Solid-state NMR investigations of Si-29 and N-15 enriched silicon nitride

We compare 29Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra from the two modifications of silicon nitride, α-Si3N4 and β-Si3N4, with that of a fully (29Si, 15N)-enriched sample 29Si315N4, as well as 15N NMR spectra of Si315N4 (having 29Si at natural abundance) and 29Si315N4. We show that the 15N NMR peak-widths from the latter are dominated by J(29Si-15N) through-bond interactions, leading to significantly broader NMR signals compared to those of Si315N4. By fitting calculated 29Si NMR spectra to experimental ones, we obtained an estimated coupling constant J(29Si-15N) of 20 Hz. We provide 29Si spin-lattice (T1) relaxation data for the 29Si315N4 sample and chemical shift anisotropy results for the 29Si site of β-Si3N4. Various factors potentially contributing to the 29Si and 15N NMR peak-widths of the various silicon nitride specimens are discussed. We also provide powder X-ray diffraction (XRD) and mass spectrometry data of the samples.