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Stabilization of hBN/SiC heterostructures with vacancies and transition-metal atoms

Arsalan Hashemi1,2,3,*, Nima Ghafari Cherati4,5, Sadegh Ghaderzadeh6, Yanzhou Wang7, Mahdi Ghorbani-Asl8, and Tapio Ala-Nissila7,9,†

  • 1Department of Applied Physics, MSP Group, Quantum Technology Finland Center of Excellence, Aalto University, P.O. Box 15600, FI-00076 Espoo, Finland
  • 2European Laboratory for Learning and Intelligent Systems (ELLIS) Institute Finland, Maarintie 8, 02150 Espoo, Finland
  • 3Department of Technical Physics, University of Eastern Finland, P.O. Box 1627, FI-70211 Kuopio, Finland
  • 4HUN-REN Wigner Research Centre for Physics, PO Box 49, H-1525 Budapest, Hungary
  • 5Department of Atomic Physics, Institute of Physics, Budapest University of Technology and Economics, Műegyetem rkp. 3, H-1111 Budapest, Hungary
  • 6School of Chemistry, University of Nottingham, Nottingham NG7 2RD, United Kingdom
  • 7Department of Applied Physics, MSP Group, Quantum Technology Finland Center of Excellence, Aalto University, FI-00076 Espoo, Finland
  • 8Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, 01328 Dresden, Germany
  • 9Department of Mathematical Sciences and Interdisciplinary Centre for Mathematical Modelling, Loughborough University, Loughborough, Leicestershire LE11 3TU, United Kingdom

  • *Contact author: arsalan.hashemi@aalto.fi
  • †Contact author: tapio.ala-nissila@aalto.fi
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Phys. Rev. Materials 10, 045801 – Published 13 April, 2026

DOI: https://doi.org/10.1103/lymz-nlbf

Abstract

When two-dimensional atomic layers of different materials are brought into close proximity to form van der Waals (vdW) heterostructures, interlayer interactions can strongly influence their physicochemical properties. These effects are particularly pronounced when the interface exhibits local order and near-perfect structural alignment, giving rise to moiré patterns. Using density-functional theory calculations, we investigate a bilayer heterostructure composed of hexagonal boron nitride (hBN) and silicon carbide (SiC). We predict that introducing a boron vacancy, VB, at specific lattice sites alters the interlayer interaction from weak vdW coupling to localized silicon-nitrogen covalent bonding. Motivated by this mechanism, we examine the binding of transition-metal adatoms and identify principles for enhancing surface reactivity and stabilizing isolated single-metal atoms. Machine-learning molecular dynamics at finite temperature further demonstrate rapid and effectively irreversible trapping of Cu at VB sites, and show how the VB:Cu ratio governs the transition from single-atom isolation to vacancy-directed aggregation. These results suggest the hBN/SiC heterostructure as a versatile platform for atomically precise transition-metal functionalization, with implications for catalytic energy-conversion materials.

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References (121)

  1. A. K. Geim and I. V. Grigorieva, Van der Waals heterostructures, Nature (London) 499, 419 (2013).
  2. J.-Y. You, B. Gu, G. Su, and Y. P. Feng, Two-dimensional topological superconductivity candidate in a van der Waals layered material, Phys. Rev. B 103, 104503 (2021).
  3. K. S. Burch, D. Mandrus, and J.-G. Park, Magnetism in two-dimensional van der Waals materials, Nature (London) 563, 47 (2018).
  4. J. Qi, Z. Wu, W. Wang, K. Bao, L. Wang, J. Wu, C. Ke, Y. Xu, and Q. He, Fabrication and applications of van der Waals heterostructures, Int. J. Extreme Manuf. 5, 022007 (2023).
  5. A. Castellanos-Gomez, X. Duan, Z. Fei, H. Rodriguez Gutierrez, Y. Huang, X. Huang, J. Quereda, Q. Qian, E. Sutter, and P. Sutter, Van der Waals heterostructures, Nat. Rev. Methods Primers 2, 58 (2022).
  6. R. Cheng, F. Wang, L. Yin, Z. Wang, Y. Wen, T. A. Shifa, and J. He, High-performance, multifunctional devices based on asymmetric van der Waals heterostructures, Nat. Electron. 1, 356 (2018).
