Abstract
Ultrawide bandgap semiconductor, e.g., diamond, is considered as the next generation of semiconductor. Here, a new orthorhombic carbon allotrope (P212121-C16) with ultrawide bandgap and ultra-large hardness is identified. The stability of the newly designed carbon is confirmed by the energy, phonon spectrum, ab-initio molecular dynamics and elastic constants. The hardness ranges from 88 GPa to 93 GPa according to different models, which is comparable to diamond. The indirect bandgap reaches 6.23 eV, which is obviously larger than that of diamond, and makes it a promising ultra-wide bandgap semiconductor. Importantly, the experimental possibility is confirmed by comparing the simulated X-ray diffraction with experimental results, and two hypothetical transformation paths to synthesize it from graphite are proposed.
![](http://media.springernature.com/lw685/springer-static/image/art%3A10.1007%2Fs11467-022-1204-z/MediaObjects/11467_2022_1204_Fig1_HTML.jpg)
Similar content being viewed by others
References
J. Millan, P. Godignon, X. Perpina, A. Perez-Tomas, and J. Rebollo, A survey of wide bandgap power semiconductor devices, IEEE Trans. Power Electron. 29(5), 2155 (2014)
H. Okumura, A roadmap for future wide bandgap semiconductor power electronics, MRS Bull. 40(5), 439 (2015)
P. R. Wilson, B. Ferreira, J. Zhang, and C. DiMarino, IEEE ITRW: International technology roadmap for wide-bandgap power semiconductors: An overview, IEEE Power Electron. Mag. 5(2), 22 (2018)
J. Y. Tsao, S. Chowdhury, M. A. Hollis, D. Jena, N. M. Johnson, K. A. Jones, R. J. Kaplar, S. Rajan, C. G. Van de Walle, E. Bellotti, C. L. Chua, R. Collazo, M. E. Coltrin, J. A. Cooper, K. R. Evans, S. Graham, T. A. Grotjohn, E. R. Heller, M. Higashiwaki, M. S. Islam, P. W. Juodawlkis, M. A. Khan, A. D. Koehler, J. H. Leach, U. K. Mishra, R. J. Nemanich, R. C. N. Pilawa-Podgurski, J. B. Shealy, Z. Sitar, M. J. Tadjer, A. F. Witulski, M. Wraback, and J. A. Simmons, Ultrawidebandgap semiconductors: Research opportunities and challenges, Adv. Electron. Mater. 4(1), 1600501 (2018)
B. J. Baliga, Semiconductors for high-voltage, vertical channel field-effect transistors, J. Appl. Phys. 53(3), 1759 (1982)
X. Shi, C. He, C. J. Pickard, C. Tang, and J. Zhong, Stochastic generation of complex crystal structures combining group and graph theory with application to carbon, Phys. Rev. B 97(1), 014104 (2018)
P. Gao, B. Gao, S. Lu, H. Liu, J. Lv, Y. Wang, and Y. Ma, Structure search of two-dimensional systems using CALYPSO methodology, Front. Phys. 17(2), 23203 (2022)
R.-S. Zhang and J.-W. Jiang, The art of designing carbon allotropes, Front. Phys. 14(1), 13401 (2019)
W. Tong, Q. Wei, H.-Y. Yan, M.-G. Zhang, and X.-M. Zhu, Accelerating inverse crystal structure prediction by machine learning: A case study of carbon allotropes, Front. Phys. 15(6), 63501 (2020)
H. W. Kroto, J. R. Heath, S. C. O’Brien, R. F. Curl, and R. E. Smalley, C60: Buckminsterfullerene, Nature 318(6042), 162 (1985)
S. Iijima, Helical microtubules of graphitic carbon, Nature 354(6348), 56 (1991)
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, Electric field effect in atomically thin carbon films, Science 306(5696), 666 (2004)
