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. Our work confirms that nitrogen can act to passivate cubic hafnia for applications in electronics.
- Authors:
-
- Argonne National Lab. (ANL), Lemont, IL (United States)
- 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. https://doi.org/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. https://doi.org/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. https://doi.org/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. 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}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journalFigures / Tables:
FIG. 1: GGA+U and DMC total energies for the $V^{+2}_{O}$ defect state as a function of parameter Δd in units of Å. The data were fitted with a polynomial function, shown as a solid line (GGA+U) and as a dashed line (DMC).
All figures and tables
(14 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Vacancy and interstitial defects in hafnia
journal, May 2002
- Foster, A. S.; Lopez Gejo, F.; Shluger, A. L.
- Physical Review B, Vol. 65, Issue 17
Dielectric properties of dysprosium- and scandium-doped hafnium dioxide thin films
journal, October 2007
- Adelmann, C.; Sriramkumar, V.; Van Elshocht, S.
- Applied Physics Letters, Vol. 91, Issue 16
Quantum Monte Carlo simulations of solids
journal, January 2001
- Foulkes, W. M. C.; Mitas, L.; Needs, R. J.
- Reviews of Modern Physics, Vol. 73, Issue 1
High-K materials and metal gates for CMOS applications
journal, February 2015
- Robertson, John; Wallace, Robert M.
- Materials Science and Engineering: R: Reports, Vol. 88
Dataset for Defect Energetics of Cubic Hafnia from Quantum Monte Carlo Simulations
dataset, January 2019
- Chimata, Raghuveer; Shin, Hyeondeok; Benali, Anouar
- Materials Data Facility
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
Fixed‐node quantum Monte Carlo for molecules a) b)
journal, December 1982
- Reynolds, Peter J.; Ceperley, David M.; Alder, Berni J.
- The Journal of Chemical Physics, Vol. 77, Issue 11
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo
journal, April 2015
- Santana, Juan A.; Krogel, Jaron T.; Kim, Jeongnim
- The Journal of Chemical Physics, Vol. 142, Issue 16
Many-Body Problem with Strong Forces
journal, June 1955
- Jastrow, Robert
- Physical Review, Vol. 98, Issue 5
First-principles study of native point defects in hafnia and zirconia
journal, March 2007
- Zheng, J. X.; Ceder, G.; Maxisch, T.
- Physical Review B, Vol. 75, Issue 10
Ferromagnetism Driven by Intrinsic Point Defects in
journal, June 2005
- Das Pemmaraju, Chaitanya; Sanvito, S.
- Physical Review Letters, Vol. 94, Issue 21
Electronic properties of doped and defective NiO: A quantum Monte Carlo study
journal, December 2017
- Shin, Hyeondeok; Luo, Ye; Ganesh, Panchapakesan
- Physical Review Materials, Vol. 1, Issue 7
A novel approach to low-temperature synthesis of cubic HfO2 nanostructures and their cytotoxicity
journal, August 2017
- Kumar, Neeraj; George, Blassan Plackal Adimuriyil; Abrahamse, Heidi
- Scientific Reports, Vol. 7, Issue 1
Gd-doping effect on performance of HfO2 based resistive switching memory devices using implantation approach
journal, January 2011
- Zhang, Haowei; Liu, Lifeng; Gao, Bin
- Applied Physics Letters, Vol. 98, Issue 4
Role of Nitrogen Atoms in Reduction of Electron Charge Traps in Hf-Based High- $\kappa$ Dielectrics
journal, May 2007
- Umezawa, N.; Shiraishi, K.; Torii, K.
- IEEE Electron Device Letters, Vol. 28, Issue 5
Effect of nitrogen passivation/pre nitration on interface properties of atomic layer deposited HfO2
journal, February 2018
- Maurya, Savita
- Journal of Materials Science: Materials in Electronics, Vol. 29, Issue 9
Jastrow correlation factor for atoms, molecules, and solids
journal, December 2004
- Drummond, N. D.; Towler, M. D.; Needs, R. J.