  7. X. Sun, C. Zhu, J. Yi, L. Xiang, C. Ma, H. Liu, B. Zheng, Y. Liu, W. You, W. Zhang, et al., Reconfigurable logic-in-memory architectures based on a two-dimensional van der Waals heterostructure device, Nat. Electron. 5, 752 (2022).
  8. Y. Liu, N. O. Weiss, X. Duan, H.-C. Cheng, Y. Huang, and X. Duan, Van der Waals heterostructures and devices, Nat. Rev. Mater. 1, 16042 (2016).
  9. N. Mounet, M. Gibertini, P. Schwaller, D. Campi, A. Merkys, A. Marrazzo, T. Sohier, I. E. Castelli, A. Cepellotti, G. Pizzi, et al., Two-dimensional materials from high-throughput computational exfoliation of experimentally known compounds, Nat. Nanotechnol. 13, 246 (2018).
  10. H. Yang, S. O. Valenzuela, M. Chshiev, S. Couet, B. Dieny, B. Dlubak, A. Fert, K. Garello, M. Jamet, D.-E. Jeong, et al., Two-dimensional materials prospects for non-volatile spintronic memories, Nature (London) 606, 663 (2022).
  11. Y. Liu, X. Duan, H.-J. Shin, S. Park, Y. Huang, and X. Duan, Promises and prospects of two-dimensional transistors, Nature (London) 591, 43 (2021).
  12. M. S. Hybertsen, Role of interface strain in a lattice-matched heterostructure, Phys. Rev. Lett. 64, 555 (1990).
  13. Y. Lu, J. Chen, M. J. Coupin, S. Sinha, and J. H. Warner, Lattice-mismatch-driven small-angle moiré twists in epitaxially grown 2D vertical layered heterostructures, Adv. Mater. 34, 2205403 (2022).
  14. W. Li, T. Brumme, and T. Heine, Relaxation effects in transition metal dichalcogenide bilayer heterostructures, npj 2D Mater. Appl. 8, 43 (2024).
  15. H. Wang, Z. Li, D. Li, P. Chen, L. Pi, X. Zhou, and T. Zhai, Van der Waals integration based on two-dimensional materials for high-performance infrared photodetectors, Adv. Funct. Mater. 31, 2103106 (2021).
  16. B. V. Lotsch, Vertical 2D heterostructures, Annu. Rev. Mater. Res. 45, 85 (2015).
  17. D. N. Futaba, Hexagonal boron nitride heterostructures go large, Nat. Electron. 6, 104 (2023).
  18. Y. Kubota, K. Watanabe, O. Tsuda, and T. Taniguchi, Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure, Science 317, 932 (2007).
  19. C. Wang, J. Guo, L. Dong, A. Aiyiti, X. Xu, and B. Li, Superior thermal conductivity in suspended bilayer hexagonal boron nitride, Sci. Rep. 6, 25334 (2016).
  20. H. Xu, B. Ding, Y. Xu, Z. Huang, D. Wei, S. Chen, T. Lan, Y. Pan, H.-M. Cheng, and B. Liu, Magnetically tunable and stable deep-ultraviolet birefringent optics using two-dimensional hexagonal boron nitride, Nat. Nanotechnol. 17, 1091 (2022).
  21. N. Ding, X. Chen, and C.-M. L. Wu, Mechanical properties and failure behaviors of the interface of hybrid graphene/hexagonal boron nitride sheets, Sci. Rep. 6, 31499 (2016).
  22. S. Moon, J. Kim, J. Park, S. Im, J. Kim, I. Hwang, and J. K. Kim, Hexagonal boron nitride for next-generation photonics and electronics, Adv. Mater. 35, 2204161 (2023).
  23. M. Li, G. Huang, X. Chen, J. Yin, P. Zhang, Y. Yao, J. Shen, Y. Wu, and J. Huang, Perspectives on environmental applications of hexagonal boron nitride nanomaterials, Nano Today 44, 101486 (2022).
  24. Y. Gong, Z.-Q. Xu, D. Li, J. Zhang, I. Aharonovich, and Y. Zhang, Two-dimensional hexagonal boron nitride for building next-generation energy-efficient devices, ACS Energy Lett. 6, 985 (2021).
