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Origin of Ferroelectricity in BiFeO3-Based Solid Solutions.

Yuji Noguchi1, Hiroki Matsuo2

  • 1Division of Information and Energy, Faculty of Advanced Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555, Japan.

Nanomaterials (Basel, Switzerland)
|December 11, 2022
PubMed
Summary

The origin of ferroelectricity in BiFeO3-LaFeO3 systems is linked to Bi lone pair electron accommodation. Electronic hybridization determines spontaneous polarization (Ps) in rhombohedral and tetragonal phases.

Keywords:
BiFeO3Bloch functionferroelectrichybridizationorthorhombicperovskitepolarizationrhombohedralsolid solutiontetragonal

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Area of Science:

  • Materials Science
  • Solid-State Physics
  • Computational Materials Science

Background:

  • Ferroelectricity in perovskite oxides like BiFeO3-LaFeO3 is crucial for device applications.
  • Understanding the electronic origins of ferroelectricity is key to designing new materials.
  • The BiFeO3-LaFeO3 system exhibits complex phase behavior with varying La content.

Purpose of the Study:

  • Investigate the fundamental origins of ferroelectricity in BiFeO3-LaFeO3 systems.
  • Compare electronic structures across different crystallographic symmetries (rhombohedral, tetragonal, orthorhombic).
  • Elucidate the role of Bi lone pair electrons and hybridization in determining spontaneous polarization (Ps).

Main Methods:

  • Ab initio density functional theory (DFT) calculations.
  • Analysis of electronic band structures and orbital hybridization.
  • Comparison of ferroelectric (R3c, P4mm) and paraelectric (Pnma) phases.

Main Results:

  • Coherent accommodation of Bi lone pair electrons is detrimental to ferroelectricity.
  • Spontaneous polarization (Ps) in the rhombohedral phase originates from Bi 6p-Fe 3d hybridization via O 2p.
  • Tetragonal phase Ps arises from Bi 6p-O 2p hybridization, with Fe 3d playing a minor role.
  • Orthorhombic phase exhibits paraelectricity due to staggered Bi lone pair accommodation.

Conclusions:

  • The electronic structure, specifically Bi lone pair behavior and hybridization, dictates ferroelectricity in BiFeO3-LaFeO3.
  • La doping influences Ps differently in rhombohedral and tetragonal phases due to distinct electronic origins.
  • DFT calculations provide crucial insights into structure-property relationships in ferroelectric materials.