Structural phase purification of bulk HfO2:Y through pressure cycling

J. L. Musfeldt; Sobhit Singh; Shiyu Fan; Yanhong Gu; Xianghan Xu; S. W. Cheong; Z. Liu; David Vanderbilt; Karin M. Rabe

doi:10.1073/pnas.2312571121

Structural phase purification of bulk HfO₂:Y through pressure cycling

J. L. Musfeldt
, Sobhit Singh
, Shiyu Fan
, Yanhong Gu
, Xianghan Xu
, S. W. Cheong
, Z. Liu
, David Vanderbilt
, Karin M. Rabe

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO₂:7%Y from the mixed monoclinic (P2₁/c) + antipolar orthorhombic (Pbca) phase to pure antipolar orthorhombic (Pbca) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the Pbca metastable state at 300 K. Compression also drives polar orthorhombic (Pca2₁) hafnia into the tetragonal (P4₂/nmc) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape.

Original language	English (US)
Article number	e2312571121
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	121
Issue number	5
DOIs	https://doi.org/10.1073/pnas.2312571121
State	Published - 2024
Externally published	Yes

Bibliographical note

Publisher Copyright:
Copyright © 2024 the Author(s). Published by PNAS. This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).

Keywords

competing phases
hafnia
phase purification
pressure cycling
vibrational spectroscopies

Publisher link

10.1073/pnas.2312571121

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@article{1d88fc578d0e4834a2162068a9f01436,

title = "Structural phase purification of bulk HfO2:Y through pressure cycling",

abstract = "We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO2:7\%Y from the mixed monoclinic (P21/c) + antipolar orthorhombic (Pbca) phase to pure antipolar orthorhombic (Pbca) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the Pbca metastable state at 300 K. Compression also drives polar orthorhombic (Pca21) hafnia into the tetragonal (P42/nmc) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape.",

keywords = "competing phases, hafnia, phase purification, pressure cycling, vibrational spectroscopies",

author = "Musfeldt, \{J. L.\} and Sobhit Singh and Shiyu Fan and Yanhong Gu and Xianghan Xu and Cheong, \{S. W.\} and Z. Liu and David Vanderbilt and Rabe, \{Karin M.\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2024 the Author(s). Published by PNAS. This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND).",

year = "2024",

doi = "10.1073/pnas.2312571121",

language = "English (US)",

volume = "121",

journal = "Proceedings of the National Academy of Sciences of the United States of America",

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TY - JOUR

T1 - Structural phase purification of bulk HfO2:Y through pressure cycling

AU - Musfeldt, J. L.

AU - Singh, Sobhit

AU - Fan, Shiyu

AU - Gu, Yanhong

AU - Xu, Xianghan

AU - Cheong, S. W.

AU - Liu, Z.

AU - Vanderbilt, David

AU - Rabe, Karin M.

PY - 2024

Y1 - 2024

N2 - We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO2:7%Y from the mixed monoclinic (P21/c) + antipolar orthorhombic (Pbca) phase to pure antipolar orthorhombic (Pbca) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the Pbca metastable state at 300 K. Compression also drives polar orthorhombic (Pca21) hafnia into the tetragonal (P42/nmc) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape.

AB - We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO2:7%Y from the mixed monoclinic (P21/c) + antipolar orthorhombic (Pbca) phase to pure antipolar orthorhombic (Pbca) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the Pbca metastable state at 300 K. Compression also drives polar orthorhombic (Pca21) hafnia into the tetragonal (P42/nmc) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape.

KW - competing phases

KW - hafnia

KW - phase purification

KW - pressure cycling

KW - vibrational spectroscopies

UR - https://www.scopus.com/pages/publications/85183335183

UR - https://www.scopus.com/pages/publications/85183335183#tab=citedBy

U2 - 10.1073/pnas.2312571121

DO - 10.1073/pnas.2312571121

M3 - Article

C2 - 38266049

AN - SCOPUS:85183335183

SN - 0027-8424

VL - 121

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

IS - 5

M1 - e2312571121

ER -