The formation of a pre-silicide layer below Ni1−xPtxSi films is reported with structure and composition distinctly different from previously observed diffusion layers. It was found that during two-step rapid thermal annealing Ni interstitial diffusion can kinetically dominate over the formation of Ni silicide, which results in a metastable pre-silicide layer. Aberration corrected scanning transmission electron microscopy experiments have revealed Ni to occupy interstitial and substitutional sites in the pre-silicide layer. Rapid thermal annealing and Pt alloying determines the stoichiometry and thickness of the layer, while the point defect configurations give rise to lowering of the associated Schottky barrier heights. The pre-silicide layer effectively limits diffusion of Ni into the substrate and therefore allows for the low-temperature growth of Ni2Si and NiSi.