Novel Non-Diamond Isoelectronic B-C-O Metastable Phases under High Pressure: B2CO5 and B3CO3

LIU Dan; GAO Pengyue

doi:10.11858/gywlxb.20261148

Volume 40 Issue 11

Nov 2026

Turn off MathJax

Article Contents

Chinese Journal of High Pressure Physics > 2026 > 40(11): 110110.

LIU Dan, GAO Pengyue. Novel Non-Diamond Isoelectronic B-C-O Metastable Phases under High Pressure: B2CO5 and B3CO3[J]. Chinese Journal of High Pressure Physics, 2026, 40(11): 110110. doi: 10.11858/gywlxb.20261148

Citation:

LIU Dan, GAO Pengyue. Novel Non-Diamond Isoelectronic B-C-O Metastable Phases under High Pressure: B₂CO₅ and B₃CO₃[J]. Chinese Journal of High Pressure Physics, 2026, 40(11): 110110. doi: 10.11858/gywlxb.20261148

Citation:

PDF( 4959 KB)

Novel Non-Diamond Isoelectronic B-C-O Metastable Phases under High Pressure: B₂CO₅ and B₃CO₃

doi: 10.11858/gywlxb.20261148

LIU Dan^{1, 2
,},
GAO Pengyue^{1,*
,
,}

1.
State Key Laboratory of High Pressure and Superhard Materials, College of Physics, Jilin University, Changchun 130012, Jilin, China
2.
Key Laboratory of Material Simulation Methods and Software of the Ministry of Education, College of Physics, Jilin University, Changchun 130012, Jilin, China

Received Date: 19 Aug 2026
Rev Recd Date: 20 Oct 2026

Available Online: 27 Oct 2026

Issue Publish Date: 05 Nov 2026

Abstract

Abstract

B-C-O compounds are considered one of the ideal systems for exploring and designing novel superhard materials due to the readily formed strong covalent bonds among the light elements B, C, and O. In this work, the CALYPSO structure prediction method, combined with first-principles calculations, was employed to systematically investigate the stability of ternary B-C-O compounds under high pressure. Two novel metastable compounds, B₂CO₅ and B₃CO₃, were identified. Among them, the formation energy of B₂CO₅ is only 6 meV/atom above the thermodynamic convex hull. Both B₂CO₅ and B₃CO₃ are non-diamond isoelectronic compounds and exhibit novel bonding configurations. The crystal structure of B₂CO₅ consists of sp²-hybridized planar triangular CO₃ units and sp³-hybridized BO₄ tetrahedra, which are interconnected through shared O atoms. In contrast, the crystal structure of B₃CO₃ contains sp³-hybridized BCO₃ tetrahedral units. Mechanical property analysis reveals that B₂CO₅ exhibits pronounced elastic anisotropy along different crystallographic planes, whereas B₃CO₃ maintains elastic isotropy on the (001) plane. Hardness calculations indicate that B₃CO₃ has a Vickers hardness of approximately 36.4 GPa at 0 GPa, suggesting its potential for applications as a superhard material. Electronic structure calculations show that both B₂CO₅ and B₃CO₃ exhibit wide-band-gap semiconducting characteristics at 25 GPa, with PBE-calculated (Perdew-Burke-Ernzerhof-calculated) band gaps of 4.49 and 5.46 eV, respectively, while the corresponding values obtained using the HSE06 (Heyd-Scuseria-Ernzerhof 2006) hybrid functional are 6.77 and 7.07 eV. This study enriches the diversity of bonding configurations in B-C-O compounds and provides theoretical insights and data for the design of novel superhard materials under high-pressure conditions.
- B-C-O system,
- CALYPSO,
- structure prediction,
- high pressure

FullText(HTML)

References(59)

