High pressure modifications in amorphous boron suboxide: An ab initio study

Using constant pressure ab initio calculations, we probe the high-pressure modifications in amorphous boron suboxide (B₆O) consisting of glassy boron trioxide (B₂O₃) and boron (B) domains up to a theoretical pressure of 100 GPa. At this pressure, the structure remains amorphous. We find a steady increase in the average coordination of both B and oxygen (O) atoms. O atoms mostly attain threefold coordination as in B₂O₃ glass at high pressures. On the other hand, the mean coordination number of B-atoms reaches six at high pressures and the structural changes in B-rich regions are perceived to be quite analogous to those of amorphous B. B₁₂ clusters are found to persevere during the pressurizing process and the high-pressure modifications occur predominantly around O-atoms and the regions that connect the pentagonal pyramid-like motifs to each other. Upon pressure release, some high-pressure configurations persist in the model and another noncrystalline structure being about 10% denser than the original state is recovered, suggesting a permanent densification and a possible irreversible amorphous-to-amorphous phase transformation in B₆O. The recovered network shows slightly better mechanical properties than the uncompressed model. During the compression and decompression processes, amorphous B₆O remains semiconducting. The delocalization of some band tail states is seen at high pressures.