KrF excimer laser annealing on ultrathin hydrogenated amorphous Si films with various initial Si thicknesses is carried out to obtain a single layer of nanocrystalline Si structures. It is found that Si nanograins can be obtained with the area density as high as 1011 cm-2 under the irradiation with suitable laser fluence. Raman and planar transmission electron microscopy are used to characterize the formation process of Si nanocrystals from amorphous phase. Moreover, a strong photoluminescence is observed at room temperature from well-relaxed nanocrystalline Si structures.