The authors have studied the reaction between a Ge (100) substrate and thin layers of Ni ranging from 2 to 10 nm in thickness. The formation of metal-rich Ni5Ge3 was found to precede that of the monogermanide NiGe by means of real-time in situ x-ray diffraction during ramp-annealing and ex situ x-ray pole figure analyses for phase identification. The observed sequential growth of Ni5Ge3 and NiGe with such thin Ni layers is different from the previously reported simultaneous growth with thicker Ni layers. The phase transformation from Ni5Ge3 to NiGe was found to be nucleation-controlled for Ni thicknesses <5 nm, which is well supported by thermodynamic considerations. Specifically, the temperature for the NiGe formation increased with decreasing Ni (rather Ni5Ge3) thickness below 5 nm. In combination with sheet resistance measurement and microscopic surface inspection of samples annealed with a standard rapid thermal processing, the temperature range for achieving morphologically stable NiGe layers was identified for this standard annealing process. As expected, it was found to be strongly dependent on the initial Ni thickness.