First-principles study on the electronic, elastic and thermodynamic properties of three novel germanium nitrides

The ultrasoft pseudo-potential plane wave method combined with the quasi-harmonic approach have been used to study the electronic, elastic and thermodynamic properties of the tetragonal, monoclinic and or- thorhombic Ge3N4. The negative formation enthalpies, the satisfactory of Born＇s criteria and the linear variations of elastic constants with pressure indicate that the three polymorphs can retain their stabilities in the pressure range of 0-25 GPa. The three GeaN4 are brittle solids at 0 GPa, while they behave in ductile manners in the pressure range of 5-25 GPa. t- and o-GeaN4 are hard materials but anisotropic, m-Ge3N4 has the largest ductility among the three phases. The results reveal that m-Ge3N4 belongs to an indirect band gap semiconductor, while t- and o-Ge3N4 have direct band gaps. For the thermal properties, several interesting features can be observed above 300 K. o-GeaN4 exhibits the largest heat capacity, while m-Ge3N4 shows the highest Debye temperature. The results predicted in this work can provide reference data for future experiments.