Doping-induced Polyamorphic Transitions in Fluorite Oxides

Fuente: arXiv
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Main Authors: Yang, Hao, Luan, Qiaotong, Zhang, Qing, Yue, Yuhao, Xu, Yawen, Liu, Xiaohui, Wen, Zheng, Sun, Zhaoru
Format: Preprint
Published: 2025
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author Yang, Hao
Luan, Qiaotong
Zhang, Qing
Yue, Yuhao
Xu, Yawen
Liu, Xiaohui
Wen, Zheng
Sun, Zhaoru
author_facet Yang, Hao
Luan, Qiaotong
Zhang, Qing
Yue, Yuhao
Xu, Yawen
Liu, Xiaohui
Wen, Zheng
Sun, Zhaoru
contents Fluorite oxides such as HfO$_2$ exhibit rich and tunable phase behavior, making them promising candidates for next generation electronic devices. A key challenge is to design amorphous HfO$_2$-based high-$k$ materials with both structural and performance stability. Here, using molecular dynamics simulations supported by experimental measurements, we reveal that Ba doping stimulates a polyamorphic transition in HfO$_2$, yielding a semi-ordered amorphous (SA) phase characterized by disordered oxygens embedded within an ordered metal sublattice. We find that this phase arises from degenerate short-range symmetry breaking modes, consistent with Pauling's parsimony rule. Notably, the SA structure is thermodynamically stable and displays a wider bandgap and higher dielectric constant than conventional random-packing amorphous structure, owing to suppressed subgap states and increased Born effective charges. We further demonstrate that this structural motif generalizes to Ba-, Sr-, and Ca-doped HfO$_2$ and ZrO$_2$, establishing a broadly applicable strategy for designing high-performance amorphous dielectrics.
format Preprint
id arxiv_https___arxiv_org_abs_2506_18333
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Doping-induced Polyamorphic Transitions in Fluorite Oxides
Yang, Hao
Luan, Qiaotong
Zhang, Qing
Yue, Yuhao
Xu, Yawen
Liu, Xiaohui
Wen, Zheng
Sun, Zhaoru
Materials Science
Statistical Mechanics
Fluorite oxides such as HfO$_2$ exhibit rich and tunable phase behavior, making them promising candidates for next generation electronic devices. A key challenge is to design amorphous HfO$_2$-based high-$k$ materials with both structural and performance stability. Here, using molecular dynamics simulations supported by experimental measurements, we reveal that Ba doping stimulates a polyamorphic transition in HfO$_2$, yielding a semi-ordered amorphous (SA) phase characterized by disordered oxygens embedded within an ordered metal sublattice. We find that this phase arises from degenerate short-range symmetry breaking modes, consistent with Pauling's parsimony rule. Notably, the SA structure is thermodynamically stable and displays a wider bandgap and higher dielectric constant than conventional random-packing amorphous structure, owing to suppressed subgap states and increased Born effective charges. We further demonstrate that this structural motif generalizes to Ba-, Sr-, and Ca-doped HfO$_2$ and ZrO$_2$, establishing a broadly applicable strategy for designing high-performance amorphous dielectrics.
title Doping-induced Polyamorphic Transitions in Fluorite Oxides
topic Materials Science
Statistical Mechanics
url https://arxiv.org/abs/2506.18333