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Title: The Structure of Liquid and Amorphous Hafnia

Abstract

Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that show density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO6,7 polyhedra resembling that observed in the monoclinic phase.

Authors:
 [1];  [2];  [1];  [1];  [3];  [3];  [2];  [4];  [5];  [6];  [1]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Argonne Leadership Computing Facility
  3. Univ. of California, Davis, CA (United States). Peter A. Rock Thermochemistry Lab. NEAT ORU
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Global Security Sciences
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Computing, Environment and Life Sciences
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of California, Davis, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); ANL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
OSTI Identifier:
1422595
Grant/Contract Number:  
AC02-06CH11357; 1506229
Resource Type:
Accepted Manuscript
Journal Name:
Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 1996-1944
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; X-ray diffraction; neutron diffraction; molecular dynamics; liquid structure; amorphous materials; nanoparticles; hafnium oxide

Citation Formats

Gallington, Leighanne, Ghadar, Yasaman, Skinner, Lawrie, Weber, J., Ushakov, Sergey, Navrotsky, Alexandra, Vazquez-Mayagoitia, Alvaro, Neuefeind, Joerg, Stan, Marius, Low, John, and Benmore, Chris. The Structure of Liquid and Amorphous Hafnia. United States: N. p., 2017. Web. doi:10.3390/ma10111290.
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Gallington, Leighanne, Ghadar, Yasaman, Skinner, Lawrie, Weber, J., Ushakov, Sergey, Navrotsky, Alexandra, Vazquez-Mayagoitia, Alvaro, Neuefeind, Joerg, Stan, Marius, Low, John, & Benmore, Chris. The Structure of Liquid and Amorphous Hafnia. United States. https://doi.org/10.3390/ma10111290
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Gallington, Leighanne, Ghadar, Yasaman, Skinner, Lawrie, Weber, J., Ushakov, Sergey, Navrotsky, Alexandra, Vazquez-Mayagoitia, Alvaro, Neuefeind, Joerg, Stan, Marius, Low, John, and Benmore, Chris. Fri . "The Structure of Liquid and Amorphous Hafnia". United States. https://doi.org/10.3390/ma10111290. https://www.osti.gov/servlets/purl/1422595.
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@article{osti_1422595,
title = {The Structure of Liquid and Amorphous Hafnia},
author = {Gallington, Leighanne and Ghadar, Yasaman and Skinner, Lawrie and Weber, J. and Ushakov, Sergey and Navrotsky, Alexandra and Vazquez-Mayagoitia, Alvaro and Neuefeind, Joerg and Stan, Marius and Low, John and Benmore, Chris},
abstractNote = {Understanding the atomic structure of amorphous solids is important in predicting and tuning their macroscopic behavior. Here, we use a combination of high-energy X-ray diffraction, neutron diffraction, and molecular dynamics simulations to benchmark the atomic interactions in the high temperature stable liquid and low-density amorphous solid states of hafnia. The diffraction results reveal an average Hf–O coordination number of ~7 exists in both the liquid and amorphous nanoparticle forms studied. The measured pair distribution functions are compared to those generated from several simulation models in the literature. We have also performed ab initio and classical molecular dynamics simulations that show density has a strong effect on the polyhedral connectivity. The liquid shows a broad distribution of Hf–Hf interactions, while the formation of low-density amorphous nanoclusters can reproduce the sharp split peak in the Hf–Hf partial pair distribution function observed in experiment. The agglomeration of amorphous nanoparticles condensed from the gas phase is associated with the formation of both edge-sharing and corner-sharing HfO6,7 polyhedra resembling that observed in the monoclinic phase.},
doi = {10.3390/ma10111290},
journal = {Materials},
number = 11,
volume = 10,
place = {United States},
year = {2017},
month = {11}
}
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