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Synthesis of cubic silicon nitride

Nature volume 400, pages 340–342 (1999)Cite this article

Abstract

Silicon nitride (Si3N4) is used in a variety of important technological applications. The high fracture toughness, hardness and wear resistance of Si3N4-based ceramics are exploited in cutting tools and anti-friction bearings1; in electronic applications, Si3N4 is used as an insulating, masking and passivating material2. Two polymorphs of silicon nitride are known, both of hexagonal structure: α- and β-Si3N4. Here we report the synthesis of a third polymorph of silicon nitride, which has a cubic spinel structure. This new phase, c-Si3N4, is formed at pressures above 15 GPa and temperatures exceeding 2,000 K, yet persists metastably in air at ambient pressure to at least 700 K. First-principles calculations of the properties of this phase suggest that the hardness of c-Si3N4 should be comparable to that of the hardest known oxide (stishovite3, a high-pressure phase of SiO2), and significantly greater than the hardness of the two hexagonal polymorphs.

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Figure 1: High-pressure Raman spectra of silicon nitride phases synthesized by heating elemental silicon and molecular nitrogen in a diamond cell.
Figure 2: Selected-area electron diffraction pattern of zone [001] of the new cubic silicon nitride.
Figure 3: Calculated energy-versus-volume data for three Si3N4 structures.

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Acknowledgements

We thank O. Tschauner and I.-W. Chen for discussions, and Bayer AG for providing the β-Si3N4 powder. This work was supported by the Deutsche Forschungsgemeinschaft, Bonn, Germany, and the Fonds der Chemischen Industrie, Frankfurt, Germany.

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Authors and Affiliations

  1. Fachgebiet Disperse Feststoffe, Fachbereich Materialwissenschaft, Technische Universität Darmstadt, Petersenstrasse 23, D-64287, Darmstadt, Germany

    Andreas Zerr, Marcus Schwarz, Edwin Kroke & Ralf Riedel

  2. Fachgebiet Strukturforschung, Fachbereich Materialwissenschaft, Technische Universitt Darmstadt, Petersenstrasse 23, D-64287, Darmstadt, Germany

    Gerhard Miehe & Hartmut Fueß

  3. Max-Planck-Institut fr Chemie, Postfach 3060, D-55020, Mainz, Germany

    George Serghiou & Reinhard Boehler

  4. Department of Chemistry, Cornell University, Baker Laboratory, Ithaca, 14853-1301, New York, USA

    Peter Kroll

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  1. Andreas Zerr
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Correspondence to Ralf Riedel.

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Zerr, A., Miehe, G., Serghiou, G. et al. Synthesis of cubic silicon nitride. Nature 400, 340–342 (1999). https://doi.org/10.1038/22493

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