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

First-principles molecular dynamics is employed to describe the atomic structure of amorphous SiN, a non-stoichiometric compound belonging to the SixNy 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 Si3N4 since N is mostly threefold coordinated with Si. Si atoms can also be found coordinated to four N atoms as in Si3N4, 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 literature 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.

Automated summary

First-principles molecular dynamics is used to study the atomic structure of amorphous SiN. The Car-Parrinello approach is not suitable due to the peculiar electronic structure of SiN, so the Born-Oppenheimer approach is utilized to achieve significant ionic diffusion. Amorphous states are obtained at room temperature through rapid quenching. The atomic environment of N atoms is similar to that in stoichiometric Si3N4, and Si atoms can form both polar and non-polar bonds.