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Comparative study for effect of Ti, Nb and W incorporation on the electronic and optical properties of pristine hafnia (m-HfO2): DFT theoretical prospective

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Abstract

First-principles calculations using the Hubbard approach (DFT + U) with PBEsol correlation were performed to compare the effects of incorporating 3d, 4d, and 5d metal atoms on the electronic and optical properties of m-HfO2. Incorporating metal atoms in the HfO2 crystal structure shifted the band gap edges and lowered the conduction band minimum, reducing the band gap as follows: 5.24 eV for HfO2, 3.26 eV for HfO2:Ti, 1.12 eV for HfO2:W, and 0.92 eV for HfO2:Nb. Total and partial density of states calculations showed that the valence band maximum of pristine HfO2 is mainly constructed from O 2p states, while the conduction band minimum is mainly from Hf 4d states. For doped crystals, the conduction band minimum is mainly from 3d states of Ti, 4d states of Nb, and 5d states of W. For pristine HfO2, the calculated dielectric constant, reflectivity and refractive index match available experimental and theoretical data. For doped systems, incorporating Nb (4d metal) and W (5d metal) had similar effects on the electronic and optical properties of HfO2, differing more from incorporating Ti (3d metal). HfO2 absorption roughly doubled upon Ti atom insertion (HfO2:Ti). Based on the results of this study, we would like to emphasize that these results provide a solid theoretical starting point that motivates further experimental studies into the application potential of these doped metal oxide systems.

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The datasets generated and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

Authors of this work would like to thank King Abdulaziz University in Saudi Arabia for the technical support of this research.

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  1. Department of Chemistry, Faculty of Science, Ain-Shams University, Cairo, Egypt

    El-Sayed R. Khattab, Tamer S. El-Shazly, Magdy A. M. Ibrahim & Sayed S. Abd El Rehim

  2. Department of Chemistry, Faculty of Science, Cairo University, Giza, 12613, Egypt

    Walid M. I. Hassan

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E–SK (corresponding author) contributed to DFT calculations, manuscript writing, results interpretation, data analysis, drawing and modifying figures and tables, also he was responsible for article submission and contacting with journal reviewers and editors. TE-S played a role in result interpretation, introduction writing, results improving, and sha** the final form. WH, MI and SSAER participated in the final review and incorporated the modifications proposed by the journal.

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Dedication: We would like to dedicate this work to the soul of Professor Ahmed M. El-Nahas, professor of quantum chemistry, Menoufia University.

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Khattab, ES.R., Hassan, W.M.I., El-Shazly, T.S. et al. Comparative study for effect of Ti, Nb and W incorporation on the electronic and optical properties of pristine hafnia (m-HfO2): DFT theoretical prospective. J Comput Electron 22, 1615–1625 (2023). https://doi.org/10.1007/s10825-023-02103-y

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