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Investigation of local structures of silicon oxynitride glasses prepared from aerogels

  • Invited Paper: Fundamentals of sol-gel and hybrid materials processing
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Abstract

Oxynitride glasses in Si-Al-O-N system were synthesized to investigate atomic arrangements in those glasses. Aerogels of silica (SiO2) and silica-alumina (SiO2-Al2O3) system were fabricated by drying wet gels in supercritical CO2 condition. The SiO2 gels were prepared from the silicon alkoxide with CH3 groups and the SiO2-Al2O3 gels were prepared from silicone and aluminum alkoxides. Ammonolysis were performed at TN = 750–1400 °C to synthesize oxynitride glasses. The nitrogen concentration in the resultant glasses increased with the increase in the ammonolysis temperatures and exceeded 34 eq.% by ammonolysis at 1300 °C. The specific surface area of these aerogels has been 1941 and 1159 m2 g−1, respectively. The glass structures were investigated by adopting 29Si and 27Al NMR measurements. In silicon oxynitride glasses, it was revealed that only one N atom occupies the nearest neighbor site around Si after ammonolysis at TN < 1200 °C, while two or more N atoms occupy the nearest neighbor site around Si after ammonolysis at TN > 1300 °C. In Si-Al-O-N glasses, the number of N atoms at around neighboring to Si atom varied with ammonolysis temperature but any traces of Al-N bonds were not found, indicating the bridging N in the form of Si-N-Al was absent in the glasses.

Nitrogen contents of oxynitride glasses prepared from silica-based aerogels with CH3 groups (ON-CH3) and those doped with Al and Eu ions (ON-AE) increased with increase of ammonolysis temperature. The 29Si NMR spectra differed between ON-CH3 and ON-AE.

Highlights

  • Silicon-based oxynitride glasses were prepared from aerogels via ammonolysis at high temperature.

  • Nitrogen contents of the oxynitride glasses reached to higher than 34 eq.%.

  • The local structures of the oxynitride glasses were investigated by 29Si and 27Al NMR measurements.

  • It was found that most of inserted nitrogen was bonded to Si atoms.

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Acknowledgements

This work was supported by the MEXT Elements Strategy Initiative to Form Core Research Center for Electronic Materials: Tokodai Institute of Elements Strategy, Japan, Grant Number JPMXP0112101001.

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Authors and Affiliations

  1. National Institute of Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan

    Hiroyo Segawa, Yuta Osawa, Shunsuke Watanabe, Sadaki Samitsu, Kenzo Deguchi, Shinobu Ohki & Naoki Ohashi

  2. Tokyo University of Science, 6-3-1 Nijyuku, Katsushika-ku, Tokyo, 125-8585, Japan

    Hiroyo Segawa, Yuta Osawa, Shunsuke Watanabe, Shingo Machida, Ken-ichi Katsumata & Atsuo Yasumori

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  1. Hiroyo Segawa
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  2. Yuta Osawa
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Segawa, H., Osawa, Y., Watanabe, S. et al. Investigation of local structures of silicon oxynitride glasses prepared from aerogels. J Sol-Gel Sci Technol 104, 503–511 (2022). https://doi.org/10.1007/s10971-022-05903-z

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