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Real-time atomistic observation of structural phase transformations in individual hafnia nanorods

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms15316· OSTI ID:1376500
 [1];  [2];  [3];  [4];  [4];  [3];  [5]
  1. Univ. of Kentucky, Lexington, KY (United States). Dept. of Chemistry
  2. Univ. at Buffalo, NY (United States). Dept. of Chemistry
  3. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry. Dept. of Materials Science and Engineering
  4. Texas A & M Univ., College Station, TX (United States). Dept. of Materials Science and Engineering
  5. Univ. of Kentucky, Lexington, KY (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

High-temperature phases of hafnium dioxide have exceptionally high dielectric constants and large bandgaps, but quenching them to room temperature remains a challenge. Scaling the bulk form to nanocrystals, while successful in stabilizing the tetragonal phase of isomorphous ZrO2, has produced nanorods with a twinned version of the room temperature monoclinic phase in HfO2. Here we use in situ heating in a scanning transmission electron microscope to observe the transformation of an HfO2 nanorod from monoclinic to tetragonal, with a transformation temperature suppressed by over 1000°C from bulk. When the nanorod is annealed, we observe with atomic-scale resolution the transformation from twinned-monoclinic to tetragonal, starting at a twin boundary and propagating via coherent transformation dislocation; the nanorod is reduced to hafnium on cooling. Unlike the bulk displacive transition, nanoscale size-confinement enables us to manipulate the transformation mechanism, and we observe discrete nucleation events and sigmoidal nucleation and growth kinetics.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Aeronautics and Space Administration (NASA) (United States); National Science Foundation (NSF) (United States); Air Force Office of Scientific Research (AFOSR) (United States)
Contributing Organization:
Univ. at Buffalo, NY (United States)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1376500
Journal Information:
Nature Communications, Journal Name: Nature Communications Vol. 8; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (11)

Elucidating the Crystallite Size Dependence of the Thermochromic Properties of Nanocomposite VO2 Thin Films journal October 2018
Atomic Structure of Domain and Interphase Boundaries in Ferroelectric HfO$_2$ preprint January 2017
Healing of Planar Defects in 2D Materials via Grain Boundary Sliding journal February 2019
Atomic Structure of Domain and Interphase Boundaries in Ferroelectric HfO 2 journal January 2018
Effect of Annealing Ferroelectric HfO 2 Thin Films: In Situ, High Temperature X-Ray Diffraction journal May 2018
Nucleation-Limited Ferroelectric Orthorhombic Phase Formation in Hf 0.5 Zr 0.5 O 2 Thin Films journal December 2018
Thermodynamic and Kinetic Origins of Ferroelectricity in Fluorite Structure Oxides journal December 2018
Size, structure, and luminescence of Nd2Zr2O7 nanoparticles by molten salt synthesis journal June 2019
Understanding the formation of the metastable ferroelectric phase in hafnia–zirconia solid solution thin films journal January 2018
Epitaxial stabilization versus interdiffusion: synthetic routes to metastable cubic HfO 2 and HfV 2 O 7 from the core–shell arrangement of precursors journal January 2019
The impact of nano-bubbles on the laser performance of hafnia films deposited by oxygen assisted ion beam sputtering method journal December 2019

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