References

[1]	VEPŘEK S. The search for novel, superhard materials [J]. Journal of Vacuum Science & Technology A, 1999, 17(5): 2401–2420. doi: 10.1116/1.581977
[2]	ZHAO Z S, XU B, TIAN Y J. Recent advances in superhard materials [J]. Annual Review of Materials Research, 2016, 46: 383–406. doi: 10.1146/annurev-matsci-070115-031649
[3]	YEUNG M T, MOHAMMADI R, KANER R B. Ultraincompressible, superhard materials [J]. Annual Review of Materials Research, 2016, 46: 465–485. doi: 10.1146/annurev-matsci-070115-032148
[4]	KVASHNIN A G, ALLAHYARI Z, OGANOV A R. Computational discovery of hard and superhard materials [J]. Journal of Applied Physics, 2019, 126(4): 040901. doi: 10.1063/1.5109782
[5]	LE GODEC Y, COURAC A, SOLOZHENKO V L. High-pressure synthesis of superhard and ultrahard materials [J]. Journal of Applied Physics, 2019, 126(15): 151102. doi: 10.1063/1.5111321
[6]	ROBINSON P J, LIU G X, CIBOROWSKI S, et al. Mystery of three borides: differential metal-boron bonding governing superhard structures [J]. Chemistry of Materials, 2017, 29(23): 9892–9896. doi: 10.1021/acs.chemmater.7b04378
[7]	MA T, LI H, ZHENG X, et al. Ultrastrong boron frameworks in ZrB₁₂: a highway for electron conducting [J]. Advanced Materials, 2017, 29(3): 1604003. doi: 10.1002/adma.201604003
[8]	SAMSONOV G V. Boron: its compounds and alloys [M]. Washington: Office of Technical Services, Department of Commerce, 1962.
[9]	KURAKEVYCH O O. Superhard phases of simple substances and binary compounds of the B-C-N-O system: from diamond to the latest results (a review) [J]. Journal of Superhard Materials, 2009, 31(3): 139–157. doi: 10.3103/S1063457609030010
[10]	LIU C, CHEN M W, HE J L, et al. Superhard B₂CO phases derived from carbon allotropes [J]. RSC Advances, 2017, 7(82): 52192–52199. doi: 10.1039/c7ra09277f
[11]	SOLOZHENKO V L, DUB S N, NOVIKOV N V. Mechanical properties of cubic BC₂N, a new superhard phase [J]. Diamond and Related Materials, 2001, 10(12): 2228–2231. doi: 10.1016/S0925-9635(01)00513-1
[12]	SOLOZHENKO V L, ANDRAULT D, FIQUET G, et al. Synthesis of superhard cubic BC₂N [J]. Applied Physics Letters, 2001, 78(10): 1385–1387. doi: 10.1063/1.1337623
[13]	ZHAO Y, HE D W, DAEMEN L L, et al. Superhard B-C-N materials synthesized in nanostructured bulks [J]. Journal of Materials Research, 2002, 17(12): 3139–3145. doi: 10.1557/JMR.2002.0454
[14]	LIU L L, ZHAO Z Y, YU T, et al. Hexagonal BC₂N with remarkably high hardness [J]. The Journal of Physical Chemistry C, 2018, 122(12): 6801–6807. doi: 10.1021/acs.jpcc.8b00252
[15]	GARVIE L A J, HUBERT H, PETUSKEY W T, et al. High-pressure, high-temperature syntheses in the B-C-N-O system [J]. Journal of Solid State Chemistry, 1997, 133(2): 365–371. doi: 10.1006/jssc.1997.7583
[16]	BOLOTINA N B, DYUZHEVA T I, BENDELIANI N A. Atomic structure of boron suboxycarbide B(C, O)_0.155 [J]. Crystallography Reports, 2001, 46(5): 734–740. doi: 10.1134/1.1405858
[17]	GLADKAYA I S, DYUZHEVA T I, EKIMOV E A, et al. Crystal growth at high pressure and the problem of characterization of the interstitial phases in the B-C-O system [J]. Journal of Alloys and Compounds, 2001, 329: 153–156. doi: 10.1016/S0925-8388(01)01612-7
[18]	LI Y W, LI Q, MA Y M. B₂CO: a potential superhard material in the B-C-O system [J]. Europhysics Letters, 2011, 95(6): 66006. doi: 10.1209/0295-5075/95/66006
[19]	LIU C, ZHAO Z S, LUO K, et al. Superhard orthorhombic phase of B₂CO compound [J]. Diamond and Related Materials, 2017, 73: 87–92. doi: 10.1016/j.diamond.2016.07.010
[20]	QIAO L P, JIN Z, YAN G Y, et al. Density-functional-studying of oP8-, tI16-, and tP4-B₂CO physical properties under pressure [J]. Journal of Solid State Chemistry, 2019, 270: 642–650. doi: 10.1016/j.jssc.2018.12.012
