Metal–silicon and silicide–silicon diodes were fabricated by depositing thin layers of the metals Hf, Zr, Mn, Ni, and Rh on 〈111〉 epilayers of silicon, and annealing to transform the metal–silicon junctions to silicide–silicon junctions. A formation of the silicides was followed, and the stoichiometries were determined by ion back‐scatter analysis. The compositions and approximate formation temperatures were (HfSi, 700 °C; HfSi2, 850 °C), (ZrSi2, 700 °C), (MnSi, ≈ 500 °C; MnSi1.7, 800 °C), (NiSi, ≈ 600 °C; NiSi2, 850 °C), (RhSi, 600 °C). These temperatures are below those of the liquid phase eutectica hence indicating that the silicide forms in solid–solid reactions. The barrier heights were measured by the photoelectric method, giving the values: (Hf, 0.81 eV; HfSi 0.73 eV), (Mn, 0.77 eV; MnSi, 0.76 eV; MnSi1.7, 0.72 eV), (Ni, 0.75 eV; NiSi2, 0.70 eV), (Rh, 0.80 eV; RhSi, 0.70 eV).