  25. M. Zahoor, S. Khan, P. M. Ismail, L. Qiao, M. Haneef, J. Akbar, M. Bououdina, C. Zeng, and S. Ali, in Hexagonal Boron Nitride, Micro and Nano Technologies, edited by K. Deshmukh, M. Pandey, and C. Mustansar Hussain (Elsevier, Amsterdam, Netherlands, 2024), pp. 3–28.
  26. Z. Balta and E. B. Simsek, in Hexagonal Boron Nitride, Micro and Nano Technologies, edited by K. Deshmukh, M. Pandey, and C. Mustansar Hussain (Elsevier, Amsterdam, Netherlands, 2024), pp. 205–233.
  27. C. R. Dean, A. F. Young, I. Meric, C. Lee, L. Wang, S. Sorgenfrei, K. Watanabe, T. Taniguchi, P. Kim, K. L. Shepard, et al., Boron nitride substrates for high-quality graphene electronics, Nat. Nanotechnol. 5, 722 (2010).
  28. M. Yankowitz, Q. Ma, P. Jarillo-Herrero, and B. J. LeRoy, van der Waals heterostructures combining graphene and hexagonal boron nitride, Nat. Rev. Phys. 1, 112 (2019).
  29. I. G. Juma, G. Kim, D. Jariwala, and S. K. Behura, Direct growth of hexagonal boron nitride on non-metallic substrates and its heterostructures with graphene, iScience 24, 103374 (2021).
  30. S. Ogawa, S. Fukushima, and M. Shimatani, Hexagonal-boron nitride/graphene van der Waals heterostructure-based wavelength-selective infrared absorbers using plasmonic metasurfaces for multi-spectral infrared photodetectors, J. Opt. Soc. Am. B 39, 3149 (2022).
  31. Z. Wang, Y. B. Wang, J. Yin, E. Tóvári, Y. Yang, L. Lin, M. Holwill, J. Birkbeck, D. J. Perello, S. Xu, J. Zultak, R. V. Gorbachev, A. V. Kretinin, T. Taniguchi, K. Watanabe, S. V. Morozov, M. Anđelković, S. P. Milovanović, L. Covaci, F. M. Peeters, et al., Composite super-moiré lattices in double-aligned graphene heterostructures, Sci. Adv. 5, eaay8897 (2019).
  32. S. Moore, C. Ciccarino, D. Halbertal, L. McGilly, N. Finney, K. Yao, Y. Shao, G. Ni, A. Sternbach, E. Telford, et al., Nanoscale lattice dynamics in hexagonal boron nitride moiré superlattices, Nat. Commun. 12, 5741 (2021).
  33. R. V. Kamat, A. L. Sharpe, M. Pendharkar, J. Hu, S. J. Tran, G. Zaborski, M. Hocking, J. Finney, K. Watanabe, T. Taniguchi, M. A. Kastner, A. J. Mannix, T. Heinz, and D. Goldhaber-Gordon, Deterministic fabrication of graphene hexagonal boron nitride moiré superlattices, Proc. Natl. Acad. Sci. USA 121, e2410993121 (2024).
  34. E. M. O'Sullivan, N. Grobert, and M. Swart, Density functional theory investigation of 2D phase separated graphene/hexagonal boron nitride monolayers; band gap, band edge positions, and photo activity, J. Phys. Chem. C 129, 638 (2025).
  35. P. Huang, E. Riccardi, S. Messelot, H. Graef, F. Valmorra, J. Tignon, T. Taniguchi, K. Watanabe, S. Dhillon, B. Placais, et al., Ultra-long carrier lifetime in neutral graphene-hBN van der Waals heterostructures under mid-infrared illumination, Nat. Commun. 11, 863 (2020).
  36. K. Zollner, A. W. Cummings, S. Roche, and J. Fabian, Graphene on two-dimensional hexagonal BN, AlN, and GaN: Electronic, spin-orbit, and spin relaxation properties, Phys. Rev. B 103, 075129 (2021).
  37. J. Li, M. Ghorbani-Asl, K. Lasek, V. Pathirage, A. V. Krasheninnikov, and M. Batzill, A van der Waals heterostructure with an electronically textured moiré pattern: PtSe2/PtTe2, ACS Nano 17, 5913 (2023).
  38. M. K. Jat, P. Tiwari, R. Bajaj, I. Shitut, S. Mandal, K. Watanabe, T. Taniguchi, H. Krishnamurthy, M. Jain, and A. Bid, Higher order gaps in the renormalized band structure of doubly aligned hBN/bilayer graphene moiré superlattice, Nat. Commun. 15, 2335 (2024).
