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Title: The Structure of Liquid and Amorphous Hafnia

Journal Article · · Materials
DOI: https://doi.org/10.3390/ma10111290 · OSTI ID:1422595
 [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
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Univ. of California, Davis, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); ANL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357; 1506229
OSTI ID:
1422595
Journal Information:
Materials, Vol. 10, Issue 11; ISSN 1996-1944
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

References (79)

Area detector corrections for high quality synchrotron X-ray structure factor measurements
  • 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 https://doi.org/10.1016/j.nima.2011.09.031
journal January 2012
Generalized Gradient Approximation Made Simple journal October 1996
Constant pressure molecular dynamics for molecular systems journal December 1983
Hafnia and hafnia-toughened ceramics journal January 1992
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
Thermodynamic modeling of the Hf–Si–O system journal December 2006
Computer "Experiments" on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules journal July 1967
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
Molecular dynamics simulation of amorphous HfO 2 for resistive RAM applications journal July 2014
Isothermal-isobaric molecular dynamics using stochastic velocity rescaling journal February 2009
Amorphous Alumina Nanoparticles: Structure, Surface Energy, and Thermodynamic Phase Stability journal August 2013
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
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
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
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
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
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
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
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
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037
journal September 2012
In situ Study of the Crystallization from Amorphous to Cubic Zirconium Oxide:  Rietveld and Reverse Monte Carlo Analyses journal June 2007
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
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
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
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
Two-dimensional detector software: From real detector to idealised image or two-theta scan journal January 1996
Über die Schmelzpunkte des Zirkonoxydes und des Hafniumoxydes journal February 1932
Der Schmelzpunkt des Hafniumoxydes journal July 1925
MDTraj: A Modern Open Library for the Analysis of Molecular Dynamics Trajectories journal October 2015
Atomic and electronic structures of amorphous ZrO2 and HfO2 films journal August 2005
Area detector corrections for high quality synchrotron X-ray structure factor measurements
  • 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 https://doi.org/10.1016/j.nima.2011.09.031
journal January 2012
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
  • Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037
journal September 2012
Phase stability of hafnium oxide and zirconium oxide on silicon substrate journal August 2007
Strain-induced room-temperature ferroelectricity in SrTiO3 membranes journal June 2020
Orthogonal colloidal quantum dot inks enable efficient multilayer optoelectronic devices journal September 2020
Few-layer bismuth selenide cathode for low-temperature quasi-solid-state aqueous zinc metal batteries journal February 2022
Newly engineered alumina quantum dot-based nanofluid in enhanced oil recovery at reservoir conditions journal June 2022
Atomic and electronic structure of amorphous and crystalline hafnium oxide: X-ray photoelectron spectroscopy and density functional calculations journal March 2007
First principles study of the structural, electronic, and dielectric properties of amorphous HfO 2 journal September 2011
Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q -range journal February 2013
Ion migration in crystalline and amorphous HfO X journal March 2017
Constant pressure molecular dynamics for molecular systems journal December 1983
Cutoff Errors in the Ewald Summation Formulae for Point Charge Systems journal January 1992
A charge transfer ionic–embedded atom method potential for the O–Al–Ni–Co–Fe system journal May 2005
Molecular dynamics simulation of amorphous HfO 2 for resistive RAM applications journal July 2014
Diffusionless Phase Transformations in Zirconia and Hafnia journal September 1963
Proposed Phase Relations in the HfO 2 -Rich Portion of the System Hf-HfO 2 journal November 1973
The System HfO2-TiO2 journal June 1987
The Zirconia?Hafnia System: DTA Measurements and Thermodynamic Calculations journal December 2006
Synchrotron X-ray Scattering Measurements of Disordered Materials journal January 2016
Structural and dielectric properties of amorphous ZrO2 and HfO2 text January 2006
QUICKSTEP: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach text January 2005

Cited By (4)

Combined computational and experimental investigation of high temperature thermodynamics and structure of cubic ZrO2 and HfO2 journal October 2018
Temperature gradients for thermophysical and thermochemical property measurements to 3000 °C for an aerodynamically levitated spheroid journal January 2019
Characterizing the Charge Trapping across Crystalline and Amorphous Si/SiO 2 /HfO 2 Stacks from First-Principle Calculations journal December 2019
In‐situ determination of the HfO 2 –Ta 2 O 5 ‐temperature phase diagram up to 3000°C journal January 2019

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Related Subjects

36 MATERIALS SCIENCE
X-ray diffraction
neutron diffraction
molecular dynamics
liquid structure
amorphous materials
nanoparticles
hafnium oxide