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ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure.

Yoshinori Kuno1, Cédric Tassel1,2, Koji Fujita1

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Journal of the American Chemical Society
|December 15, 2016
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Researchers synthesized a new oxynitride, ZnTaO2N, exhibiting a stable high-temperature LiNbO3-type structure. This discovery sheds light on phase transitions in related materials and offers insights into novel coordination structures.

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Area of Science:

  • Solid State Chemistry
  • Materials Science
  • Crystallography

Background:

  • The LiNbO3-type structure is crucial in various applications.
  • Understanding phase transitions in related materials is essential for materials design.

Purpose of the Study:

  • To synthesize and characterize a new oxynitride, ZnTaO2N.
  • To investigate the structural stability and phase transition mechanisms of ZnTaO2N.
  • To explore the factors stabilizing specific crystallographic structures.

Main Methods:

  • High-pressure synthesis.
  • Synchrotron and neutron diffraction.
  • Transmission electron microscopy.
  • First-principles calculations.

Main Results:

  • A new oxynitride, ZnTaO2N, was prepared, crystallizing in a centrosymmetric (R3̅c) high-temperature LiNbO3-type (HTLN) structure.
  • The HTLN-type structure was stabilized down to 20 K, allowing study of its phase transition to a noncentrosymmetric (R3c) LiNbO3-type (LN) structure.
  • Zn was found at a disordered 12c site, indicating an order-disorder mechanism for the phase transition.
  • The closed d-shell of Zn2+ and high-valent Ta5+ stabilize the HTLN-type structure, forming a novel quasitriangular ZnO2N coordination.
  • A minor Zn substitution (3%) in MnTaO2N induced a phase transition from LN- to HTLN-type, suggesting energetic proximity of the two phases.

Conclusions:

  • ZnTaO2N provides a new platform for studying phase transitions in LiNbO3-type materials.
  • The electronic configuration of ions and coordination geometry play key roles in stabilizing crystal structures.
  • The findings suggest potential for tuning structural properties through controlled substitution.