skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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) (SC-22); 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.
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. doi:10.3390/ma10111290.
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. doi:10.3390/ma10111290. https://www.osti.gov/servlets/purl/1422595.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Area detector corrections for high quality synchrotron X-ray structure factor measurements
journal, January 2012

  • Skinner, Lawrie B.; Benmore, Chris J.; Parise, John B.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 662, Issue 1
  • DOI: 10.1016/j.nima.2011.09.031

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
  • DOI: 10.1103/PhysRevLett.77.3865

Constant pressure molecular dynamics for molecular systems
journal, December 1983


Hafnia and hafnia-toughened ceramics
journal, January 1992

  • Wang, J.; Li, H. P.; Stevens, R.
  • Journal of Materials Science, Vol. 27, Issue 20
  • DOI: 10.1007/BF00541601

Crystal Structure of Monoclinic Hafnia and Comparison with Monoclinic Zirconia
journal, March 1970


Diffusionless Phase Transformations in Zirconia and Hafnia
journal, September 1963


Calorimetric Measurements of Surface Energy of Amorphous HfO 2 Nanoparticles Produced by Gas Phase Condensation
journal, May 2017

  • Sharma, Geetu; Ushakov, Sergey V.; Li, Hui
  • The Journal of Physical Chemistry C, Vol. 121, Issue 19
  • DOI: 10.1021/acs.jpcc.7b01262

Thermodynamic modeling of the Hf–Si–O system
journal, December 2006


The System HfO2-TiO2
journal, June 1987


Joint diffraction and modeling approach to the structure of liquid alumina
journal, January 2013


Monoclinic Crystal Structures of ZrO2 and HfO2 Refined from X-ray Powder Diffraction Data
journal, October 1985


Synchrotron X-ray Scattering Measurements of Disordered Materials
journal, January 2016

  • Kohara, Shinji; Ohara, Koji; Tajiri, Hiroo
  • Zeitschrift für Physikalische Chemie, Vol. 230, Issue 3
  • DOI: 10.1515/zpch-2015-0654

Molecular dynamics simulation of amorphous HfO 2 for resistive RAM applications
journal, July 2014

  • Broglia, G.; Ori, G.; Larcher, L.
  • Modelling and Simulation in Materials Science and Engineering, Vol. 22, Issue 6
  • DOI: 10.1088/0965-0393/22/6/065006

Isothermal-isobaric molecular dynamics using stochastic velocity rescaling
journal, February 2009

  • Bussi, Giovanni; Zykova-Timan, Tatyana; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 130, Issue 7
  • DOI: 10.1063/1.3073889

Amorphous Alumina Nanoparticles: Structure, Surface Energy, and Thermodynamic Phase Stability
journal, August 2013

  • Tavakoli, Amir H.; Maram, Pardha Saradhi; Widgeon, Scarlett J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 33
  • DOI: 10.1021/jp405820g

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


The Zirconia?Hafnia System: DTA Measurements and Thermodynamic Calculations
journal, December 2006


Synthesis of nanophase ZnO, Eu2O3, and ZrO2 by gas-phase condensation with cw-CO2 laser heating
journal, July 1995


Der Schmelzpunkt des Hafniumoxydes
journal, July 1925


Oxygen-related defects in amorphous HfO2 gate dielectrics
journal, September 2007


Proposed Phase Relations in the HfO 2 -Rich Portion of the System Hf-HfO 2
journal, November 1973


Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

Neutron scattering lengths and cross sections
journal, January 1992


Low Cation Coordination in Oxide Melts
journal, April 2014


Amorphous HfO 2 and Hf 1 x Si x O via a melt-and-quench scheme using ab initio molecular dynamics
journal, May 2008


PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data
journal, July 2004

  • Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L.
  • Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678
  • DOI: 10.1107/S0021889804011744

Evolutionary Optimization of a Charge Transfer Ionic Potential Model for Ta/Ta-Oxide Heterointerfaces
journal, April 2017


