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Title: Defect energetics of cubic hafnia from quantum Monte Carlo simulations

Abstract

Cubic hafnia (HfO2) is of great interest for a number of applications in electronics because of its high dielectric constant. However, common defects in such applications degrade the properties of hafina. We have investigated the electronic properties of oxygen vacancies and nitrogen substitution in cubic HfO2 using first-principles calculations based on density functional theory (DFT) and many-body diffusion Monte Carlo (DMC) methods. We investigate five different charge defect states of oxygen vacancies, as well as substitutional N defects which can lead to local magnetic moments. Both DMC and DFT calculations shows that an oxygen vacancy induces strong lattice relaxations around the defect. Finally, we compare defect formation energies, charge and spin densities obtained from DMC with results obtained using DFT. While the obtained formation energies from DMC are 0.6–1.5 eV larger than those from GGA+U, the agreement for the most important defects, neutral and positively charged oxygen vacancies, and nitrogen substitutional defect, under oxygen-poor conditions are in reasonably good agreement. Lastly, our work confirms that nitrogen can act to passivate cubic hafnia for applications in electronics.

Authors:
 [1];  [1];  [1];  [2]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern-Argonne Institute for Science and Engineering, Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1545380
Alternate Identifier(s):
OSTI ID: 1545423; OSTI ID: 1558516
Grant/Contract Number:  
AC02-06CH11357; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 7; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Chimata, Raghuveer, Shin, Hyeondeok, Benali, Anouar, and Heinonen, Olle. Defect energetics of cubic hafnia from quantum Monte Carlo simulations. United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.075005.
Chimata, Raghuveer, Shin, Hyeondeok, Benali, Anouar, & Heinonen, Olle. Defect energetics of cubic hafnia from quantum Monte Carlo simulations. United States. doi:10.1103/PhysRevMaterials.3.075005.
Chimata, Raghuveer, Shin, Hyeondeok, Benali, Anouar, and Heinonen, Olle. Thu . "Defect energetics of cubic hafnia from quantum Monte Carlo simulations". United States. doi:10.1103/PhysRevMaterials.3.075005. https://www.osti.gov/servlets/purl/1545380.
@article{osti_1545380,
title = {Defect energetics of cubic hafnia from quantum Monte Carlo simulations},
author = {Chimata, Raghuveer and Shin, Hyeondeok and Benali, Anouar and Heinonen, Olle},
abstractNote = {Cubic hafnia (HfO2) is of great interest for a number of applications in electronics because of its high dielectric constant. However, common defects in such applications degrade the properties of hafina. We have investigated the electronic properties of oxygen vacancies and nitrogen substitution in cubic HfO2 using first-principles calculations based on density functional theory (DFT) and many-body diffusion Monte Carlo (DMC) methods. We investigate five different charge defect states of oxygen vacancies, as well as substitutional N defects which can lead to local magnetic moments. Both DMC and DFT calculations shows that an oxygen vacancy induces strong lattice relaxations around the defect. Finally, we compare defect formation energies, charge and spin densities obtained from DMC with results obtained using DFT. While the obtained formation energies from DMC are 0.6–1.5 eV larger than those from GGA+U, the agreement for the most important defects, neutral and positively charged oxygen vacancies, and nitrogen substitutional defect, under oxygen-poor conditions are in reasonably good agreement. Lastly, our work confirms that nitrogen can act to passivate cubic hafnia for applications in electronics.},
doi = {10.1103/PhysRevMaterials.3.075005},
journal = {Physical Review Materials},
number = 7,
volume = 3,
place = {United States},
year = {2019},
month = {7}
}

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