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Title: Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo

Abstract

We have applied the many-body ab-initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure, and the energetics of the oxygen vacancy, zinc interstitial and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O 2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type, and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMCmore » and hybrid functionals can differ by more than 0.5 eV.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division, Center for Nanophase Materials Sciences, and Computer Science and Mathematics Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1185536
Alternate Identifier(s):
OSTI ID: 1228606
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Santana, Juan A., Krogel, Jaron T., Kim, Jeongnim, Kent, Paul R. C., and Reboredo, Fernando A. Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo. United States: N. p., 2015. Web. doi:10.1063/1.4919242.
Santana, Juan A., Krogel, Jaron T., Kim, Jeongnim, Kent, Paul R. C., & Reboredo, Fernando A. Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo. United States. doi:10.1063/1.4919242.
Santana, Juan A., Krogel, Jaron T., Kim, Jeongnim, Kent, Paul R. C., and Reboredo, Fernando A. Tue . "Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo". United States. doi:10.1063/1.4919242. https://www.osti.gov/servlets/purl/1185536.
@article{osti_1185536,
title = {Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo},
author = {Santana, Juan A. and Krogel, Jaron T. and Kim, Jeongnim and Kent, Paul R. C. and Reboredo, Fernando A.},
abstractNote = {We have applied the many-body ab-initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure, and the energetics of the oxygen vacancy, zinc interstitial and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type, and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.},
doi = {10.1063/1.4919242},
journal = {Journal of Chemical Physics},
number = 16,
volume = 142,
place = {United States},
year = {2015},
month = {4}
}

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