First-Principles Investigations of the Physical Properties of Experimentally Feasible Novel Aluminum Nitride Polytypes

We present the results of a first-principles study on the structural stability and electronic and optical properties of new aluminum nitride (AlN) polytypes. The study includes the experimentally or theoretically known phases of AlN wurtzite (WZ), zincblende (ZB), and rock salt (RS) structures, which complement the pressure-dependent phase diagram of this industrially important compound. In addition to the structures of AlN considered in previous studies, we evaluated the dynamic stability of various novel phases: viz., SiC(4H), ZnS(15R), BeO, 5-5, TiAs, NiAs, MoC, Li₂O₂, and NiS. These were predicted recently in a high-pressure data-mining study of more than 140000 variations of the AlN structure, which claimed that they were either stable or nearly stable, on the basis of first-principles calculations. On the basis of the new AlN polytypes, the physical properties of all considered phases were compared, and the common trends and differences were determined. According to the phonon band structure calculations, nine phases of these new polytypes are free from imaginary frequencies. This indicates an adequate dynamic stability and the experimental accessibility of the polytypes. Additionally, the calculated cohesive energies of the dynamically stable phases are comparable to those of WZ-AlN and those specified in the available literature. Furthermore, the observed electronic structures and optical properties indicate that the polytypism of AlN can be a practical tool for refining its physical and chemical properties. The new phases show significant potential for use in future electronic and optoelectronic applications of AlN.