Polyamorphism in Aluminum Nitride: A First Principles Molecular Dynamics Study

The high‐pressure behavior of amorphous aluminum nitride is investigated for the first time by means of ab initio molecular dynamics simulations. It is found to undergo two successive first‐order phase transformations with the application of pressure. The first one is a polyamorphic phase transition in which the low‐density amorphous phase transforms into a high‐density amorphous phase having an average coordination number of about 4.6. The high‐density amorphous structure transforms back to a low‐coordinated amorphous network upon pressure release but its density is higher than that of the original low‐density amorphous phase. The second phase change is the crystallization of the high‐density amorphous state into a rocksalt structure. A careful analysis suggests that the hexagonal‐like nanoclusters presented in amorphous aluminum nitride prevent the formation of a very dense amorphous phase (about sixfold coordinated) during the first phase transition and they act as a nucleation center for the crystallization process.