Ultrathin nanosheets of Mn₃O₄: A new two-dimensional ferromagnetic material with strong magnetocrystalline anisotropy

Abstract

Two-dimensional (2D) materials with robust ferromagnetism have played a key role in realizing nextgeneration spin-electronic devices, but many challenges remain, especially the lack of intrinsic ferromagnetic behavior in almost all 2D materials. Here, we highlight ultrathin Mn₃O₄ nanosheets as a new 2D ferromagnetic material with strong magnetocrystalline anisotropy. Magnetic measurements along the in-plane and out-of-plane directions confirm that the out-of-plane direction is the easy axis. The 2D-confined environment and Rashba-type spin-orbit coupling are thought to be responsible for the magnetocrystalline anisotropy. The robust ferromagnetism in 2D Mn₃O₄ nanosheets with magnetocrystalline anisotropy not only paves a new way for realizing the intrinsic ferromagnetic behavior in 2D materials but also provides a novel candidate for building next-generation spin-electronic devices.

Keywords

2D ferromagnetic material / topochemical conversion / magnetocrystalline anisotropy

References

[1] 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)

[2] Q. H. Wang, K. Kalantarzadeh, A. Kis, J. N. Coleman, and M. S. Strano, Electronicsand optoelectronics of twodimensional transition metal dichalcogenides, Nat. Nanotechnol. 7(11), 699 (2012)

[3] P. Ajayan, P. Kim, and K. Banerjee, Two-dimensional van der Waals materials, Phys. Today 69(9), 38 (2016)

[4] S. Rudin and D. C. Mattis, Absence of ferromagnetism in the two-dimensional Hubbard model, Phys. Lett. A 110(5), 273 (1985)

[5] K. Xu, X. Li, P. Chen, D. Zhou, C. Wu, Y. Guo, L. Zhang, J. Zhao, X. Wu, and Y. Xie, Hydrogen dangling bonds induce ferromagnetism in two-dimensional metalfree graphitic-C₃N₄ nanosheets, Chem. Sci. 6(1), 283 (2015)

[6] X. Zhu, Y. Guo, H. Cheng, J. Dai, X. An, J. Zhao, K. Tian, S. Wei, X. Cheng Zeng, C. Wu, and Y. Xie, Signature of coexistence of superconductivity and ferromagnetism in two-dimensional NbSe₂ triggered by surface molecular adsorption, Nat. Commun. 7, 11210 (2016)

[7] L. Cai, J. He, Q. Liu, T. Yao, L. Chen, W. Yan, F. Hu, Y. Jiang, Y. Zhao, T. Hu, Z. Sun, and S. Wei, Vacancy-induced ferromagnetism of MoS₂ nanosheets, J. Am. Chem. Soc. 137(7), 2622 (2015)

[8] B. Li, T. Xing, M. Zhong, L. Huang, N. Lei, J. Zhang, J. Li, and Z. Wei, A two-dimensional Fe-doped SnS₂ magnetic semiconductor, Nat. Commun. 8(1), 1958 (2017)

[9] 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)

[10] 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)

[11] J. L. Miller, Ancient clues help quantify modern methane, Phys. Today 70, 16 (2017)

[12] H. T. Jeng and G. Y. Guo, First-principles investigations of the electronic structure and magnetocrystalline anisotropy in strained magnetite Fe₃O₄, Phys. Rev. B 65(9), 094429 (2002)

[13] K. Dwight and N. Menyuk, Magnetic properties of and the canted spin problem, Phys. Rev. 119(5), 1470 (1960)

[14] T. Jeng and G. Y. Guo, First-principles investigations of the electronic structure and magnetocrystalline anisotropy in strained magnetite Fe₃O₄, Phys. Rev. B 65(9), 094429 (2002)

[15] X. Peng, Y. Guo, Q. Yin, J. Wu, J. Zhao, C. Wang, S. Tao, W. Chu, C. Wu, and Y. Xie, Double-exchange effect in two-dimensional MnO₂ nanomaterials, J. Am. Chem. Soc. 139(14), 5242 (2017)

[16] W. Cheng, J. He, T. Yao, Z. Sun, Y. Jiang, Q. Liu, S. Jiang, F. Hu, Z. Xie, B. He, W. Yan, and S. Wei, Half-unit-cell α-Fe₂O₃ semiconductor nanosheets with intrinsic and robust ferromagnetism, J. Am. Chem. Soc. 136(29), 10393 (2014)

[17] Y. Sun, Q. Liu, S. Gao, H. Cheng, F. Lei, Z. Sun, Y. Jiang, H. Su, S. Wei, and Y. Xie, Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation, Nat. Commun. 4, 2899 (2013)

[18] L. Liang, J. Zhang, Y. Zhou, J. Xie, X. Zhang, M. Guan, B. Pan, and Y. Xie, High-performance flexible electrochromic device based on facile semiconductorto-metal transition realized by WO₃·2H₂O ultrathin nanosheets, Sci. Rep. 3(1), 1936 (2013)

[19] G. Srinivasan and M. S. Seehra, Magnetic properties of Mn₃O₄ and a solution of the canted-spin problem, Phys. Rev. B 28(1), 1 (1983)

[20] L. Ren, S. Wu, M. Yang, W. Zhou, and S. Li, Magnetic properties of Mn₃O₄ film under compressive stress grown on MgAl₂O₄ (001) by molecular beam epitaxy, J. Appl. Phys. 114(5), 053907 (2013)

[21] Y. Yafet and C. Kittel, Antiferromagnetic arrangements in ferrites, Phys. Rev. 87(2), 290 (1952)

[22] L. Ren, M. Yang, W. Zhou, S. Wu, and S. Li, Influence of stress and defect on magnetic properties of Mn3O4 films grown on MgAl₂O₄ (001) by molecular beam epitaxy, J. Phys. Chem. C 118(1), 243 (2014)

[23] L. Ren, W. Zhou, Y. Wang, M. Meng, S. Wu, and S. Li, Magnetic properties of Mn₃O₄ film with a coexistence of two preferential orientations, J. Appl. Phys. 116(2), 023906 (2014)

[24] U. H. Pi, K. Won Kim, J. Y. Bae, S. C. Lee, Y. J. Cho, K. S. Kim, and S. Seo, Tilting of the spin orientation induced by Rashba effect in ferromagnetic metal layer, Appl. Phys. Lett. 97(16), 162507 (2010)

[25] H. Y. Hwang, Y. Iwasa, M. Kawasaki, B. Keimer, N. Nagaosa, and Y. Tokura, Emergent phenomena at oxide interfaces, Nat. Mater. 11(2), 103 (2012)

RIGHTS & PERMISSIONS

2018 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature