EFFECTS OF VACANCY DEFECTS ON MONOLAYER HBN: A DENSITY FUNCTIONAL THEORY STUDY
DOI:
https://doi.org/10.18173/2354-1059.2026-0035Keywords:
monolayer hBN, nitrogen vacancy, boron vacancy, electronic structure, projected density of states (PDOS), DFTAbstract
Density functional theory (DFT) calculations were performed to investigate the structural and electronic properties of pristine monolayer hexagonal boron nitride (hBN) containing neutral B and N vacancies. Both types of vacancies preserve the overall planar configuration of the monolayer but induce distinct local structural reconstructions. The N vacancy slightly elongates the neighboring B–N bonds, whereas the B vacancy causes bond contraction accompanied by angular distortion. The calculated vacancy removal energies indicate that V_N@hBN is energetically more favorable than V_B@hBN. Notably, both the vacancies introduce localized in-gap states and induce spin-dependent electronic properties. In V_B@hBN, these states predominantly originate from the px-and py- orbitals of the three N atoms surrounding the vacancy, whereas those of V_N@hBN are primarily associated with the pz- orbitals. These findings demonstrate that vacancy defects can effectively modulate the electronic structure and spin properties of monolayer hBN.
References
[1] K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotkevich, S. V. Morozov & A. K. Geim, “Two-dimensional atomic crystals”, Proc Natl Acad Sci U S A., vol. 102, no. 30, pp. 10451-10453, 2005. DOI: 10.1073/pnas.0502848102
[2] T. T. Thoa, V. C. Tuan, H. V. Hung, W.F. Huang, P. T. Hoan & N. T. M. Hue, “How are hydroxyl groups localized on a graphene sheet?”, ACS Omega, vol. 7, no. 42, pp. 37221-37228, 2022. DOI: 10.1021/acsomega.2c03447
[3] G. A. Q. Abdulrahman, A. Aziz, N. A. A. Qasem & A. Alazzam, “2D materials: Synthesis, properties, and energy-related applications”, Coordination Chemistry Reviews, vol. 544, p. 216950, 2025. DOI: 10.1016/j.ccr.2025.216950
[4] D. L. Quyen & N. A. Duc, “Controlled growth and characterization of monolayer MoS₂ by using metal-organic chemical vapor deposition”, HNUE Journal of Science. Natural Sciences, vol. 66, no. 1, pp. 49-56, 2021. DOI: 10.18173/2354-1059.2021-0006 (in Vietnamese).
[5] D. O. Byrne & F. I. Allen, “Atomic engineering of triangular nanopores in monolayer hBN for membrane applications: A decoupled seeding and growth approach”, ACS Applied Nano Materials, vol. 8, no. 9, pp. 4565-4572, 2025. DOI: 10.1021/acsanm.4c06998
[6] A. Zobelli, C. P. Ewels, A. Gloter & G. Seifert, “Vacancy migration in hexagonal boron nitride”, Physical Review B, vol. 75, no. 8, pp. 094104, 2007. DOI: 10.1103/PhysRevB.75.094104
[7] J. Ryou, J. Park & S. Hong, “Investigations of vacancy structures related to their growth in h-BN sheet”, Nanoscale Research Letters, vol. 12, pp. 445, 2017. DOI: 10.1186/s11671-017-2194-6
[8] R. F. Liu & C. Cheng, “Ab initio studies of possible magnetism in a BN sheet by nonmagnetic impurities and vacancies”, Physical Review B, vol. 76, p. 014405, 2007. DOI: 10.1103/PhysRevB.76.014405
[9] Q. A. Asif, A. Hussain, A. Nabi, M. Tayyab & H. M. Rafique, “Computational study of X-doped hexagonal boron nitride (h-BN): Structural and electronic properties (X = P, S, O, F, Cl)”, Journal of Molecular Modeling, vol. 27, no. 31, 2021. DOI: 10.1007/s00894-020-04659-z
[10] G. Kresse & J. Furthmüller, http://cms.mpi.unive.ac.at/vasp.
[11] J. P. Perdew, K. Burke & M. Ernzerhof, “Generalized gradient approximation made simple”, Physical Review Letters, vol. 77, no. 18, pp. 3865-3868, 1996. DOI: 10.1103/PhysRevLett.77.3865
[12] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple”, Physical Review Letters, vol. 78, no. 17, pp. 1396, 1997. DOI: 10.1103/PhysRevLett.78.1396
[13] M. Dion, H. Rydberg, E. Schroder, D.C. Langreth & B.I. Lundqvist, “Van der Waals density functional for general geometries”, Physical Review Letters, vol. 92, no. 16, pp. 246401, 2004. DOI: 10.1103/PhysRevLett.92.246401
[14] K. Jirí, R. B. David & M. Angelos, “Chemical accuracy for the van der Waals density functional”, Journal of Physics: Condensed Matter, vol. 22, no. 2, pp. 022201, 2010. DOI: 10.1088/0953-8984/22/2/022201
[15] J. Klimeš, D. R. Bowler & A. Michaelides, “Van der Waals density functionals applied to solids”, Physical Review B, vol. 83, no. 25, p. 195131, 2011. DOI: 10.1103/PhysRevB.83.195131
[16] D. Chakraborty, K. Berland, T. Thonhauser, “Next-generation nonlocal van der Waals density functional”, Journal of Chemical Theory and Computation, vol. 16, no. 9, pp. 5893-5911, 2020. DOI: 10.1021/acs.jctc.0c00471
[17] M. Morscher, M. Corso, T. Greber, J. Osterwalder, “Formation of single layer h-BN on Pd(1 1 1)”, Surface Science, vol. 600, no. 16, pp. 3280-3284, 2006. DOI: 10.1016/j.susc.2006.06.016
[18] B. Chettri, P. K. Patra, N. N. Hieu & P. Rai, “Hexagonal boron nitride (h-BN) nanosheet as a potential hydrogen adsorption material: A density functional theory (DFT) study”, Surfaces and Interfaces, vol. 24, p. 101043, 2021. DOI: 10.1016/j.surfin.2021.101043
