101. ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure
- Author
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Artem M. Abakumov, Fumitaka Takeiri, Hiroshi Kageyama, Katsuhisa Tanaka, Clemens Ritter, Takafumi Yamamoto, Yoji Kobayashi, Ryu Abe, Cédric Tassel, Akihide Kuwabara, Daichi Watabe, Craig M. Brown, Koji Fujita, Dmitry Batuk, Kazuki Shitara, Yoshinori Kuno, and Hiroki Moriwake
- Subjects
Phase transition ,Chemistry ,Neutron diffraction ,02 engineering and technology ,General Chemistry ,Type (model theory) ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,Biochemistry ,Catalysis ,Synchrotron ,0104 chemical sciences ,Ion ,law.invention ,Crystallography ,Colloid and Surface Chemistry ,Transmission electron microscopy ,law ,Phase (matter) ,X-ray crystallography ,0210 nano-technology - Abstract
By using a high-pressure reaction, we prepared a new oxynitride ZnTaO2N that crystallizes in a centrosymmetric (R (3) over barc) high-temperature LiNbO3-type structure (HTLN-type). The stabilization of the HTLN-type structure down to low temperatures (at least 20 K) makes it possible to investigate not only the stability of this phase, but also the phase transition to a noncentrosymmetric (R3c) LiNbO3-type structure (LN-type) which is yet to be clarified. Synchrotron and neutron diffraction studies in combination with transmission electron microscopy show that Zn is located at a disordered 12c site instead of 6a, implying an order disorder mechanism of the phase transition. It is found that the dosed d-shell of Zn2+, as well as the high-valent Ta5+ ion, is responsible for the stabilization of the HTLN-type structure, affording a novel quasitriangular ZnO2N coordination. Interestingly, only 3% Zn substitution for MnTaO2N induces a phase transition from LN- to HTLN-type structure, implying the proximity in energy between the two structural types, which is supported by the first-principles calculations.
- Published
- 2016