H. Tang, X. Yuan, Y. Cheng, H. Fei, F. Liu, T. Liang, Z. Zeng, T. Ishii, M.-S. Wang, T. Katsura, H. Sheng, and H. Gou, Synthesis of paracrystalline diamond, Nature 599(7886), 605 (2021)
X. -L. Sheng, Q. -B. Yan, F. Ye, Q. -R. Zheng, and G. Su, T-carbon: A novel carbon allotrope, Phys. Rev. Lett. 106(15), 155703 (2011)
F. Occelli, P. Loubeyre, and R. Letoullec, Properties of diamond under hydrostatic pressures up to 140 GPa, Nat. Mater. 2(3), 151 (2003)
X. -Y. Ding, C. Zhang, D. -Q. Wang, B. -S. Li, Q. Wang, Z. G. Yu, K. -W. Ang, and Y. -W. Zhang, A new carbon allotrope: T5-carbon, Scr. Mater. 189, 72 (2020)
M. Liao, F. Wang, J. Zhu, Z. Lai, and Y. Liu, P2221-C8: A novel carbon allotrope denser than diamond, Scr. Mater. 212, 114549 (2022)
J. T. Wang, C. Chen, and H. Mizuseki, Body centered cubic carbon BC14: An all-sp3 bonded full-fledged pentadiamond, Phys. Rev. B 102(18), 184106 (2020)
J. Liu, Q. Gao, and Z. Hu, HSH-carbon: A novel sp2-sp3 carbon allotrope with an ultrawide energy gap, Front. Phys. 17(6), 63505 (2022)
R. Lv, X. Yang, D. Yang, C. Niu, C. Zhao, J. Qin, J. Zang, F. Dong, L. Dong, and C. Shan, Computational prediction of a novel superhard sp3 trigonal carbon allotrope with bandgap larger than diamond, Chin. Phys. Lett. 38(7), 076101 (2021)
C. He, X. Shi, S. J. Clark, J. Li, C. J. Pickard, T. Ouyang, C. Zhang, C. Tang, and J. Zhong, Complex low energy tetrahedral polymorphs of group IV elements from first principles, Phys. Rev. Lett. 121(17), 175701 (2018)
Q. Zhu, A. R. Oganov, M. A. Salvadó, P. Pertierra, and A. O. Lyakhov, Denser than diamond: Ab initio search for superdense carbon allotropes, Phys. Rev. B 83(19), 193410 (2011)
X. Zhang, Y. Wang, J. Lv, C. Zhu, Q. Li, M. Zhang, Q. Li, and Y. Ma, First-principles structural design of superhard materials, J. Chem. Phys. 138(11), 114101 (2013)
J. Wang, C. Chen, and Y. Kawazoe, Orthorhombic carbon allotrope of compressed graphite: Ab initio calculations, Phys. Rev. B 85(3), 033410 (2012)
C. J. Pickard and R. J. Needs, Ab initio random structure searching, J. Phys.: Condens. Matter 23(5), 053201 (2011)
A. J. Karttunen, T. F. Fässler, M. Linnolahti, and T. A. Pakkanen, Structural principles of semiconducting group 14 clathrate frameworks, Inorg. Chem. 50(5), 1733 (2011)
H. Yin, X. Shi, C. He, M. Martinez-Canales, J. Li, C. J. Pickard, C. Tang, T. Ouyang, C. Zhang, and J. Zhong, Stone-Wales graphene: A two-dimensional carbon semimetal with magic stability, Phys. Rev. B 99(4), 041405 (2019)
S. J. Clark, M. D. Segall, C. J. Pickard, P. J. Hasnip, M. I. J. Probert, K. Refson, and M. C. Payne, First principles methods using CASTEP, Z. Kristallogr. 220, 567 (2005)
J. E. Peralta, J. Heyd, G. E. Scuseria, and R. L. Martin, Spin-orbit splittings and energy band gaps calculated with the Heyd-Scuseria-Ernzerhof screened hybrid functional, Phys. Rev. B 74(7), 073101 (2006)
J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77(18), 3865 (1996)
D. R. Hamann, M. Schlüter, and C. Chiang, Norm-conserving pseudopotentials, Phys. Rev. Lett. 43(20), 1494 (1979)
D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue formalism, Phys. Rev. B 41(11), 7892 (1990)
B. G. Pfrommer, M. Côté, S. G. Louie and M. L. Cohen, Relaxation of crystals with the quasi-Newton method, J. Comput. Phys. 131(1), 233 (1997)
