrand; Garvie, Laurence A. J. Nature, Vol. 391, Issue 6665 https://doi.org/10.1038/34885	journal	January 1998
Identification and design principles of low hole effective mass p-type transparent conducting oxides Hautier, Geoffroy; Miglio, Anna; Ceder, Gerbrand Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3292	journal	August 2013
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Boron suboxide: As hard as cubic boron nitride He, Duanwei; Zhao, Yusheng; Daemen, L. Applied Physics Letters, Vol. 81, Issue 4 https://doi.org/10.1063/1.1494860	journal	July 2002
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Structure refinement of the boron suboxide B6O by the Rietveld method Bolmgren, H.; Lundström, T.; Okada, S. AIP Conference Proceedings https://doi.org/10.1063/1.40868	conference	January 1991
Crystal structure of B6O Higashi, Iwami; Kobayashi, Masayoshi; Bernhard, Jonte AIP Conference Proceedings https://doi.org/10.1063/1.40870	conference	January 1991
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Icosahedral Boron‐Rich Solids Emin, David Physics Today, Vol. 40, Issue 1 https://doi.org/10.1063/1.881112	journal	January 1987
Absence of defect clusters in electron irradiated boron carbide Stoto, T.; Zuppiroli, L.; Pelissier, J. Radiation Effects, Vol. 90, Issue 3-4 https://doi.org/10.1080/00337578508222528	journal	January 1985
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Thermal Conductivity of Boron and Some Boron Compounds Slack, Glen A.; Oliver, D. W.; Horn, F. H. Physical Review B, Vol. 4, Issue 6 https://doi.org/10.1103/PhysRevB.4.1714	journal	September 1971
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Improved tetrahedron method for Brillouin-zone integrations Blöchl, Peter E.; Jepsen, O.; Andersen, O. K. Physical Review B, Vol. 49, Issue 23 https://doi.org/10.1103/PhysRevB.49.16223	journal	June 1994
Defect clustering and self-healing of electron-irradiated boron-rich solids Carrard, M.; Emin, D.; Zuppiroli, L. Physical Review B, Vol. 51, Issue 17 https://doi.org/10.1103/PhysRevB.51.11270	journal	May 1995
Electronic structure and optical properties of theB12O2crystal Li, Dong; Ching, W. Y. Physical Review B, Vol. 54, Issue 3 https://doi.org/10.1103/PhysRevB.54.1451	journal	July 1996
Isotope dependencies of Raman spectra of B 12 As 2 , B 12 P 2 , B 12 O 2 , and B 1 2 + x C 3 − x : Bonding of intericosahedral chains Aselage, T. L.; Tallant, D. R.; Emin, D. Physical Review B, Vol. 56, Issue 6 https://doi.org/10.1103/PhysRevB.56.3122	journal	August 1997
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Thermodynamics of impurities in semiconductors Estreicher, S. K.; Sanati, M.; West, D. Physical Review B, Vol. 70, Issue 12 https://doi.org/10.1103/PhysRevB.70.125209	journal	September 2004
Electronic structure and defect properties of B 6 O from hybrid functional and many-body perturbation theory calculations: A possible ambipolar transparent conductor Varley, J. B.; Lordi, V.; Miglio, A. Physical Review B, Vol. 90, Issue 4 https://doi.org/10.1103/PhysRevB.90.045205	journal	July 2014
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Hard boron–suboxide-based films deposited in a sputter-sourced, high-density plasma deposition system Doughty, C.; Gorbatkin, S. M.; Tsui, T. Y. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 15, Issue 5 https://doi.org/10.1116/1.580933	journal	September 1997
The Existence and Formation of the Solid B[sub 6]O Rizzo, H. F.; Simmons, W. C.; Bielstein, H. O. Journal of The Electrochemical Society, Vol. 109, Issue 11 https://doi.org/10.1149/1.2425241	journal	January 1962
Growth of boron suboxide crystals in the B–B₂O₃ system at high pressure and high temperature He, Duanwei; Akaishi, Minoru; Scott, Brian L. Journal of Materials Research, Vol. 17, Issue 2 https://doi.org/10.1557/JMR.2002.0041	journal	February 2002
sumo: Command-line tools for plotting and analysis of periodic ab initio calculations M. Ganose, Alex; J. Jackson, Adam; O. Scanlon, David Journal of Open Source Software, Vol. 3, Issue 28 https://doi.org/10.21105/joss.00717	journal	August 2018
Thermoelectric Properties of Hot-pressed Boron Suboxide (B₆O) Akashi, Takaya; Itoh, Tsuyoshi; Gunjishima, Itaru MATERIALS TRANSACTIONS, Vol. 43, Issue 7 https://doi.org/10.2320/matertrans.43.1719	journal	January 2002
Experimental study and critical review of structural, thermodynamic and mechanical properties of superhard refractory boron suboxide B6O Kurakevych, O. O.; Solozhenko, V. L. Journal of Superhard Materials, Vol. 33, Issue 6 https://doi.org/10.3103/S106345761206007X	journal	December 2011

Similar Records

Effects of interface bonding and defects on boron diffusion at Si/SiO{sub 2} interface

Journal Article · Fri Dec 13 23:00:00 EST 2013 · Journal of Applied Physics · OSTI ID:22266175

Synthesis of boron suboxide from boron and boric acid under mild pressure and temperature conditions

Journal Article · Sun May 15 00:00:00 EDT 2011 · Materials Research Bulletin · OSTI ID:22210059

Synthesis of boron suboxide (B{sub 6}O) with ball milled boron oxide (B{sub 2}O{sub 3}) under lower pressure and temperature

Journal Article · Thu Jul 15 00:00:00 EDT 2010 · Journal of Solid State Chemistry · OSTI ID:21421564

Related Subjects

36 MATERIALS SCIENCE
Chemical structure
Defects
Energy
Lattices
Potential energy

Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Citation Formats

References (44)

Similar Records

Related Subjects