  39. Y. Ma, M. Huang, X. Zhang, W. Hu, Z. Zhou, K. Feng, W. Li, Y. Chen, C. Lou, W. Zhang, et al., Magnetic bloch states at integer flux quanta induced by super-moiré potential in graphene aligned with twisted boron nitride, Nat. Commun. 16, 1860 (2025).
  40. Z. Lu, T. Han, Y. Yao, Z. Hadjri, J. Yang, J. Seo, L. Shi, S. Ye, K. Watanabe, T. Taniguchi, et al., Extended quantum anomalous Hall states in graphene/hBN moiré superlattices, Nature (London) 637, 1090 (2025).
  41. J. Hafner, C. Wolverton, and G. Ceder, Toward computational materials design: The impact of density functional theory on materials research, MRS Bull. 31, 659 (2006).
  42. R. Dingreville, R. A. Karnesky, G. Puel, and J.-H. Schmitt, Review of the synergies between computational modeling and experimental characterization of materials across length scales, J. Mater. Sci. 51, 1178 (2016).
  43. Q. Li, L. Xu, K.-W. Luo, X.-F. Li, W.-Q. Huang, L.-L. Wang, and Y.-B. Yu, Electric-field-induced widely tunable direct and indirect band gaps in hBN/MoS2 van der Waals heterostructures, J. Mater. Chem. C 5, 4426 (2017).
  44. C.-M. Liu, S.-Y. Hsu, H.-S. Chen, C.-C. Hsu, Y.-W. Lan, H.-C. Chiu, and W.-C. Lin, Enhanced stability of Gr, h-BN and Gr/h-BN protected MoS2 flakes under laser illumination, Appl. Surf. Sci. Adv. 25, 100687 (2025).
  45. J.-X. Duan, C.-B. Wang, Y. Tian, and L.-L. Zhang, Augmenting anisotropic gas sensitivity in Borophene/hBN van der Waals heterostructures via transition metal doping for advanced sensing applications, Mater. Sci. Eng., B 317, 118129 (2025).
  46. X. Zhao, Z. Cui, A. Ge, X. Lu, X. Guan, J. Zhang, H. Zhen, L. Sun, S. Wang, and W. Lu, Exciton–polaritons of hBN/WS2 heterostructure in cavity observed at room temperature, Appl. Phys. Lett. 121, 231106 (2022).
  47. Y. Li, P. Jiang, X. Liu, H. Wu, X. Lyu, X. Li, H. Lin, J. Tang, Q. Lyu, H. Yang, C. Wu, G. Lu, P.-H. Tan, L.-Y. Peng, Y. Gao, X. Hu, and Q. Gong, Defect-assisted photoemission in the hBN and TMDs/hBN heterostructures, J. Phys. Chem. C 128, 4286 (2024).
  48. M. Le Ster, T. Maerkl, P. J. Kowalczyk, and S. A. Brown, Moiré patterns in van der Waals heterostructures, Phys. Rev. B 99, 075422 (2019).
  49. T. Rakib, P. Pochet, E. Ertekin, and H. T. Johnson, Moiré engineering in van der Waals heterostructures, J. Appl. Phys. 132, 120901 (2022).
  50. X. Wang, G. Zhao, X. Lv, M. Zhao, W. Wei, and G. Liu, Effect of doping and defects on the electronic properties of MoS2/WSe2 bilayer heterostructure: A first-principles study, Phys. Chem. Chem. Phys. 26, 18402 (2024).
  51. N. Alem, R. Erni, C. Kisielowski, M. D. Rossell, W. Gannett, and A. Zettl, Atomically thin hexagonal boron nitride probed by ultrahigh-resolution transmission electron microscopy, Phys. Rev. B 80, 155425 (2009).
  52. A. L. Gibb, N. Alem, J.-H. Chen, K. J. Erickson, J. Ciston, A. Gautam, M. Linck, and A. Zettl, Atomic resolution imaging of grain boundary defects in monolayer chemical vapor deposition-grown hexagonal boron nitride, J. Am. Chem. Soc. 135, 6758 (2013).