- Physical Review B, Vol. 70, Issue 23
Reduction of Monoclinic HfO 2 : A Cascading Migration of Oxygen and Its Interplay with a High Electric Field
journal, October 2016
- Traoré, Boubacar; Blaise, Philippe; Sklénard, Benoît
- The Journal of Physical Chemistry C, Vol. 120, Issue 43
Zirconia and hafnia polymorphs: Ground-state structural properties from diffusion Monte Carlo
journal, July 2018
- Shin, Hyeondeok; Benali, Anouar; Luo, Ye
- Physical Review Materials, Vol. 2, Issue 7
Negative-U property of oxygen vacancy in cubic HfO2
journal, August 2005
- Feng, Y. P.; Lim, A. T. L.; Li, M. F.
- Applied Physics Letters, Vol. 87, Issue 6
Resistive switching characteristics of nickel silicide layer embedded HfO 2 film
journal, March 2012
- Panda, Debashis; Huang, Chun-Yang; Tseng, Tseung-Yuen
- Applied Physics Letters, Vol. 100, Issue 11
Finite-Size Error in Many-Body Simulations with Long-Range Interactions
journal, August 2006
- Chiesa, Simone; Ceperley, David M.; Martin, Richard M.
- Physical Review Letters, Vol. 97, Issue 7
Thermal stability and electrical characteristics of ultrathin hafnium oxide gate dielectric reoxidized with rapid thermal annealing
journal, April 2000
- Lee, Byoung Hun; Kang, Laegu; Nieh, Renee
- Applied Physics Letters, Vol. 76, Issue 14
Oxygen-modulated quantum conductance for ultrathin -based memristive switching devices
journal, October 2016
- Zhong, Xiaoliang; Rungger, Ivan; Zapol, Peter
- Physical Review B, Vol. 94, Issue 16
A charge transport study in diamond, surface passivated by high- k dielectric oxides
journal, November 2014
- Kovi, Kiran Kumar; Majdi, Saman; Gabrysch, Markus
- Applied Physics Letters, Vol. 105, Issue 20
Finite-size errors in continuum quantum Monte Carlo calculations
journal, September 2008
- Drummond, N. D.; Needs, R. J.; Sorouri, A.
- Physical Review B, Vol. 78, Issue 12
Variational quantum Monte Carlo nonlocal pseudopotential approach to solids: Formulation and application to diamond, graphite, and silicon
journal, August 1990
- Fahy, S.; Wang, X. W.; Louie, Steven G.
- Physical Review B, Vol. 42, Issue 6
The energy and elastic dipole tensor of defects in ionic crystals calculated by the supercell method
journal, February 1985
- Leslie, M.; Gillan, N. J.
- Journal of Physics C: Solid State Physics, Vol. 18, Issue 5
Dielectric functions and optical bandgaps of high-K dielectrics for metal-oxide-semiconductor field-effect transistors by far ultraviolet spectroscopic ellipsometry
journal, April 2002
- Lim, Seung-Gu; Kriventsov, Stas; Jackson, Thomas N.
- Journal of Applied Physics, Vol. 91, Issue 7
Stabilization of the cubic phase of HfO2 by Y addition in films grown by metal organic chemical vapor deposition
journal, July 2006
- Rauwel, E.; Dubourdieu, C.; Holländer, B.
