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Engineering Polar Oxynitrides: Hexagonal Perovskite BaWON2.

Judith Oró-Solé1, Ignasi Fina1, Carlos Frontera1

  • 1Institut de Ciència de Materials de Barcelona(ICMAB-CSIC), Campus UAB, 08193, Bellaterra, Spain.

Angewandte Chemie (International Ed. in English)
|July 11, 2020
PubMed
Summary

The first hexagonal perovskite oxynitride, BaWON2, exhibits a polar structure. This discovery opens avenues for novel electronic materials due to its non-centrosymmetric polar properties and semiconductor characteristics.

Keywords:
Jahn-Teller distortionsmaterials scienceoxynitridesperovskite phasestungsten

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Crystallography

Background:

  • Non-centrosymmetric polar compounds are crucial for technological applications.
  • Existing perovskite oxynitrides typically display centrosymmetric structures.
  • High permittivities in some oxynitrides are linked to local dipole ordering.

Purpose of the Study:

  • To report the synthesis and structural characterization of the first hexagonal perovskite oxynitride.
  • To investigate the origin of its polar nature and potential technological properties.
  • To explore its electronic and dielectric characteristics.

Main Methods:

  • Synchrotron X-ray and neutron powder diffraction for structural determination.
  • Annular bright-field scanning transmission electron microscopy (ABF-STEM) for microstructural analysis.
  • First-principles calculations to support theoretical understanding of electronic structure and bonding.

Main Results:

  • Discovery of a novel hexagonal perovskite oxynitride, BaWON2, with a polar 6H polytype.
  • Determination of its non-centrosymmetric space group P63mc, featuring ordered nitride and oxide ions.
  • Identification of a synergetic second-order Jahn-Teller effect, anion order, and cation repulsions driving spontaneous polarization.

Conclusions:

  • BaWON2 is the first reported hexagonal perovskite oxynitride with a polar structure.
  • Its non-centrosymmetric nature arises from specific ordering of anions and electronic effects.
  • The material is a semiconductor with a 1.1 eV band gap and exhibits large permittivity.