In the course of a systematic investigation of heavy ion-irradiated Fe/Si layers, we have studied atomic transport and phase formation induced by 22-keV 14N2+ ion implantation in 57Fe(30 nm)/Si bilayers at high fluences. We report here results obtained by Rutherford backscattering spectroscopy, X-ray diffraction, and conversion electron Mössbauer spectroscopy after implantation and post-implantation annealing treatments. The irradiations caused little sputtering, but significant interface mixing. During implantation, iron nitrides, but no silicides were formed, even at the highest nitrogen fluence of 2 × 1017 ions/cm 2. When heating these samples in vacuo up to 700°C, the iron-rich phases ε-Fe3N and γ-Fe4N were produced. Starting at 600°C the suicide phase β-FeSi2 was also identified.