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 buildup of these fluctuations is measured in real time. Small-angle scattering measurements reveal snapshots of the spontaneous nucleation of nanoscale voids within a metastable liquid and support theoretical predictions of the ablation process. DOI: 10.1103/PhysRevLett.100.135502 PACS numbers: 79.20.Ds, 61.05.cp, 61.20.Lc, 64.60.ÿi The liquid state of matter can be both supercooled below its freezing point and superheated above its boiling point. Although these are nonequilibrium states, their lifetime is longer than typical laboratory observation times and they are thus classified as metastable, stuck in a local minimum of the free energy. Despite their apparent stability, these systems exhibit localized fluctuations, corresponding to nuclei of the lower energy phase which rapidly form and dissolve, a process for which there exists a critical size for stable growth of the equilibrium phase, typically of nanoscale dimensions [1-3] (depending on the degree of superheating). When the transition does occur, it occurs rapidly, as is familiar to anyone who has observed the catastrophic boiling that suddenly occurs in superheated liquid water [4]. The development of ultrafast, atomic-scale sensitive techniques enables one to capture these transient, intermediate states, which under current laboratory methods, may spontaneously transform to lower energy stable states on inaccessible time scales. Techniques like time-resolved x-ray or electron scattering record these intermediate states in the form of a diffuse scattering pattern whose shape reflects the local atomic-scale structure that characterizes the transforming material. As a result of the orientational isotropy in the system and the short correlation lengths, these are typically broad diffraction rings, in contrast to the well-defined diffracted beams one obtains from a crystalline system. The radially averaged diffracted intensity as a function of scattering angle (normalized by atomic scattering factors) is a direct measure of the liquid structure factor S Q , where Q 4 sin = is the momentum transfer, 2 is the scattering angle, and is the wavelength, which directly encodes the short-range correlations in disordered materials.Recent experiments probing atomic-scale dynamics in disordered systems using electron diffraction techniques have focused on gas-phase photochemical reactions [5],