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Synthesis of cubic zirconium and hafnium nitride having Th3P4 structure

Nature Materials volume 2, pages 185–189 (2003)Cite this article

Abstract

High-pressure synthesis is a powerful method for the preparation of novel materials with high elastic moduli and hardness. Additionally, such materials may exhibit interesting thermal, optoelectronic, semiconductuing, magnetic or superconducting properties. Here, we report on the high-pressure synthesis of zirconium and hafnium nitrides with the stoichiometry M3N4, where M = Zr, Hf. Synthesis experiments were performed in a laser-heated diamond anvil cell at pressures up to 18 GPa and temperatures up to 3,000 K. We observed formation of cubic Zr3N4 and Hf3N4 (c-M3N4) with a Th3P4-structure, where M-cations are eightfold coordinated by N anions. The c-M3N4 phases are the first binary nitrides with such a high coordination number. Both compounds exhibit high bulk moduli around 250 GPa, which indicates high hardness. Moreover, the new nitrides, c-Zr3N4 and c-Hf3N4, may be the first members of a larger group of transition metal and/or lanthanide nitrides with interesting ferromagnetic or superconducting behaviour.

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Figure 1: Sample assemblage in a laser-heated diamond anvil cell.
Figure 2: Raman spectrum of c-Hf3N4 synthesized at 18 GPa.
Figure 3: X-ray powder diffractogram of c-Hf3N4 with an admixture of δ-HfN.
Figure 4: Raman spectrum of c-Zr3N4 synthesized at 16 GPa.

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Acknowledgements

We thank R. Boehler for technical support. We are grateful to R. Feile and M. A. Strzhemechny for fruitful discussions and to V. Hillgren for comments. The work was financially supported by the Deutsche Forschungsgemeinschaft (Bonn, Germany) and by the Fonds der Chemischen Industrie (Frankfurt, Germany).

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Authors and Affiliations

  1. Fachgebiet Disperse Feststoffe, Fachbereich Material und Geowissenschaften, Technische Universität Darmstadt, Petersenstrasse 23, Darmstadt, 64287, Germany

    Andreas Zerr & Ralf Riedel

  2. Fachgebiet Strukturforschung, Fachbereich Material und Geowissenschaften, Technische Universität Darmstadt, Petersenstrasse 23, Darmstadt, 64287, Germany

    Gerhard Miehe

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Correspondence to Andreas Zerr.

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Zerr, A., Miehe, G. & Riedel, R. Synthesis of cubic zirconium and hafnium nitride having Th3P4 structure. Nature Mater 2, 185–189 (2003). https://doi.org/10.1038/nmat836

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