  53. N. Alem, Q. M. Ramasse, C. R. Seabourne, O. V. Yazyev, K. Erickson, M. C. Sarahan, C. Kisielowski, A. J. Scott, S. G. Louie, and A. Zettl, Subangstrom edge relaxations probed by electron microscopy in hexagonal boron nitride, Phys. Rev. Lett. 109, 205502 (2012).
  54. J. He, N. Jiao, C. Zhang, H. Xiao, X. Chen, and L. Sun, Spin switch of the transition-metal-doped boron nitride sheet through H/F chemical decoration, J. Phys. Chem. C 118, 8899 (2014).
  55. J. Zhang, R. Sun, D. Ruan, M. Zhang, Y. Li, K. Zhang, F. Cheng, Z. Wang, and Z.-M. Wang, Point defects in two-dimensional hexagonal boron nitride: A perspective, J. Appl. Phys. 128, 100902 (2020).
  56. C. Cholsuk, A. Zand, A. Çakan, and T. Vogl, The hBN defects database: A theoretical compilation of color centers in hexagonal boron nitride, J. Phys. Chem. C 128, 12716 (2024).
  57. L. Zeng, S. Zhang, J. Meng, J. Chen, J. Jiang, Y. Shi, J. Huang, Z. Yin, J. Wu, and X. Zhang, Single-photon emission from point defects in hexagonal boron nitride induced by plasma treatment, ACS Appl. Mater. Interfaces 16, 24899 (2024).
  58. T. J. Smart, K. Li, J. Xu, and Y. Ping, Intersystem crossing and exciton–defect coupling of spin defects in hexagonal boron nitride, npj Comput. Mater. 7, 59 (2021).
  59. H. Chen, Y. Kang, D. Pu, M. Tian, N. Wan, Y. Xu, B. Yu, W. Jie, and Y. Zhao, Introduction of defects in hexagonal boron nitride for vacancy-based 2D memristors, Nanoscale 15, 4309 (2023).
  60. R. Babar, G. Barcza, A. Pershin, H. Park, O. Bulancea Lindvall, G. Thiering, Ö. Legeza, J. H. Warner, I. A. Abrikosov, A. Gali, et al., Low-symmetry vacancy-related spin qubit in hexagonal boron nitride, npj Comput. Mater. 10, 184 (2024).
  61. S. Yu, L. Li, Z. Lai, J. Hao, and K. Zhang, A coupling effects of vacancy and Al (Ga, In) dopant on electronic structures of hexagonal boron nitride monolayer, Mater. Res. Express 4, 116302 (2017).
  62. X. Lian, X. Tang, H. Liao, W. Guo, Y. Zhang, and G. Gao, Theoretical screening of double-atom metals anchored on defective boron nitride for N2 reduction, React. Kinet. Mech. Catal. 137, 3241 (2024).
  63. S.-Y. Zhong, S.-Y. Wu, X.-Y. Yu, G.-Q. Shen, L. Yan, and K.-L. Xu, First-principles studies of the adsorption and catalytic properties for gas molecules on h-BN monolayer doped with various transition metal atoms, Catal. Surv. Asia 26, 69 (2022).
  64. J. Wu, L. Yin, and L. Zhang, Tuning the electronic structure, bandgap energy and photoluminescence properties of hexagonal boron nitride nanosheets via a controllable Ce3+ ions doping, RSC Adv. 3, 7408 (2013).
  65. L. Khalil, C. Ernandes, J. Avila, A. Rousseau, P. Dudin, N. D. Zhigadlo, G. Cassabois, B. Gil, F. Oehler, J. Chaste, and A. Ouerghi, High p doped and robust band structure in Mg-doped hexagonal boron nitride, Nanoscale Adv. 5, 3225 (2023).
  66. R. Kozubek, P. Ernst, C. Herbig, T. Michely, and M. Schleberger, Fabrication of defective single layers of hexagonal boron nitride on various supports for potential applications in catalysis and DNA sequencing, ACS Appl. Nano Mater. 1, 3765 (2018).
  67. Y. Lu, B. Li, N. Xu, Z. Zhou, Y. Xiao, Y. Jiang, T. Li, S. Hu, Y. Gong, and Y. Cao, One-atom-thick hexagonal boron nitride co-catalyst for enhanced oxygen evolution reactions, Nat. Commun. 14, 6965 (2023).
