Vacancy Induced Magnetism in Tetragonal Structure ZrO₂ Based on First-Principles Study

Abstract:

Tetragonal zirconia (t-ZrO₂) has broad applications for structural ceramics, such as solid oxide fuel cells, electrolysis materials, membranes, and biomedical applications. However, its electronics and magnetics properties are rarely well studied. We carried out spin-polarized calculations to understand the vacancy characteristics in t-ZrO₂. We apply neutral single Zr vacancy (V_Zr) and O vacancy (V_O) for supercell calculations up to 108 atoms. The calculated band gap of t-ZrO₂ is 3.81 eV, which becomes a narrowing band gap by V_Zr. We find that both vacancies systems induce outward relaxations of atoms near vacancies, creating lower symmetry from pristine D_4h to D_2d and C_2v for V_Zr and V_O cases, respectively. The calculated magnetic moment V_Zr is 4 mB due to four electrons of the valence band being occupied in the majority state. Four oxygen electrons of p-orbitals dominate the spin densities near V_Zr. In contrast, the magnetic moment in the case of V_O is 0 µB. Thus, since they have a high magnetic moment in the case of V_Zr, t-ZrO₂ is potentially used as material for diluted magnetic semiconductors.

• Periodical: Key Engineering Materials (Volume 1015)
• Pages: 11-16
• DOI: https://doi.org/10.4028/p-EZPwg0
• Online since: June 2025
• Authors: Muhammad Yusuf Hakim Widianto*, Retno Asih, Suminar Pratapa
• Keywords: Diluted Magnetic Semiconductors, First-Principles, Tetragonal ZrO₂, Vacancy

References

[1] T. Dietl, H. Ohno, F. Matsukura, J. Cibert, and D. Ferrand, Science 287, 1019 (2000).

[2] H. Ohno, J. Appl. Phys. 113, 136509 (2013).

[3] Y. Ogawa, H. Akinaga, F. Takano, T. Arima, and Y. Tokura, J. Phys. Soc. Jpn. 73, 2389 (2004).

[4] J. M. D. Coey, Solid State Mater. Sci. 10, 83 (2006).

[5] K. P. McKenna and D. M. Ramo, Phys. Rev. B 92, 205124 (2015).

[6] N. H. Hong, J. Sakai, N. Poirot, and V. Brizé, Phys. Rev. B 73, 132404 (2006).

[7] N. H. Hong, N. Poirot, and J. Sakai, Phys. Rev. B 77, 033205 (2008).

[8] K. Potzger, S. Zhou, J. Grenzer, M. Helm, and J. Fassbender, Appl. Phys. Lett. 92, 182504 (2008).

DOI: 10.1063/1.2938419

[9] S. M. Evans, N. C. Giles, L. E. Halliburton, and L. A. Kappers, J. Appl. Phys. 103, 043710 (2008).

[10] Y. Liu, L. Jiang, G. Wang, S. Zuo, W. Wang, and X. Chen, Appl. Phys. Lett. 100, 122401 (2012).

[11] P. Dev, Y. Xue, and P. Zhang, Phys. Rev. Lett. 100, 117204 (2008).

[12] C. Madhu, A. Sundaresan, and C. N. R. Rao, Phys. Rev. B 77, 201306(R) (2008).

[13] M. Y. H. Widianto, H. P. Kadarisman, A. M. Yatmeidhy, and M. Saito, Japanese Journal of Applied Physics 59, 071001 (2020).

[14] O. Volnianska and P. Boguslawski, Phys. Rev. B 83, 205205 (2011).

[15] O. Volnianska and P. Boguslawski, J. Phys.: Condens. Matter 22, 073202 (2010).

[16] P. Dev and P. Zhang, Phys. Rev. B 81, 085207 (2010).

[17] F. Máca, J. Kudrnovský, V. Drchal, and G. Bouzerar, Applied Physics Letters 92, 212503 (2008).

DOI: 10.1063/1.2936858

[18] M. Boujnah, H. Labrim, K. Allam, et al., J. Supercond. Nov. Magn. 26, 2429–2434 (2013).

[19] T. Archer, C. D. Pemmaraju, and S. Sanvito, J. Magn. Magn. Mater. 316, e188 (2007).

[20] T. Yamasaki, A. Kuroda, T. Kato, J. Nara, J. Koga, T. Uda, K. Minami, and T. Ohno, Computer Physics Communications 244, 264 (2019).

DOI: 10.1016/j.cpc.2019.04.008

[21] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).

[22] Musyarofah, N. D. Lestari, R. Nurlaila, N. F. Muwwaqor, Triwikantoro, and S. Pratapa, Ceramics International 45, 6639 (2019).

DOI: 10.1016/j.ceramint.2018.12.152

[23] M. Y. H. Widianto and M. Saito, Japanese Journal of Applied Physics 61, 035503 (2022).

[24] X. Lu, K. Liang, S. Gu, Y. Zheng, and H. Fang, Journal of Materials Science 32, 6653–6656 (1997).

[25] H. Kwak and S. Chaudhuri, Surface Science 604, 2116 (2010).

[26] S. Fabris, A. T. Paxton, and M. W. Finnis, Acta Materialia 50, 5171 (2002).

[27] Q. Wang, Q. Sun, G. Chen, Y. Kawazoe, and P. Jena, Phys. Rev. B 77, 205411 (2008).

[28] D. Y. Pratama, B. Hariyanto, S. Y. Purwaningsih, A. M. Hatta, and S. Pratapa, Physica Scripta 99, 085971 (2024).

DOI: 10.1088/1402-4896/ad6246

[29] C. C.W. K.-Gamage and F. Ramezanipour, J. Phys. Chem. Sol. 171, 111013 (2022).

[30] K. Kliemt, J.D. Reusch, M. Bolte, and C. Krellner, J. Mag. Mag. Mat. 552, 169199 (2022).

[31] S. Pattanaik, D. K. Mishra, M. K. Sharma and R. Chatterjee, Inor. Chem. Commun. 118, 1080 (2020).