S. Baroni, S. de Gironcoli, A. Dal Corso, and P. Giannozzi, Phonons and related crystal properties from density-functional perturbation theory, Rev. Mod. Phys. 73(2), 515 (2001)
M. Liao, Y. Liu, F. Zhou, T. Han, D. Yang, N. Qu, and Z. Lai, A high-efficient strain-stress method for calculating higher-order elastic constants from first-principles, Comput. Phys. Commun. 280, 108478 (2022)
M. Liao, Y. Liu, S.-L. Shang, F. Zhou, N. Qu, Y. Chen, Z. Lai, Z.-K. Liu, and J. Zhu, Elastic3rd: A tool for calculating third-order elastic constants from first-principles calculations, Comput. Phys. Commun. 261, 107777 (2021)
M. Liao, Y. Liu, Y. Wang, F. Zhou, N. Qu, T. Han, D. Yang, Z. Lai, Z.-K. Liu, and J. Zhu, Revisiting the third-order elastic constants of diamond: The higher-order effect, Diam. Relat. Mater. 117, 108490 (2021)
R. Hill, The elastic behaviour of a crystalline aggregate, Proc. Phys. Soc. Sect. A 65(5), 349 (1952)
M. Liao, Y. Liu, P. Cui, N. Qu, F. Zhou, D. Yang, T. Han, Z. Lai, and J. Zhu, Modeling of alloying effect on elastic properties in BCC Nb-Ti-V-Zr solid solution: From unary to quaternary, Comput. Mater. Sci. 172, 109289 (2020)
F. Gao, J. He, E. Wu, S. Liu, D. Yu, D. Li, S. Zhang, and Y. Tian, Hardness of covalent crystals, Phys. Rev. Lett. 91(1), 015502 (2003)
V. A. Blatov, A. P. Shevchenko, and D. M. Proserpio, Applied topological analysis of crystal structures with the program package topospro, Cryst. Growth Des. 14(7), 3576 (2014)
V. A. Blatov, O. A. Blatova, F. Daeyaert, and M. W. Deem, Nanoporous materials with predicted zeolite topologies, RSC Adv. 10(30), 17760 (2020)
R. Hoffmann, A. A. Kabanov, A. A. Golov, and D. M. Proserpio, Homo citans and carbon allotropes: For an ethics of citation, Angew. Chemie Int. Ed. 55(37), 10962 (2012)
M. Al-Fahdi, A. Rodriguez, T. Ouyang, and M. Hu, High-throughput computation of new carbon allotropes with diverse hybridization and ultrahigh hardness, Crystals 11(7), 783 (2021)
N. A. Anurova, V. A. Blatov, G. D. Ilyushin, and D. M. Proserpio, Natural tilings for zeolite-type frameworks, J. Phys. Chem. C 114(22), 10160 (2010)
O. Delgado-Friedrichs and M. O’Keeffe, Identification of and symmetry computation for crystal nets, Acta Crystallogr. Sect. A Found. Crystallogr. 59(4), 351 (2003)
J.-T. Wang, H. Weng, S. Nie, Z. Fang, Y. Kawazoe, and C. Chen, Body-centered orthorhombic C16: A novel topological node-line semimetal, Phys. Rev. Lett. 116(19), 195501 (2012)
N. N. Matyushenko, V. E. Strel’Nitskiǐ, and V. A. Gusev, A dense new version of crystalline carbon C8, JETP Lett. 30(4), 199 (1979)
R. L. Johnston and R. Hoffmann, Superdense carbon, C8: supercubane or analog of. gamma. -silicon? J. Am. Chem. Soc. 111(3), 810 (1989)
Z.-Z. Li, C.-S. Lian, J. Xu, L.-F. Xu, J.-T. Wang, and C. Chen, Computational prediction of body-centered cubic carbon in an all-sp3 six-member ring configuration, Phys. Rev. B 91(21), 214106 (2015)
J. -T. Wang, C. Chen, E. Wang, and Y. Kawazoe, A new carbon allotrope with six-fold helical chains in all-sp2 bonding networks, Sci. Rep. 4(1), 4339 (2015)
F. Mouhat and F.-X. Coudert, Necessary and sufficient elastic stability conditions in various crystal systems, Phys. Rev. B 90(22), 224104 (2014)
S. F. Pugh, XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals, London, Edinburgh, Dublin Philos. Mag. J. Sci. 45(367), 823 (1954)