  68. A. Gottscholl, M. Diez, V. Soltamov, C. Kasper, D. Krauße, A. Sperlich, M. Kianinia, C. Bradac, I. Aharonovich, and V. Dyakonov, Spin defects in hBN as promising temperature, pressure and magnetic field quantum sensors, Nat. Commun. 12, 4480 (2021).
  69. H.-H. Fang, X.-J. Wang, X. Marie, and H.-B. Sun, Quantum sensing with optically accessible spin defects in van der Waals layered materials, Light Sci. Appl. 13, 303 (2024).
  70. M. Fischer, J. M. Caridad, A. Sajid, S. Ghaderzadeh, M. Ghorbani-Asl, L. Gammelgaard, P. Bøggild, K. S. Thygesen, A. V. Krasheninnikov, S. Xiao, et al., Controlled generation of luminescent centers in hexagonal boron nitride by irradiation engineering, Sci. Adv. 7, eabe7138 (2021).
  71. S. J. White, T. Yang, N. Dontschuk, C. Li, Z.-Q. Xu, M. Kianinia, A. Stacey, M. Toth, and I. Aharonovich, Electroluminescence from pure resonant states in hBN-based vertical tunneling junctions, Light Sci. Appl. 11, 186 (2022).
  72. C. M. Polley, H. Fedderwitz, T. Balasubramanian, A. A. Zakharov, R. Yakimova, O. Bäcke, J. Ekman, S. P. Dash, S. Kubatkin, and S. Lara-Avila, Bottom-up growth of monolayer honeycomb SiC, Phys. Rev. Lett. 130, 076203 (2023).
  73. Y. Da, R. Luo, B. Lei, W. Ji, and W. Zhou, Controlled fabrication of freestanding monolayer SiC by electron irradiation, Chin. Phys. B 33, 086802 (2024).
  74. E. Mokhov, V. Y. Davydov, A. Smirnov, and S. Nagaluk, Growth of hexagonal boron nitride (hBN) on silicon carbide substrates by the physical vapor transport method, Semiconductors 57, 483 (2023).
  75. J. Zhao, P. Ji, Y. Li, R. Li, K. Zhang, H. Tian, K. Yu, B. Bian, L. Hao, X. Xiao, et al., Ultrahigh-mobility semiconducting epitaxial graphene on silicon carbide, Nature (London) 625, 60 (2024).
  76. G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47, 558 (1993).
  77. P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50, 17953 (1994).
  78. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
  79. J. Heyd, G. E. Scuseria, and M. Ernzerhof, Hybrid functionals based on a screened Coulomb potential, J. Chem. Phys. 118, 8207 (2003).
  80. J. Heyd and G. E. Scuseria, Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional, J. Chem. Phys. 121, 1187 (2004).
  81. See Supplemental Material at http://link.aps.org/supplemental/10.1103/lymz-nlbf for validation of the vdW methods; machine-learning datasets; fundamental properties of hBN, SiC, and the hBN/SiC interface; molecular-dynamics trajectory analyses; transition-metal adsorption energy profiles; the influence of bulk SiC(0001) on defective hBN/SiC interfaces; and supplemental movies, which also includes Refs. [72, 76, 83, 84, 85, 120, 121].
  82. S. Grimme, S. Ehrlich, and L. Goerigk, Effect of the damping function in dispersion corrected density functional theory, J. Comput. Chem. 32, 1456 (2011).
  83. R. S. Pease, An X-ray study of boron nitride, Acta Crystallogr. 5, 356 (1952).
  84. W. Paszkowicz, J. Pelka, M. Knapp, T. Szyszko, and S. Podsiadlo, Lattice parameters and anisotropic thermal expansion of hexagonal boron nitride in the 10–297.5K temperature range, Appl. Phys. A 75, 431 (2002).
  85. V. Korsaks, Hexagonal boron nitride luminescence dependent on vacuum level and surrounding gases, Mater. Res. Bull. 70, 976 (2015).
  86. S. Chahal, T. K. Sahu, S. Kar, S. J. Ray, V. Biju, and P. Kumar, Transition metal-doped boron nitride atomic sheets with an engineered bandgap and magnetization, J. Phys. Chem. C 126, 21084 (2022).
  87. K. Zhang, Y. Feng, F. Wang, Z. Yang, and J. Wang, Two dimensional hexagonal boron nitride (2D-hBN): Synthesis, properties and applications, J. Mater. Chem. C 5, 11992 (2017).