[21]	YAN H Y, ZHANG M G, WEI Q, et al. A new orthorhombic ground-state phase and mechanical strengths of ternary B₂CO compound [J]. Chemical Physics Letters, 2018, 701: 86–92. doi: 10.1016/j.cplett.2018.04.041
[22]	CHEN M W, LIU C, LIU M L, et al. Exploring the electronic, mechanical, and anisotropy properties of novel tetragonal B₂CO phase [J]. Journal of Materials Research, 2019, 34(21): 3617–3626. doi: 10.1557/jmr.2019.271
[23]	LIU C, LIU L Y, YING P. Stability, deformation, physical properties of novel hard B₂CO phases [J]. Journal of Materials Science, 2022, 57(20): 9231–9245. doi: 10.1007/s10853-022-07242-4
[24]	ZHANG M G, YAN H Y, ZHENG B B, et al. Influences of carbon concentration on crystal structures and ideal strengths of B₂C_xO compounds in the B-C-O system [J]. Scientific Reports, 2015, 5(1): 15481. doi: 10.1038/srep15481
[25]	WANG S N, OGANOV A R, QIAN G R, et al. Novel superhard B-C-O phases predicted from first principles [J]. Physical Chemistry Chemical Physics, 2016, 18(3): 1859–1863. doi: 10.1039/c5cp05367f
[26]	NURUZZAMAN M, ALAM M A, SHAH M A H, et al. Investigation of thermodynamic stability, mechanical and electronic properties of superhard tetragonal B₄CO₄ compound: ab initio calculations [J]. Computational Condensed Matter, 2017, 12: 1–8. doi: 10.1016/j.cocom.2017.05.005
[27]	ZHENG B B, ZHANG M G, WANG C J. Exploring the mechanical anisotropy and ideal strengths of tetragonal B₄CO₄ [J]. Materials, 2017, 10(2): 128. doi: 10.3390/ma10020128
[28]	QIAO L P, JIN Z. Two B-C-O compounds: structural, mechanical anisotropy and electronic properties under pressure [J]. Materials, 2017, 10(12): 1413. doi: 10.3390/ma10121413
[29]	刘超, 应盼. 压力和碳含量调控BC_xO化合物物理性质的机理研究 [J]. 高压物理学报, 2021, 35(6): 061101. doi: 10.11858/gywlxb.20210792 LIU C, YING P. Mechanism of pressure and carbon content regulating physical properties of BC_xO compounds [J]. Chinese Journal of High Pressure Physics, 2021, 35(6): 061101. doi: 10.11858/gywlxb.20210792
[30]	刘超, 陈明伟, 梁彤祥. B-C-O化合物硬质结构的理论设计与性质研究 [M]. 北京: 冶金工业出版社, 2020. LIU C, CHEN M W, LIANG T X. Theoretical design and properties of hard structures of B-C-O compounds [M]. Beijing: Metallurgical Industry Press, 2020.
[31]	XING M J, LI X Z. BC₂O in C2/m phase: light element compound with direct band gaps [J]. Journal of Solid State Chemistry, 2021, 304: 122590. doi: 10.1016/j.jssc.2021.122590
[32]	LIU C, CHEN M W, YANG Y, et al. Theoretical exploring the mechanical and electrical properties of tI12-B₆C₄O₂ [J]. Computational Materials Science, 2018, 150: 259–264. doi: 10.1016/j.commatsci.2018.04.020
[33]	LIU C, YING P. Theoretical study of novel B-C-O compounds with non-diamond isoelectronic [J]. Chinese Physics B, 2022, 31(2): 026201. doi: 10.1088/1674-1056/ac0cd2
[34]	MUKHERJEE M, SAHU H, LOSEGO M D, et al. Informatics-driven design of superhard B-C-O compounds [J]. ACS Applied Materials & Interfaces, 2024, 16(8): 10372–10379. doi: 10.1021/acsami.3c18105
[35]	WANG Y C, LYU J, ZHU L, et al. Crystal structure prediction via particle-swarm optimization [J]. Physical Review B, 2010, 82(9): 094116. doi: 10.1103/PhysRevB.82.094116
[36]	WANG Y C, LYU J, ZHU L, et al. CALYPSO: a method for crystal structure prediction [J]. Computer Physics Communications, 2012, 183(10): 2063–2070. doi: 10.1016/j.cpc.2012.05.008
[37]	ZHANG X H, WANG S, BERGARA A, et al. Li-F polarity-driven stabilization of -Ⅶ oxidation state of gold at high pressure [J]. Nature Communications, 2025, 16(1): 11566. doi: 10.1038/s41467-025-67973-1
[38]	SUN Y B, LU Y H, LI Z M, et al. Automatic hydrogen clathrate recognition neural networks for high-pressure superconductor prediction [J]. Journal of Materials Chemistry C, 2026, 14(15): 6232–6239. doi: 10.1039/d5tc04470g
