The origin of the ferroelectric-like orthorhombic phase in oxygen-deficient HfO2-y nanoparticles

TL;DR

This study investigates the origin of ferroelectric-like orthorhombic phase in oxygen-deficient HfO2-y nanoparticles, linking structural symmetry, defects, and polarization through experimental and theoretical analysis.

Contribution

It combines experimental XRD and EPR analysis with DFT calculations and an effective LGD model to explain ferroelectric-like behavior in HfO2-y nanoparticles, highlighting the role of defects and impurities.

Findings

Ferroelectric-like orthorhombic phase observed in oxygen-deficient HfO2-y nanoparticles.

Small HfO2 nanoparticles can become polar, especially with impurities and oxygen vacancies.

The modified LGD model aligns with experimental and DFT results, aiding development of ferroelectric nanomaterials.

Abstract

In this work we established the relationship between the crystalline structure symmetry, point defects and possible appearance of the ferroelectric-like polarization in HfO2-y nanoparticles. Notably, that XRD and EPR analysis revealed the formation of the ferroelectric-like orthorhombic phase in the oxygen-deficient HfO2-y nanoparticles (pure and doped with rare-earth element yttrium). DFT calculations showed that small HfO2 nanoparticles may become polar, especially in the presence of impurity atoms and/or oxygen vacancies. To explain the experimental results, we have modified the effective LGD model through the parameterization approach, focusing on the Landau expansion coefficients associated with the polar (FE) and antipolar (AFE) orderings, which agrees with the performed DFT calculations. The effective LGD model can be useful for the development of the novel generation of silicon-compatible ferroelectric nanomaterials based on the HfxZr1-xO2-y.