Reaction characteristics of ultra-thin Ni films (5nm and 10nm) on undoped and highly doped (As-doped and B-doped) Si (100) substrates are investigated in this work. The sheet resistance (Rs) measurements confirm the existence of a NiSi salicidation process window with low Rs values within a certain annealing temperature range for all the samples except the one of Ni (5nm) on P+-Si (100) substrate (abnormal sample). The experimental results also show that the transition reaction to low resistivity phase NiSi is retarded on highly doped Si substrates regardless of the initial Ni film thickness. Micro-Raman and x-ray diffraction (XRD) measurement show that NiSi forms in the process window and NiSi2 forms in a higher temperature annealing process for all normal substrates. Auger electron spectroscopy (AES) results for the abnormal sample show that the high resistivity of the formation film is due to the formation of NiSi2.