Crystalline phase and orientation control of manganese nitride grown on MgO(001) by molecular beam epitaxy

The phase and orientation of manganese nitride grown on MgO(001) using molecular beam epitaxy are shown to be controllable by the manganese/nitrogen flux ratio as well as the substrate temperature. The most N-rich phase, θ phase (MnN), is obtained at very low Mn/N flux ratio. At increased Mn/N flux ratio, the next most N-rich phase, the η phase (Mn3N2), is obtained having its c axis normal to the surface plane. Further increasing the Mn/N flux ratio, the η phase (Mn3N2) having its c axis in the surface plane is obtained. Finally, the ε phase (Mn4N) is obtained at yet higher Mn/N flux ratio. The structural phase variation with Mn/N flux ratio is due to the kinetic control of the surface chemical composition, which determines the energetically most favorable phase. For a given Mn/N flux ratio, the phase is also found to be a function of the substrate temperature, with the less N-rich phase occurring at the higher substrate temperature. The change of phase with temperature is attributed to the change in the chemical composition resulting from the diffusion of N vacancies. Since the magnetic properties of MnxNy depend on the phase, the Mn/N flux ratio provides a way of directly controlling the magnetic properties. A phase diagram for molecular beam epitaxial growth is presented.