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

Bethany M. Hudak, Sean W. Depner, Gregory R. Waetzig, Anjana Talapatra, Raymundo Arroyave, Sarbajit Banerjee () and Beth S. Guiton ()
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Bethany M. Hudak: University of Kentucky
Sean W. Depner: University at Buffalo, The State University of New York
Gregory R. Waetzig: Texas A&M University
Anjana Talapatra: Texas A&M University
Raymundo Arroyave: Texas A&M University
Sarbajit Banerjee: Texas A&M University
Beth S. Guiton: University of Kentucky

Nature Communications, 2017, vol. 8, issue 1, 1-9

Abstract: Abstract 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.

Date: 2017
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DOI: 10.1038/ncomms15316

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