First-principles investigation of two-dimensional iron molybdenum nitride: A double transition-metal cousin of MoSi₂N₄(MoN) monolayer with distinctive electronic and topological properties

Abstract

As the homologous compounds of MoSi₂N₄, the MoSi₂N₄(MoN)_n monolayers have been synthesized in a recent experiment. These systems consist of homogeneous metal nitride multilayers sandwiched between two SiN surfaces, which extends the septuple-atomic-layer MSi₂N₄ system to ultra-thick MSi₂N₄(MN)_n forms. In this paper, we perform a first-principles study on the MoSi₂N₄(FeN) monolayer, which is constructed by iron molybdenum nitride intercalated into the SiN layers. As a cousin of MoSi₂N₄(MoN), this double transition-metal system exhibits robust structural stability from the energetic, mechanical, dynamical and thermal perspectives. Different from the MoSi₂N₄(MoN) one, the MoSi₂N₄(FeN) monolayer possesses intrinsic ferromagnetism and presents a bipolar magnetic semiconducting behaviour. The ferromagnetism can be further enhanced by the surface hydrogenation, which raises the Curie temperature to 310 K around room temperature. More interestingly, the hydrogenated MoSi₂N₄(FeN) monolayer exhibits a quantum anomalous Hall (QAH) insulating behaviour with a sizeable nontrivial band gap of 0.23 eV. The nontrivial topological character can be well described by a two-band \mathit{k}\cdot \mathit{p} model, confirming a non-zero Chern number of C=1. Similar bipolar magnetic semiconducting feature and hydrogenation-induced QAH state are also present in the WSi₂N₄(FeN) monolayer. Our study demonstrates that the double transition-metal MSi₂N₄({\mathrm{M}}^{\prime }\mathrm{N}) system will be a fertile platform to achieve fascinating spintronic and topological properties.

Graphical abstract

Keywords

quantum anomalous Hall state / MA₂Z₄(M′Z) family / first-principles / double transition-metal nitride

References

[1] Y. L. Hong, Z. Liu, L. Wang, T. Zhou, W. Ma, C. Xu, S. Feng, L. Chen, M. L. Chen, D. M. Sun, X. Q. Chen, H. M. Cheng, and W. Ren, Chemical vapor deposition of layered two-dimensional MoSi₂N₄ materials, Science 369(6504), 670 (2020)

[2] Y. Yin, Q. Gong, M. Yi, and W. Guo, Emerging versatile two-dimensional MoSi₂N₄ family, Adv. Funct. Mater. 33(26), 2214050 (2023)

[3] C.C. ThoS. D. GuoS.J. LiangW.L. OngC.S. Lau L.CaoG. WangY.S. Ang, MA₂Z₄ family heterostructures: Promises and prospects, Appl. Phys. Rev. 10(4), 041307 (2023)

[4] D. Huang, F. Liang, R. Guo, D. Lu, J. Wang, H. Yu, and H. Zhang, MoSi₂N₄: A 2D regime with strong exciton–phonon coupling, Adv. Opt. Mater. 10(9), 2102612 (2022)

[5] K. S. Novoselov, Discovery of 2D van der Waals layered MoSi₂N₄ family, Natl. Sci. Rev. 7(12), 1842 (2020)

[6] B. Mortazavi, B. Javvaji, F. Shojaei, T. Rabczuk, A. V. Shapeev, and X. Zhuang, Exceptional piezoelectricity, high thermal conductivity and stiffness and promising photocatalysis in two-dimensional MoSi₂N₄ family confirmed by first-principles, Nano Energy 82, 105716 (2021)

[7] S. Li, W. Wu, X. Feng, S. Guan, W. Feng, Y. Yao, and S. A. Yang, Valley-dependent properties of monolayer MoSi₂N₄, WSi₂N₄, and MoSi₂As₄, Phys. Rev. B 102(23), 235435 (2020)

[8] C. Yang, Z. Song, X. Sun, and J. Lu, Valley pseudospin in monolayer MoSi₂N₄ and MoSi₂As₄, Phys. Rev. B 103(3), 035308 (2021)

[9] Y. Wu, Z. Tang, W. Xia, W. Gao, F. Jia, Y. Zhang, W. Zhu, W. Zhang, and P. Zhang, Prediction of protected band edge states and dielectric tunable quasiparticle and excitonic properties of monolayer MoSi₂N₄, npj Comput. Mater. 8(1), 129 (2022)

[10] J. Yu, J. Zhou, X. Wan, and Q. Li, High intrinsic lattice thermal conductivity in monolayer MoSi₂N₄, New J. Phys. 23(3), 033005 (2021)