- Applied Physics Letters, Vol. 89, Issue 1
First-principles study of structural, vibrational, and lattice dielectric properties of hafnium oxide
journal, June 2002
- Zhao, Xinyuan; Vanderbilt, David
- Physical Review B, Vol. 65, Issue 23
Hybrid algorithms in quantum Monte Carlo
journal, December 2012
- Kim, Jeongnim; Esler, Kenneth P.; McMinis, Jeremy
- Journal of Physics: Conference Series, Vol. 402
First-principles calculations for point defects in solids
journal, March 2014
- Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
- Reviews of Modern Physics, Vol. 86, Issue 1
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Intrinsic versus extrinsic ferromagnetism in and thin films
journal, October 2014
- Hildebrandt, Erwin; Yazdi, Mehrdad Baghaie; Kurian, Jose
- Physical Review B, Vol. 90, Issue 13
Germanium nanowire field-effect transistors with SiO2 and high-κ HfO2 gate dielectrics
journal, September 2003
- Wang, Dunwei; Wang, Qian; Javey, Ali
- Applied Physics Letters, Vol. 83, Issue 12
Benchmarks and Reliable DFT Results for Spin Gaps of Small Ligand Fe(II) Complexes
journal, March 2018
- Song, Suhwan; Kim, Min-Cheol; Sim, Eunji
- Journal of Chemical Theory and Computation, Vol. 14, Issue 5
Permittivity increase of yttrium-doped HfO2 through structural phase transformation
journal, March 2005
- Kita, Koji; Kyuno, Kentaro; Toriumi, Akira
- Applied Physics Letters, Vol. 86, Issue 10
Schottky defect formation energy in MgO calculated by diffusion Monte Carlo
journal, June 2005
- Alfè, D.; Gillan, M. J.
- Physical Review B, Vol. 71, Issue 22
Magnetism in hafnium dioxide
journal, July 2005
- Coey, J. M. D.; Venkatesan, M.; Stamenov, P.
- Physical Review B, Vol. 72, Issue 2
Optimization of sub 3 nm gate dielectrics grown by rapid thermal oxidation in a nitric oxide ambient
journal, January 1997
- Kumar, Kiran; Chou, Anthony I.; Lin, Chuan
- Applied Physics Letters, Vol. 70, Issue 3
Unexpected magnetism in a dielectric oxide
journal, August 2004
- Venkatesan, M.; Fitzgerald, C. B.; Coey, J. M. D.
- Nature, Vol. 430, Issue 7000
Twist-averaged boundary conditions in continuum quantum Monte Carlo algorithms
journal, June 2001
- Lin, C.; Zong, F. H.; Ceperley, D. M.
- Physical Review E, Vol. 64, Issue 1
Correlation of annealing effects on local electronic structure and macroscopic electrical properties for HfO2 deposited by atomic layer deposition
journal, November 2003
- Wilk, G. D.; Muller, D. A.
- Applied Physics Letters, Vol. 83, Issue 19
QMCPACK : an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids
journal, April 2018
- Kim, Jeongnim; Baczewski, Andrew D.; Beaudet, Todd D.
- Journal of Physics: Condensed Matter, Vol. 30, Issue 19
Electronic band structure of zirconia and hafnia polymorphs from the perspective
journal, February 2010
- Jiang, Hong; Gomez-Abal, Ricardo I.; Rinke, Patrick
- Physical Review B, Vol. 81, Issue 8
Computational investigation of the phase stability and the electronic properties for Gd-doped HfO 2
journal, May 2014
- Wang, L. G.; Xiong, Y.; Xiao, W.
- Applied Physics Letters, Vol. 104, Issue 20
Origin of the threshold voltage instability in SiO 2 /HfO 2 dual layer gate dielectrics
journal, February 2003
- Kerber, A.; Cartier, E.; Pantisano, L.
- IEEE Electron Device Letters, Vol. 24, Issue 2
Oxygen vacancy chain and conductive filament formation in hafnia
journal, April 2018
- Xue, Kan-Hao; Miao, Xiang-Shui
- Journal of Applied Physics, Vol. 123, Issue 16
Accuracy of ab initio electron correlation and electron densities in vanadium dioxide
journal, November 2017
- Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan
- Physical Review Materials, Vol. 1, Issue 6
Point defects in HfO2 high K gate oxide
journal, June 2005
- Xiong, K.; Robertson, J.
- Microelectronic Engineering, Vol. 80
Spin contamination in quantum Monte Carlo wave functions
journal, June 1998
- Huang, Chien-Jung; Filippi, Claudia; Umrigar, C. J.
- The Journal of Chemical Physics, Vol. 108, Issue 21
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.