  88. D. Chimene, D. L. Alge, and A. K. Gaharwar, Two-dimensional nanomaterials for biomedical applications: Emerging trends and future prospects, Adv. Mater. 27, 7261 (2015).
  89. A. Togo and I. Tanaka, First principles phonon calculations in materials science, Scr. Mater. 108, 1 (2015).
  90. Z. Fan, W. Chen, V. Vierimaa, and A. Harju, Efficient molecular dynamics simulations with many-body potentials on graphics processing units, Comput. Phys. Commun. 218, 10 (2017).
  91. P. Ying and Z. Fan, Combining the D3 dispersion correction with the neuroevolution machine-learned potential, J. Phys.: Condens. Matter 36, 125901 (2024).
  92. F. Mouhat and F. -X. Coudert, Necessary and sufficient elastic stability conditions in various crystal systems, Phys. Rev. B 90, 224104 (2014).
  93. W. Tang, E. Sanville, and G. Henkelman, A grid-based Bader analysis algorithm without lattice bias, J. Phys.: Condens. Matter 21, 084204 (2009).
  94. T. A. Manz, Seven confluence principles: A case study of standardized statistical analysis for 26 methods that assign net atomic charges in molecules, RSC Adv. 10, 44121 (2020).
  95. S. Mahmoudi, T. Gruene, C. Schröder, K. D. Ferjaoui, E. Fröjdh, A. Mozzanica, K. Takaba, A. Volkov, J. Maisriml, V. Paunović, et al., Experimental determination of partial charges with electron diffraction, Nature (London) 645, 88 (2025).
  96. Y.-C. Lin, A. Motoyama, S. Kretschmer, S. Ghaderzadeh, M. Ghorbani-Asl, Y. Araki, A. V. Krasheninnikov, H. Ago, and K. Suenaga, Polymorphic phases of metal chlorides in the confined 2D space of bilayer graphene, Adv. Mater. 33, 2105898 (2021).
  97. S. Back and S. Siahrostami, Noble metal supported hexagonal boron nitride for the oxygen reduction reaction: A DFT study, Nanoscale Adv. 1, 132 (2019).
  98. I. S. S. de Oliveira and R. H. Miwa, Organic molecules deposited on graphene: A computational investigation of self-assembly and electronic structure, J. Chem. Phys. 142, 044301 (2015).
  99. I. V. Vlassiouk, Y.-C. Wu, A. Puretzky, L. Liang, J. Lasseter, B. Dryzhakov, I. Gallagher, S. Ghosh, N. Lavrik, O. Dyck, A. R. Lupini, M. Checa, L. Collins, H. M. Meyer III, H. Zhao, F. Likhi, K. Xiao, I. Ivanov, D. Glasgow, A. Tselev, et al., Defect engineering in large-scale CVD-grown hexagonal boron nitride: Formation, spectroscopy, and spin relaxation dynamics, Small 22, e06874 (2026).
  100. M. Längle, B. M. Mayer, J. Madsen, D. Propst, A. Bo, C. Kofler, V. Hana, C. Mangler, T. Susi, and J. Kotakoski, Defect-engineering hexagonal boron nitride using low-energy Ar+ irradiation, arXiv:2404.07166.
  101. G. m. H. Thiering and A. Gali, Characterization of oxygen defects in diamond by means of density functional theory calculations, Phys. Rev. B 94, 125202 (2016).
  102. H. I. Rasool, C. Ophus, and A. Zettl, Atomic defects in two dimensional materials, Adv. Mater. 27, 5771 (2015).
  103. C. Linderälv, W. Wieczorek, and P. Erhart, Vibrational signatures for the identification of single-photon emitters in hexagonal boron nitride, Phys. Rev. B 103, 115421 (2021).
  104. L. Weston, D. Wickramaratne, M. Mackoit, A. Alkauskas, and C. G. Van de Walle, Native point defects and impurities in hexagonal boron nitride, Phys. Rev. B 97, 214104 (2018).
  105. N. Alem, O. V. Yazyev, C. Kisielowski, P. Denes, U. Dahmen, P. Hartel, M. Haider, M. Bischoff, B. Jiang, S. G. Louie, and A. Zettl, Probing the out-of-plane distortion of single point defects in atomically thin hexagonal boron nitride at the picometer scale, Phys. Rev. Lett. 106, 126102 (2011).
