Femtosecond time-resolved small and wide-angle x-ray diffuse scattering techniques are applied to investigate the ultrafast nucleation processes that occur during the ablation process in semiconducting materials. Following intense optical excitation, a transient liquid state of high compressibility characterized by large-amplitude density fluctuations is observed and the build-up of these fluctuations is measured in real-time. Small-angle scattering measurements reveal the first steps in the nucleation of nanoscale voids below the surface of the semiconductor and support MD simulations of the ablation process.