Neutron Diffraction Study on the Structure of Na-Si-O-N Oxynitride Glasses

The local structure of a Na₂O─SiO₂ oxide glass and a Na₂O─iO₂─Si₃N₄ oxynitride glass has been investigated by the pulsed neutron diffraction method. In the oxide glass, the first peak of radial distribution function (RDF) curves appeared at 0.1627 nm corresponding to Si─O boxh length. In the oxynitride glass, the first peak of the RDF curve was shifted to longer distances at 0.1650 nm due to the coexistence of Si─O and Si─N boxhs. The first peak in the RDF curve of the oxynitride glass was deconvoluted into two peaks whose positions are located at 0.1626 and 0.1709 nm. The one at 0.1626 nm is ascribed to Si─O boxhs and the other at 0.1709 nm to Si─N boxhs. The number of silicon atoms around a nitrogen was found to be 2.42, suggesting that not all of the nitrogen atoms are boxhed to three silicon atoms, but 58% twofold (─N─) and 42% threefold (>N─) nitrogens coexist in the present Na-Si-O-N oxynitride glass. The formation of twofold nitrogens may arise from the reaction between ≡Si─O⁻ and ≡Si₃N groups. This model is compatible with the experimental observation that the density and Vickers hardness of oxynitride glasses increase with the nitrogen content.