X. Chen, H. Niu, D. Li, and Y. Li, Modeling hardness of polycrystalline materials and bulk metallic glasses, Intermetallics 19(9), 1275 (2011)
Y. Tian, B. Xu, and Z. Zhao, Microscopic theory of hardness and design of novel superhard crystals, Int. J. Refract. Met. Hard Mater. 33, 93 (2012)
E. Mazhnik and A. R. Oganov, A model of hardness and fracture toughness of solids, J. Appl. Phys. 126(12), 125109 (2019)
M. Liao, Y. Liu, Z. Lai, and J. Zhu, Pressure and temperature dependence of second-order elastic constants from third-order elastic constants in TMC (TM=Nb, Ti, V, Zr), Ceram. Int. 47(19), 27535 (2021)
R. R. Rao and A. Padmaja, Effective second-order elastic constants of a strained crystal using the finite strain elasticity theory, J. Appl. Phys. 62(2), 440 (1987)
H. J. McSkimin and P. Andreatch, Elastic moduli of diamond as a function of pressure and temperature, J. Appl. Phys. 43(7), 2944 (1972)
B. Sundqvist, Carbon under pressure, Phys. Rep. 909, 1 (2021)
J. Wang, C. Chen, and Y. Kawazoe, Low-temperature phase transformation from graphite to sp3 orthorhombic carbon, Phys. Rev. Lett. 106(7), 075501 (2011)
J. Q. Wang, C. X. Zhao, C. Y. Niu, Q. Sun, and Y. Jia, C20-T carbon: A novel superhard sp3 carbon allotrope with large cavities, J. Phys.: Condens. Matter 28(47), 475402 (2012)
A. Mujica, C. J. Pickard and R. J. Needs, Low-energy tetrahedral polymorphs of carbon, silicon, and germanium, Phys. Rev. B 91(21), 214104 (2015)
L. D. Landau and E. M. Lifshitz, in: Electrodynamics of Continuous Media (2nd Ed.), Eds. L. D. Landau and E. M. Lifshitz, Pergamon, Amsterdam, Second Edi. (1984), Vol. 8, pp 257–289
D. Pantea, S. Brochu, S. Thiboutot, G. Ampleman, and G. Scholz, A morphological investigation of soot produced by the detonation of munitions, Chemosphere 65(5), 821 (2002)
P. Chen, F. Huang, and S. Yun, Characterization of the condensed carbon in detonation soot, Carbon 41(11), 2093 (2003)
K. Yamada, Shock synthesis of a new cubic form of carbon, Carbon 41(6), 1309 (2003)
Q. Li, Y. Ma, A. R. Oganov, H. Wang, H. Wang, Y. Xu, T. Cui, H.-K. Mao, and G. Zou, Superhard monoclinic polymorph of carbon, Phys. Rev. Lett. 102(17), 175506 (2009)
C. He, L. Sun, C. Zhang, X. Peng, K. Zhang, and J. Zhong, New superhard carbon phases between graphite and diamond, Solid State Commun. 152(16), 1560 (2012)
C. He, C. X. Zhang, L. Z. Sun, N. Jiao, K. W. Zhang, and J. Zhong, Structure, stability and electronic properties of tricycle type graphane, Phys. Status Solidi - Rapid Res. Lett. 6(11), 427 (2012)
H. Niu, X.-Q. Chen, S. Wang, D. Li, W. L. Mao, and Y. Li, Families of superhard crystalline carbon allotropes constructed via cold compression of graphite and nanotubes, Phys. Rev. Lett. 108(13), 135501 (2012)
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 51875269), and the Startup Foundation of Jiangsu University of Science and Technology (No. 202100000135).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Liao, M., Maimaitimusha, J., Zhang, X. et al. P212121-C16: An ultrawide bandgap and ultrahard carbon allotrope with the bandgap larger than diamond. Front. Phys. 17, 63507 (2022). https://doi.org/10.1007/s11467-022-1204-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11467-022-1204-z