[39]	MA C H, MA Y, WANG H, et al. Hydrogen-vacancy-induced stable superconducting niobium hydride at high pressure [J]. Journal of the American Chemical Society, 2025, 147(13): 11028–11035. doi: 10.1021/jacs.4c15868
[40]	ZHANG Z S, LIU Y B, LIU J D, et al. Electronegativity informed graph neural networks for superconducting temperature prediction with generative crystal validation [J]. Inorganic Chemistry, 2026, 65(17): 9625–9632. doi: 10.1021/acs.inorgchem.6c01169
[41]	HOHENBERG P, KOHN W. Inhomogeneous electron gas [J]. Physical Review, 1964, 136(3B): B864–B871. doi: 10.1103/PhysRev.136.B864
[42]	KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J]. Physical Review B, 1996, 54(16): 11169–11186. doi: 10.1103/PhysRevB.54.11169
[43]	KRESSE G, FURTHMÜLLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set [J]. Computational Materials Science, 1996, 6(1): 15–50. doi: 10.1016/0927-0256(96)00008-0
[44]	BLÖCHL P E. Projector augmented-wave method [J]. Physical Review B, 1994, 50(24): 17953–17979. doi: 10.1103/PhysRevB.50.17953
[45]	PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple [J]. Physical Review Letters, 1996, 77(18): 3865–3868. doi: 10.1103/PhysRevLett.77.3865
[46]	TOGO A, OBA F, TANAKA I. First-principles calculations of the ferroelastic transition between rutile-type and CaCl₂-type SiO₂ at high pressures [J]. Physical Review B, 2008, 78(13): 134106. doi: 10.1103/PhysRevB.78.134106
[47]	LE PAGE Y, SAXE P. Symmetry-general least-squares extraction of elastic data for strained materials from ab initio calculations of stress [J]. Physical Review B, 2002, 65(10): 104104. doi: 10.1103/PhysRevB.65.104104
[48]	VOIGT W. Lehrbuch der kristallphysik [M]. Leipzig: Teubner Verlag, 1928.
[49]	REUSS A. Berechnung der Fließgrenze von mischkristallen auf grund der plastizitätsbedingung für einkristalle [J]. Zeitschrift für Angewandte Mathematik und Mechanik, 1929, 9(1): 49–58. doi: 10.1002/zamm.19290090104
[50]	HILL R. The elastic behaviour of a crystalline aggregate [J]. Proceedings of the Physical Society. Section A, 1952, 65(5): 349–354. doi: 10.1088/0370-1298/65/5/307
[51]	TIAN Y, XU B, ZHAO Z. Microscopic theory of hardness and design of novel superhard crystals [J]. International Journal of Refractory Metals and Hard Materials, 2012, 33: 93–106. doi: 10.1016/j.ijrmhm.2012.02.021
[52]	OGANOV A R. Discovery of γ-B₂₈, a novel boron allotrope with partially ionic bonding [J]. MRS Online Proceedings Library, 2011, 1307(1): 201. doi: 10.1557/opl.2011.501
[53]	OGANOV A R, CHEN J H, GATTI C, et al. Ionic high-pressure form of elemental boron [J]. Nature, 2009, 457(7231): 863–867. doi: 10.1038/nature07736
[54]	JAIN A, ONG S P, HAUTIER G, et al. Commentary: the materials project: a materials genome approach to accelerating materials innovation [J]. APL Materials, 2013, 1(1): 011002. doi: 10.1063/1.4812323
[55]	DATCHI F, WECK G. X-ray crystallography of simple molecular solids up to megabar pressures: application to solid oxygen and carbon dioxide [J]. Zeitschrift für Kristallographie-Crystalline Materials, 2014, 229(2): 135–157. doi: 10.1515/zkri-2013-1669
[56]	BOLMGREN H, LUNDSTRÖM T, OKADA S. Structure refinement of the boron suboxide B₆O by the rietveld method [C]// Boron-Rich Solids. AIP Conference Proceedings, 1991, 231: 197–200.
[57]	WANG D Y, YAN Q, WANG B, et al. Predicted boron-carbide compounds: a first-principles study [J]. The Journal of Chemical Physics, 2014, 140(22): 224704. doi: 10.1063/1.4882071
[58]	DATCHI F, MALLICK B, SALAMAT A, et al. Structure of polymeric carbon dioxide CO₂-Ⅴ [J]. Physical Review Letters, 2012, 108(12): 125701. doi: 10.1103/PhysRevLett.108.125701
[59]	The Materials Project. Materials data on B₂O₃ by materials project [DS/OL]. (2020-07-15) [2025-08-06].