Polycrystalline thin films with an oriented direction of ε-Mn₄N along the (111) axis and of η-Mn₃N₂ along the (113) axis were prepared as a single phase by RF reactive magnetron sputtering method. A comparison of XPS spectral analysis with discrete Variational-Xα method showed that the N atoms in Mn-N compounds behave as a donor and govern the magnetic properties of the films. The ε-Mn₄N films was a single phase perovskait type crystal with lattice parameter 0.386 nm, and this films had properties of the ferrimagnetism with 1.1 μ_B per unit cell. The η-Mn₃N₂ films was face center tetragonal (a = 0.4205 nm, c = 1.2131 nm), and it had properties of antiferromagnetism with 0.4 μ_B per unit cell.