[11] X. Wang, W. Ju, D. Wang, X. Li, and J. Wan, Flexible MA₂Z₄ (M = Mo, W; A = Si, Ge and Z = N, P, As) monolayers with outstanding mechanical, dynamical, electronic, and piezoelectric properties and anomalous dynamic polarization, Phys. Chem. Chem. Phys. 25(27), 18247 (2023)

[12] A. Priydarshi, Y. S. Chauhan, S. Bhowmick, and A. Agarwal, Large and anisotropic carrier mobility in monolayers of the MA₂Z₄ series (M = Cr, Mo, W; A = Si, Ge; and Z = N, P), Nanoscale 14(33), 11988 (2022)

[13] L. Wang, Y. Shi, M. Liu, A. Zhang, Y. L. Hong, R. Li, Q. Gao, M. Chen, W. Ren, H. M. Cheng, Y. Li, and X. Q. Chen, Intercalated architecture of MA₂Z₄ family layered van der Waals materials with emerging topological, magnetic and superconducting properties, Nat. Commun. 12(1), 2361 (2021)

[14] Y. Ding and Y. Wang, Computational exploration of stable 4d/5d transition-metal MSi₂N₄ (M = Y−Cd and Hf−Hg) nanosheets and their versatile electronic and magnetic properties, J. Phys. Chem. C 125(35), 19580 (2021)

[15] Y. T. Ren, L. Hu, Y. T. Chen, Y. J. Hu, J. L. Wang, P. L. Gong, H. Zhang, L. Huang, and X. Q. Shi, Two-dimensional MSi₂N₄ monolayers and van der Waals heterostructures: Promising spintronic properties and band alignments, Phys. Rev. Mater. 6(6), 064006 (2022)

[16] Y. Wang, D. Legut, X. Liu, Y. Li, C. Li, Y. Sun, R. Zhang, and Q. Zhang, Mott transition and superexchange mechanism in magnetically doped XSi₂N₄ caused by large 3d orbital onsite coulomb interaction, Phys. Rev. B 106(10), 104421 (2022)

[17] Z. An, L. Lv, Y. Su, Y. Jiang, and Z. Guan, Carrier doping modulates the magnetoelectronic and magnetic anisotropic properties of two-dimensional MSi₂N₄ (M = Cr, Mn, Fe, and Co) monolayers, Phys. Chem. Chem. Phys. 26(5), 4208 (2024)

[18] Q. Cui, Y. Zhu, J. Liang, P. Cui, and H. Yang, Spin-valley coupling in a two-dimensional VSi₂N₄ monolayer, Phys. Rev. B 103(8), 085421 (2021)

[19] S. Li, Q. Wang, C. Zhang, P. Guo, and S. A. Yang, Correlation-driven topological and valley states in monolayer VSi₂P₄, Phys. Rev. B 104(8), 085149 (2021)

[20] Y. Wang and Y. Ding, Switchable valley polarization and quantum anomalous Hall state in the VN₂X₂Y₂ nanosheets (X = group-III and Y = group-VI elements), Appl. Phys. Lett. 119(19), 193101 (2021)

[21] P. Liu, S. Liu, M. Jia, H. Yin, G. Zhang, F. Ren, B. Wang, and C. Liu, Strain-driven valley states and phase transitions in Janus VSiGeN₄ monolayer, Appl. Phys. Lett. 121(6), 063103 (2022)

[22] P. Li, X. Yang, Q. S. Jiang, Y. Z. Wu, and W. Xun, Built-in electric field and strain tunable valley-related multiple topological phase transitions in VSiXN₄ (X = C, Si, Ge, Sn, Pb) monolayers, Phys. Rev. Mater. 7(6), 064002 (2023)

[23] K. Jia, X. J. Dong, S. S. Li, W. X. Ji, and C. W. Zhang, Strain-engineering induced topological phase transitions and multiple valley states in Janus monolayer VCSiN₄, J. Mater. Chem. C 11(30), 10359 (2023)

[24] Z. Gao, Y. He, and K. Xiong, Two-dimensional Janus SVAN₂ (A = Si, Ge) monolayers with intrinsic semiconductor character and room temperature ferromagnetism: Tunable electronic properties via strain and an electric field, Dalton Trans. 52(46), 17416 (2023)

[25] X. Zhou, R. W. Zhang, Z. Zhang, W. Feng, Y. Mokrousov, and Y. Yao, Sign-reversible valley-dependent berry phase effects in 2D valley-half-semiconductors, npj Comput. Mater. 7(1), 160 (2021)

