Atomic structure of amorphous SiN: combining Car-Parrinello and Born-Oppenheimer first-principles molecular dynamics

TL;DR

This study employs combined Car-Parrinello and Born-Oppenheimer molecular dynamics to accurately model the atomic structure of amorphous SiN, overcoming electronic structure challenges at high temperatures.

Contribution

It introduces a hybrid simulation approach to better capture the amorphous SiN structure, with improved statistical accuracy and room temperature relevance.

Findings

N atoms are mostly threefold coordinated with Si, similar to Si3N4.

Si atoms show diverse coordination, including homopolar Si-Si bonds.

Results align with previous models but offer higher accuracy and room temperature reference.

Abstract

First-principles molecular dynamics is employed to describe the atomic structure of amorphous SiN, a non-stoichiometric compound belonging to the Si$_x$N$_{y}$ family. To produce the amorphous state via the cooling of the liquid, both the Car-Parrinello and the Born-Oppenheimer approaches are exploited to obtain a system featuring sizeable atomic mobility. At high temperatures, due to the peculiar electronic structure of SiN, exhibiting gap closing effects, the Car-Parrinello methodology could not be followed since non-adiabatic effects involving the ionic and electronic degrees of freedom do occur. This shortcoming was surmounted by resorting to the Born-Oppenheimer approach allowing to achieve significant ionic diffusion at $T$= 2500 K. From this highly diffusive sample, an amorphous state at room temperature was obtained with a quenching rate of 10 K/ps. Four different models were created, differing by their sizes and the thermal cycles. We found that the subnetwork of atoms N has the same environment than in the stoichiometric material Si$_3$N$_4$ since N is mostly threefold coordinated with Si. Si atoms can also be found coordinated to four N atoms as in Si$_3$N$_4$, but a substantial fraction of them forms homopolar bonds with one, two, three and even four Si. Our results are not too dissimilar from former models available in the litterature but they feature a higher statistical accuracy and refer more precisely to room temperature as the reference thermodynamical condition for the analysis of the structure in the amorphous state.