Localization properties of vibrational modes in $a$-Si3N4

TL;DR

This study uses first-principles calculations to analyze vibrational mode localization in amorphous silicon nitride, revealing how specific modes relate to atomic motions and how localization varies with frequency.

Contribution

It provides a detailed first-principles analysis of vibrational mode localization and atomic motion contributions in amorphous silicon nitride, including the effects of potential N--N bonds.

Findings

Modes above 600 cm$^{-1}$ become more localized and exhibit optic-like behavior.

Infrared peaks at 471 cm$^{-1}$ and 825 cm$^{-1}$ are linked to specific atomic motions.

Localization increases with frequency, especially above 1000 cm$^{-1}$.

Abstract

We present a first-principles investigation of the localization properties of vibrational modes in amorphous silicon nitride ($a$-Si$_3$N$_4$). Our investigation further confirms that the vibrational modes underlying the peak at $\sim$471 cm$^{-1}$ in the infrared spectrum of silicon nitride mainly consist of nitrogen motion in the direction normal to the plane defined by the three Si nearest neighbors. In-plane stretching of N--Si bonds becomes largely dominant above $\sim$700 cm$^{-1}$. In particular vibrational modes underlying the infrared peak at 825 cm$^{-1}$ arise from the N--Si bond stretching motions. If N--N homopolar bonds were present, we show that N--N bond stretching occurs above $\sim$1100 cm$^{-1}$. Furthermore, we investigate the localization properties of vibrational modes by calculating their inverse participation ratio (IPR) and phase quotient. From this analysis we infer that modes above 600 cm$^{-1}$ shows a progressive increase of the localization degree and optic-like behavior, especially above 1000 cm$^{-1}$. At about 650 cm$^{-1}$, given the considerable IPR value, and on the basis of projectional analysis on silicon-breathing-like motions of the NSi$_3$ units, we suggest that vibrational modes may involve correlated motions of neighboring SiN$_4$ tetrahedra.