[26] C. Z. Chang, C. X. Liu, and A. H. MacDonald, Colloquium: Quantum anomalous Hall effect, Rev. Mod. Phys. 95(1), 011002 (2023)

[27] K. Wang, Y. Li, H. Mei, P. Li, and Z. X. Guo, Quantum anomalous Hall and valley quantum anomalous Hall effects in two-dimensional d₀ orbital XY monolayers, Phys. Rev. Mater. 6(4), 044202 (2022)

[28] P. Li, Prediction of intrinsic two dimensional ferromagnetism realized quantum anomalous Hall effect, Phys. Chem. Chem. Phys. 21(12), 6712 (2019)

[29] H. P. Wang, W. Luo, and H. J. Xiang, Prediction of high-temperature quantum anomalous Hall effect in two-dimensional transition-metal oxides, Phys. Rev. B 95(12), 125430 (2017)

[30] P. Li, X. Li, W. Zhao, H. Chen, M. X. Chen, Z. X. Guo, J. Feng, X. G. Gong, and A. H. MacDonald, Topological Dirac states beyond π-orbitals for silicene on SiC(0001) surface, Nano Lett. 17(10), 6195 (2017)

[31] Y. Ding and Y. Wang, Two-dimensional T′ MA ₂N₄ (M = Mo/W, A = Si/Ge) nanosheets: First-principles insights into the structural stability, electronic property and catalytic performance for hydrogen evolution reaction, Appl. Surf. Sci. 627, 157256 (2023)

[32] R. Islam, R. Verma, B. Ghosh, Z. Muhammad, A. Bansil, C. Autieri, and B. Singh, Switchable large-gap quantum spin Hall state in the two-dimensional MSi₂Z₄ class of materials, Phys. Rev. B 106(24), 245149 (2022)

[33] R. Islam, G. Hussain, R. Verma, M. S. Talezadehlari, Z. Muhammad, B. Singh, and C. Autieri, Fast electrically switchable large gap quantum spin Hall states in MGe₂Z₄, Adv. Electron. Mater. 9(8), 2300156 (2023)

[34] X. Wei, B. Zhao, J. Zhang, Y. Xue, Y. Li, and Z. Yang, Chern insulators without band inversion in MoS₂ monolayers with 3d adatoms, Phys. Rev. B 95(7), 075419 (2017)

[35] X. Deng, H. Yang, S. Qi, X. Xu, and Z. Qiao, Quantum anomalous Hall effect and giant Rashba spin‒orbit splitting in graphene system Co-doped with boron and 5d transition-metal atoms, Front. Phys. 13(5), 137308 (2018)

[36] M. A. Abdelati, A. A. Maarouf, and M. M. Fadlallah, Substitutional transition metal doping in MoSi₂N₄ monolayer: Structural, electronic and magnetic properties, Phys. Chem. Chem. Phys. 24(5), 3035 (2022)

[37] Y. Wang, G. Wang, M. Huang, Z. Luo, J. Wang, Z. Ding, X. Guo, and X. Liu, Electrocatalytic activity of MoSi₂N₄ monolayers decorated with single transition metal atoms: A computational study, Nanotechnology 34(24), 245705 (2023)

[38] Z. Liu, L. Wang, Y. L. Hong, X. Q. Chen, H. M. Cheng, and W. Ren, Two-dimensional superconducting MoSi₂N₄(MoN)_4n homologous compounds, Natl. Sci. Rev. 10(4), nwac273 (2023)

[39] Y. Wang and Y. Ding, Large-gap quantum spin hall state in double-transition-metal homologous compounds of WSi₂N₄: A first-principles study, Phys. Status Solidi Rapid Res. Lett. 18(3), 2300376 (2024)

[40] A. Miura, K. Tadanaga, E. Magome, C. Moriyoshi, Y. Kuroiwa, T. Takahiro, N. Kumada, and Octahedral coordination preferences in Nb-, Ta-, and W-based ABX₂ layered oxides, oxynitrides, and nitrides, J. Solid State Chem. 229, 272 (2015)

[41] E. Enriquez, Y. Zhang, A. Chen, Z. Bi, Y. Wang, E. Fu, Z. Harrell, X. Lu, P. Dowden, H. Wang, C. Chen, and Q. Jia, Epitaxial growth and physical properties of ternary nitride thin films by polymer-assisted deposition, Appl. Phys. Lett. 109(8), 081907 (2016)

[42] G. Kresse and J. Furthmuller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6(1), 15 (1996)

[43] G. C. Moore, M. K. Horton, E. Linscott, A. M. Ganose, M. Siron, D. D. O’Regan, and K. A. Persson, High-throughput determination of Hubbard U and Hund J values for transition metal oxides via the linear response formalism, Phys. Rev. Mater. 8(1), 014409 (2024)

