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The electronic structures and optical properties of the monoclinic ZrO2 (m-ZrO2) are investigated by means of first-principles local density approximation (LDA) + U approach. Without on-site Coulomb interactions, the band gap of m-ZrO2 is 3.60 eV, much lower than the experimental value (5.8 eV). By introducing the Coulomb interactions of 4d orbitals on Zr atom (Ud) and of 2p orbitals on O atom (Up), we can reproduce the experimental value of the band gap. The calculated dielectric function of m-ZrO2 exhibits a small shoulder at the edge of the band gap in its imaginary part, while in the tetragonal ZrO2 and cubic ZrO2 it is absent, which is consistent with the experimental observations. The origin of the shoulder is attributed to the difference of electronic structures near the edge of the valence and conduction bands.


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Electronic structures and optical properties of monoclinic ZrO2 studied by first-principles local density approximation + U approach

Show Author's information Jinping LIa,c( )Songhe MENGaJiahong NIUaHantao LUb,c
Center for Composite Materials and Structures, Harbin Institute of Technology, Harbin 150080, China
Center for Interdisciplinary Studies & Key Laboratory for Magnetism and Magnetic Materials of the MoE, Lanzhou University, Lanzhou 730000, China
Yukawa Institute for Theoretical Physics, Kyoto University, Kyoto, 606-8502, Japan

Abstract

The electronic structures and optical properties of the monoclinic ZrO2 (m-ZrO2) are investigated by means of first-principles local density approximation (LDA) + U approach. Without on-site Coulomb interactions, the band gap of m-ZrO2 is 3.60 eV, much lower than the experimental value (5.8 eV). By introducing the Coulomb interactions of 4d orbitals on Zr atom (Ud) and of 2p orbitals on O atom (Up), we can reproduce the experimental value of the band gap. The calculated dielectric function of m-ZrO2 exhibits a small shoulder at the edge of the band gap in its imaginary part, while in the tetragonal ZrO2 and cubic ZrO2 it is absent, which is consistent with the experimental observations. The origin of the shoulder is attributed to the difference of electronic structures near the edge of the valence and conduction bands.

Keywords:

monoclinic ZrO2 (m-ZrO2), first-principles, local density approximation (LDA) + U, electronic structure, optical properties
Received: 05 September 2016 Revised: 11 January 2018 Accepted: 12 April 2017 Published: 02 March 2017 Issue date: March 2017
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Publication history

Received: 05 September 2016
Revised: 11 January 2018
Accepted: 12 April 2017
Published: 02 March 2017
Issue date: March 2017

Copyright

© The author(s) 2016

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 11121061 and 11672087), the Strategic Programs for Innovative Research (SPIRE), the Computational Materials Science Initiative (CMSI), and the Yukawa International Program for Quark-Hadron Sciences at YITP, Kyoto University.

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