  106. H. Jónsson, G. Mills, and K. W. Jacobsen, Classical and Quantum Dynamics in Condensed Phase Simulations (World Scientific, Singapore, 1998), pp. 385–404.
  107. G. Mills, H. Jónsson, and G. K. Schenter, Reversible work transition state theory: Application to dissociative adsorption of hydrogen, Surf. Sci. 324, 305 (1995).
  108. Y. Zhou, Y. Jiang, Y. Ji, R. Lang, Y. Fang, and C.-D. Wu, The opportunities and challenges in single-atom catalysis, ChemCatChem 15, e202201176 (2023).
  109. D. Liu, X. Wan, T. Kong, W. Han, and Y. Xiong, Single-atom-based catalysts for photoelectrocatalysis: Challenges and opportunities, J. Mater. Chem. A 10, 5878 (2022).
  110. S. Weon, D. Huang, K. Rigby, C. Chu, X. Wu, and J.-H. Kim, Environmental materials beyond and below the nanoscale: Single-atom catalysts, ACS ES&T Eng. 1, 157 (2021).
  111. J. Wu, H. Shi, K. Li, and X. Guo, Advances and challenges of single-atom catalysts in environmental catalysis, Curr. Opin. Chem. Eng. 40, 100923 (2023).
  112. J. Dong, L. Gao, and Q. Fu, Hexagonal boron nitride meeting metal: A new opportunity and territory in heterogeneous catalysis, J. Phys. Chem. Lett. 12, 9608 (2021).
  113. H. Jeong, S. Shin, and H. Lee, Heterogeneous atomic catalysts overcoming the limitations of single-atom catalysts, ACS Nano 14, 14355 (2020).
  114. J. Li, C. Chen, L. Xu, Y. Zhang, W. Wei, E. Zhao, Y. Wu, and C. Chen, Challenges and perspectives of single-atom-based catalysts for electrochemical reactions, JACS Au 3, 736 (2023).
  115. Y. Zhang, C. Qin, L. Zhu, Y. Wang, and J. Cao, Adsorption of NO2, NO, NH3, and CO on noble metal (Rh, Pd, Ag, Ir, Pt, Au)-modified hexagonal boron nitride monolayers: A first-principles study, Langmuir 40, 1058 (2024).
  116. Y.-R. Lin, M. Franke, S. Parhizkar, M. Raths, V. Wen-zhe Yu, T.-L. Lee, S. Soubatch, V. Blum, F. Stefan Tautz, C. Kumpf, and F. C. Bocquet, Boron nitride on SiC(0001), Phys. Rev. Mater. 6, 064002 (2022).
  117. A. Biswas, R. Xu, G. A. Alvarez, J. Zhang, J. Christiansen-Salameh, A. B. Puthirath, K. Burns, J. A. Hachtel, T. Li, S. A. Iyengar, T. Gray, C. Li, X. Zhang, H. Kannan, J. Elkins, T. S. Pieshkov, R. Vajtai, A. G. Birdwell, M. R. Neupane, E. J. Garratt, et al., Non-linear optics at twist interfaces in h-BN/SiC heterostructures, Adv. Mater. 35, 2304624 (2023).
  118. S. Lu, P. Shen, H. Zhang, G. Liu, B. Guo, Y. Cai, H. Chen, F. Xu, T. Zheng, F. Xu, et al., Towards n-type conductivity in hexagonal boron nitride, Nat. Commun. 13, 3109 (2022).
  119. A. Hashemi, Stabilisation of hBn/SiC heterostructures with vacancies and transition-metal atoms (v.1), Zenodo (2025), doi: 10.5281/zenodo.17102508.
  120. C. Freysoldt and J. Neugebauer, First-principles calculations for charged defects at surfaces, interfaces, and two-dimensional materials in the presence of electric fields, Phys. Rev. B 97, 205425 (2018).
  121. R. Nelson, C. Ertural, J. George, V. L. Deringer, G. Hautier, and R. Dronskowski, LOBSTER: Local orbital projections, atomic charges, and chemical-bonding analysis from projector-augmented-wave-based density-functional theory, J. Comput. Chem. 41, 1931 (2020).

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Phys. Rev. Materials 10, 045801– Published 13 April, 2026
  • Received 14 September 2025
  • Revised 11 January 2026
  • Accepted 16 March 2026
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