[44] R. Panda and N. Gajbhiye, Chemical synthesis and magnetic properties of nanocrystalline FeMoN₂, J. Cryst. Growth 191(1−2), 92 (1998)

[45] A. Togo and I. Tanaka, First principles phonon calculations in materials science, Scr. Mater. 108, 1 (2015)

[46] F. Mouhat and F. M. C. X. Coudert, Necessary and sufficient elastic stability conditions in various crystal systems, Phys. Rev. B 90(22), 224104 (2014)

[47] X. Li, X. Wu, and J. Yang, Half-metallicity in MnPSe₃ exfoliated nanosheet with carrier doping, J. Am. Chem. Soc. 136(31), 11065 (2014)

[48] C. C. Tho, X. Feng, L. Cao, G. Wang, S. J. Liang, C. S. Lau, S. D. Guo, and Y. S. Ang, Ultrathick MA₂N₄(M′ N) intercalated monolayers with sublayer-protected Fermi surface conduction states: Interconnect and metal contact applications, Adv. Phys. Res. 2300156, 2300156 (2024)

[49] J. B. Goodenough, Theory of the role of covalence in the perovskite-type manganites [La,m(II)]MnO₃, Phys. Rev. 100(2), 564 (1955)

[50] Y. Wang, X. Xu, W. Ji, S. Li, Y. Li, and X. Zhao, Exploitable magnetic anisotropy and half-metallicity controls in multiferroic van der Waals heterostructure, npj Comput. Mater. 9(1), 223 (2023)

[51] C. Liu, G. Zhao, T. Hu, Y. Chen, S. Cao, L. Bellaiche, and W. Ren, Jahn‒Teller effect, and orbital order in the two-dimensional monolayer perovskite Rb₂CuCl₄, Phys. Rev. B 104, L241105 (2021)

[52] M. R. K. Akanda and R. K. Lake, Magnetic properties of NbSi₂N₄, VSi₂N₄, and VSi₂P₄ monolayers, Appl. Phys. Lett. 119(5), 052402 (2021)

[53] T. M. Henderson, J. Paier, and G. E. Scuseria, Accurate treatment of solids with the HSE screened hybrid, Phys. Status Solidi B 248(4), 767 (2011)

[54] J.LiX.Li J.Yang, A review of bipolar magnetic semiconductors from theoretical aspects, Fund. Res. 2(4), 511 (2022)

[55] T. A. Manz and N. G. Limas, Introducing ddec6 atomic population analysis. Part 1. Charge partitioning theory and methodology, RSC Adv. 6(53), 47771 (2016)

[56] A. S. Botana and M. R. Norman, Electronic structure and magnetism of transition metal dihalides: Bulk to monolayer, Phys. Rev. Mater. 3(4), 044001 (2019)

[57] T. Barnowsky, S. Curtarolo, A. V. Krasheninnikov, T. Heine, and R. Friedrich, Magnetic state control of non-van der Waals 2D materials by hydrogenation, Nano Lett. 24(13), 3874 (2024)

[58] K. Wang, K. Ren, Y. Hou, Y. Cheng, and G. Zhang, Physical insights into enhancing magnetic stability of 2D magnets, J. Appl. Phys. 133(11), 110902 (2023)

[59] Y. Wang and Y. Ding, Tunable structural phases and electronic properties of group V MSi₂N₄ (M = V, Nb, Ta) nanosheets via surface hydrogenation: A first-principles study, J. Mater. Chem. C 11(48), 17034 (2023)

[60] Y. Wu, L. Deng, J. Tong, X. Yin, F. Tian, G. Qin, and X. Zhang, Ferrovalley and topological phase transition behavior in monolayer Ru(OH)₂, J. Mater. Chem. C 11(40), 13714 (2023)

[61] X. Zhang, Q. Lu, W. Liu, W. Niu, J. Sun, J. Cook, M. Vaninger, P. F. Miceli, D. J. Singh, S. W. Lian, T. R. Chang, X. He, J. Du, L. He, R. Zhang, G. Bian, and Y. Xu, Room-temperature intrinsic ferromagnetism in epitaxial CrTe₂ ultrathin films, Nat. Commun. 12(1), 2492 (2021)

[62] H. R. Fuh, C. R. Chang, Y. K. Wang, R. F. L. Evans, R. W. Chantrell, and H. T. Jeng, New type single-layer magnetic semiconductor in transition-metal dichalcogenides VX₂ (X = S, Se and Te), Sci. Rep. 6(1), 32625 (2016)

