Amorphous zirconia at high pressure

Abstract

We show, by means of ab initio calculations, that amorphous zirconia progressively transforms to a high‐density amorphous phase with the application of pressure. The average coordination number of Zr and O atoms under pressure rises gradually to 8 and 4, respectively. The main building unit of the dense noncrystalline state is the eightfold‐coordinated Zr atoms (62.5%). When the coordinated modification of Zr atoms in the zirconia crystal at high pressure and temperature conditions is considered, it can be perceived that amorphous zirconia follows a transformation mechanism similar to the one observed at high temperature but different than the one detected at high pressure. The dense disordered phase is indeed found to be locally comparable with the high‐temperature tetragonal crystal. Upon decompression, some high‐pressure arrangements are persevered in the model and a transformation into another amorphous state whose structure is intermediate between uncompressed and dense amorphous phases is observed in the simulations. The high‐pressure amorphous structures are found to be semiconductors with a band gap smaller than that of the original model.