A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

Phase stability of hafnium oxide and zirconium oxide on silicon substrate
journal, August 2007


A comparison of various commonly used correlation functions for describing total scattering
journal, April 2001


MDTraj: A Modern Open Library for the Analysis of Molecular Dynamics Trajectories
journal, October 2015

  • McGibbon, Robert T.; Beauchamp, Kyle A.; Harrigan, Matthew P.
  • Biophysical Journal, Vol. 109, Issue 8
  • DOI: 10.1016/j.bpj.2015.08.015

Modified charge transfer–embedded atom method potential for metal/metal oxide systems
journal, January 2004


NXFit : a program for simultaneously fitting X-ray and neutron diffraction pair-distribution functions to provide optimized structural parameters
journal, September 2014

  • Pickup, David; Moss, Robert; Newport, Robert
  • Journal of Applied Crystallography, Vol. 47, Issue 5
  • DOI: 10.1107/S160057671401824X

Electrostatic potentials for metal-oxide surfaces and interfaces
journal, October 1994


Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases
journal, September 2007

  • VandeVondele, Joost; Hutter, Jürg
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2770708

Structural and dielectric properties of amorphous ZrO 2 and HfO 2
journal, September 2006


On the use of modification functions when Fourier transforming total scattering data
journal, October 2012


First principles study of the structural, electronic, and dielectric properties of amorphous HfO 2
journal, September 2011

  • Chen, Tsung-Ju; Kuo, Chin-Lung
  • Journal of Applied Physics, Vol. 110, Issue 6
  • DOI: 10.1063/1.3636362

The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012

  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
  • DOI: 10.1016/j.nimb.2012.05.037

In situ Study of the Crystallization from Amorphous to Cubic Zirconium Oxide:  Rietveld and Reverse Monte Carlo Analyses
journal, June 2007

  • Zhang, Feng; Chupas, Peter J.; Lui, Siu Lun Alan
  • Chemistry of Materials, Vol. 19, Issue 13
  • DOI: 10.1021/cm061739w

Structure and dielectric properties of amorphous high- κ oxides: HfO 2 , ZrO 2 , and their alloys
journal, June 2012


Universal Medium-Range Order of Amorphous Metal Oxides
journal, October 2013


Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


Atomic and electronic structures of amorphous ZrO2 and HfO2 films
journal, August 2005

  • Gritsenko, Vladimir; Gritsenko, Daryja; Shaimeev, Sergei
  • Microelectronic Engineering, Vol. 81, Issue 2-4
  • DOI: 10.1016/j.mee.2005.03.056

Structural, electronic, and dielectric properties of amorphous Zr O 2 from ab initio molecular dynamics
journal, February 2005


Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q -range
journal, February 2013

  • Skinner, Lawrie B.; Huang, Congcong; Schlesinger, Daniel
  • The Journal of Chemical Physics, Vol. 138, Issue 7
  • DOI: 10.1063/1.4790861

Low-temperature polymorphs of Zr O 2 and Hf O 2 : A density-functional theory study
journal, October 2005


Über die Schmelzpunkte des Zirkonoxydes und des Hafniumoxydes
journal, February 1932


A charge transfer ionic–embedded atom method potential for the O–Al–Ni–Co–Fe system
journal, May 2005


Ion migration in crystalline and amorphous HfO X
journal, March 2017

  • Schie, Marcel; Müller, Michael P.; Salinga, Martin
  • The Journal of Chemical Physics, Vol. 146, Issue 9
  • DOI: 10.1063/1.4977453

Cutoff Errors in the Ewald Summation Formulae for Point Charge Systems
journal, January 1992


Atomic and electronic structure of amorphous and crystalline hafnium oxide: X-ray photoelectron spectroscopy and density functional calculations
journal, March 2007

  • Perevalov, T. V.; Gritsenko, V. A.; Erenburg, S. B.
  • Journal of Applied Physics, Vol. 101, Issue 5
  • DOI: 10.1063/1.2464184

Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996

  • Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
  • High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
  • DOI: 10.1080/08957959608201408