[63] B. Huang, G. Clark, E. Navarro-Moratalla, D. R. Klein, R. Cheng, K. L. Seyler, D. Zhong, E. Schmidgall, M. A. McGuire, D. H. Cobden, W. Yao, D. Xiao, P. Jarillo-Herrero, and X. Xu, Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit, Nature 546(7657), 270 (2017)

[64] C. Gong, L. Li, Z. Li, H. Ji, A. Stern, Y. Xia, T. Cao, W. Bao, C. Wang, Y. Wang, Z. Q. Qiu, R. J. Cava, S. G. Louie, J. Xia, and X. Zhang, Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals, Nature 546(7657), 265 (2017)

[65] Y. Deng, Y. Yu, Y. Song, J. Zhang, N. Z. Wang, Z. Sun, Y. Yi, Y. Z. Wu, S. Wu, J. Zhu, J. Wang, X. H. Chen, and Y. Zhang, Gate-tunable room-temperature ferromagnetism in two-dimensional Fe₃GeTe₂, Nature 563(7729), 94 (2018)

[66] J. Gong, G. Ding, C. Xie, W. Wang, Y. Liu, G. Zhang, and X. Wang, Genuine Dirac half-metals in two-dimensions, Adv. Sci. 11, 2307297 (2024)

[67] X. Wang, X. P. Li, J. Li, C. Xie, J. Wang, H. Yuan, W. Wang, Z. Cheng, Z. M. Yu, and G. Zhang, Magnetic second-order topological insulator: An experimentally feasible 2D CrSiTe₃, Adv. Funct. Mater. 33(49), 2304499 (2023)

[68] Y. Yao, L. Kleinman, A. H. MacDonald, J. Sinova, T. Jungwirth, D. S. Wang, E. Wang, and Q. Niu, First principles calculation of anomalous Hall conductivity in ferromagnetic bcc Fe, Phys. Rev. Lett. 92(3), 037204 (2004)

[69] Y. Yao and Z. Fang, Sign changes of intrinsic spin Hall effect in semiconductors and simple metals: First-principles calculations, Phys. Rev. Lett. 95(15), 156601 (2005)

[70] S. J. Zhang, C. W. Zhang, S. F. Zhang, W. X. Ji, P. Li, P. J. Wang, S. S. Li, and S. S. Yan, Intrinsic Dirac half-metal and quantum anomalous Hall phase in a hexagonal metal-oxide lattice, Phys. Rev. B 96(20), 205433 (2017)

[71] X. Zhu, Y. Chen, Z. Liu, Y. Han, and Z. Qiao, Valley-polarized quantum anomalous Hall effect in van der Waals heterostructures based on monolayer jacutingaite family materials, Front. Phys. 18(2), 23302 (2023)

[72] X. Kong, L. Li, L. Liang, F. M. Peeters, and X. J. Liu, The magnetic, electronic, and light-induced topological properties in two-dimensional hexagonal FeX₂ (X = Cl, Br, I) monolayers, Appl. Phys. Lett. 116(19), 192404 (2020)

[73] H. Sun, S. S. Li, W. X. Ji, and C. W. Zhang, Valley-dependent topological phase transition and quantum anomalous valley Hall effect in single-layer RuClBr, Phys. Rev. B 105(19), 195112 (2022)

[74] Q. F. Liang, R. Yu, J. Zhou, and X. Hu, Topological states of non-Dirac electrons on a triangular lattice, Phys. Rev. B 93(3), 035135 (2016)

[75] C. Si, K. H. Jin, J. Zhou, Z. Sun, and F. Liu, Large-gap quantum spin Hall state in MXenes: d-band topological order in a triangular lattice, Nano Lett. 16(10), 6584 (2016)

[76] Z. Zhang, L. Zhao, and J. Shi, Mechanics and strategies for wrinkling suppression: A review, Front. Mech. Eng. 8, 910415 (2022)

[77] S. Yang, Y. Chen, and C. Jiang, Strain engineering of two-dimensional materials: Methods, properties, and applications, InfoMat 3(4), 397 (2021)

[78] J. Wang, L. He, Y. Zhang, H. Nong, S. Li, Q. Wu, J. Tan, and B. Liu, Locally strained 2D materials: Preparation, properties, and applications, Adv. Mater. 36(23), 2314145 (2024)

Declarations

The authors declare that they have no competing interests and there are no conflicts.

Electronic supplementary materials

The online version contains supplementary material available at https://doi.org/10.1007/s11467-024-1431-6 and https://journal.hep.com.cn/fop/EN/10.1007/s11467-024-1431-6.

Acknowledgements

The authors acknowledge the support from the National Natural Science Foundation of China (No. 11774312).

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