Probing the solute-drag effect and its role in stabilizing the orthorhombic phase in bulk La-doped HfO2 by X-ray and gamma ray spectroscopy

文献情報

出版日 2021-07-03

DOI 10.1039/D1CP00096A

インパクトファクター 3.676

著者

原文を見る

要旨

The recent observation of ferroelectricity in ultra thin films of hafnium oxide (HfO2) has been attributed to the orthorhombic (o) phase of HfO2 with space group Pca21. Although this oxide is polymorphic in nature, this polar o-phase is known to be stabilized in the doped thin film oxide. The objective of the present experiment is to stabilize the o-phases in La doped bulk polycrystalline HfO2 and investigate their evolution with the doping concentration through Time Differential Perturbed Angular Correlation (TDPAC), X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) measurements. The present work reports the presence of both the polar Pca21 phase and the antipolar Pbca phase at different La-concentrations. Two o-phases of HfO2 with space groups Pca21 and Pbca, difficult to distinguish by other complimentary methods, could be unambiguously identified by utilizing the atomic scale sensitivity of the electric field gradient (EFG) embedded in TDPAC spectroscopy. The determination of the oxidation state and the local environment of La-atoms by XANES and EXAFS measurements illuminates the microscopic role of the dopant in stabilizing the o-phase. The “solute drag model” proposes a critical crystallite size for the nucleation of the o-phase in bulk HfO2 and explains the role of the La-dopant in stabilizing the o-phase. Thus the present study shows the possibility of stabilizing the polar o-phase and hence attaining ferroelectricity in bulk HfO2 to augment the scope of future application for this ferroelectric device.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.