Novel Non-Diamond Isoelectronic B-C-O Metastable Phases under High Pressure: B2CO5 and B3CO3
-
摘要: 由于B、C和O等轻元素之间易形成较强的共价键，B-C-O化合物被认为是探索和设计新型超硬材料的理想体系之一。采用CALYPSO结构预测方法，结合第一性原理计算，系统探究了高压下B-C-O三元体系的稳定性，发现了2个新型亚稳态化合物B2CO5和B3CO3。其中，B2CO5的形成能距热力学凸包仅6 meV/atom。B2CO5和B3CO3属于非金刚石等电子化合物，并具有新型成键方式：B2CO5晶体结构由sp2杂化的CO3平面三角单元和sp3杂化的BO4四面体通过O原子共享的方式构成；而B3CO3晶体结构中包含sp3杂化的BCO3四面体。力学性能分析表明，B2CO5在不同晶面上表现出明显的弹性各向异性，而B3CO3则在(001)面保持弹性各向同性。硬度计算结果显示，在0 GPa压强下，B3CO3的维氏硬度约为36.4 GPa，具有潜在的超硬材料应用价值。电子结构计算表明，在25 GPa压强下，B2CO5和B3CO3均表现出宽带隙半导体特征，Perdew-Burke-Ernzerhof（PBE）泛函计算得到的带隙分别为4.49和5.46 eV，Heyd-Scuseria-Ernzerhof 2006（HSE06）杂化泛函结果分别为6.77和7.07 eV。本研究丰富了B-C-O化合物的成键类型，并为高压条件下设计新型超硬材料提供了理论数据。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.
-
Key words:
- B-C-O system /
- CALYPSO /
- structure prediction /
- high pressure
-
图 1 B-C-O体系在25GPa下的相图及晶体结构示意图：(a) 25 GPa下B-C-O体系的三元相图（其中，单质为Pnnm-B[52–53]、Fd$\overline 3 $m-C[54]、C2/m-O[55]；二元化合物为R$\overline 3 $m-B6O[56]、P21/m-B4C[57]、I$\overline 4 $2d-CO2[58]、Cmc21-B2O3[59]），(b) B2CO5和(c) B3CO3在25 GPa下的晶体结构及结构单元（蓝色、黑色和红色的球分别为硼、碳和氧原子）
Figure 1. Phase diagram and crystal structure schematics of the B-C-O system at 25 GPa: (a) ternary phase diagram of the B-C-O system at 25 GPa (The elemental substances are Pnnm-B[52–53], Fd$\overline 3 $m-C[54] and C2/m-O[55]; the binary compounds are R$\overline 3 $m-B6O[56], P21/m-B4C[57], I$\overline 4 $2d-CO2[58], and Cmc21-B2O3[59].); crystal structures and structural units of (b) B2CO5 and (c) B3CO3 (Blue, black, and red spheres represent boron, carbon, and oxygen atoms, respectively.)
图 2 B2CO5以及B3CO3在0和25 GPa的声子色散关系（横坐标表示沿布里渊区高对称点路径的波矢）
Figure 2. Phonon dispersion relations of B2CO5 and B3CO3 at 0 and 25 GPa (The horizontal axis represents wave vectors along high-symmetry paths in the Brillouin zone.)
图 3 B2CO5和B3CO3在不同压强下的杨氏模量二维投影图（蓝色、橙色和红色曲线分别表示0、15和25 GPa下杨氏模量二维投影图）
Figure 3. Two-dimensional (2D) projections of Young’s modulus for B2CO5 and B3CO3 under different pressures (Blue, orange, and red curves represent the 2D projections of Young’s modulus at 0, 15, and 25 GPa, respectively.)
图 4 B2CO5和B3CO3在0和25 GPa下的能带结构与分波态密度
Figure 4. Band structures and partial density of states (PDOS) of B2CO5 and B3CO3 at 0 and 25 GPa
表 1 0和25 GPa下B2CO5的弹性常数$C_{ij} $、体积模量$B $、剪切模量$G $和杨氏模量$E $
Table 1. Elastic constants $C_{ij} $, bulk modulus $B $, shear modulus $G $, and Young’s modulus $E $ of B2CO5 at 0 and 25 GPa
GPa p C11 C22 C33 C12 C13 C23 C44 C55 C66 C15 C25 C35 C46 B G E 0 137 237 66 68 18 −0.7 42 52 98 18 20 2 35 57 53 122 25 327 441 420 158 97 90 188 147 219 −35 50 −22 63 206 155 372 
下载: 导出CSV
表 2 0和25 GPa下B3CO3的弹性常数$C_{ij} $、体积模量$B $、剪切模量$G $和杨氏模量$E $
Table 2. Elastic constants $C_{ij} $, bulk modulus $B $, shear modulus $G $, and Young’s modulus $E $ of B3CO3 at 0 and 25 GPa
GPa p C11 C33 C12 C13 C44 C66 C14 C15 B G E 0 618 692 118 121 235 250 51 9 294 244 572 25 772 827 176 160 276 298 68 12 373 287 686
下载: 导出CSV
-
[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 B2CxO 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BCxO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.20210792LIU C, YING P. Mechanism of pressure and carbon content regulating physical properties of BCxO 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]. -
下载:
图(4) / 表(2)
计量
- 文章访问数: 71
- HTML全文浏览量: 16
- PDF下载量: 6
