Controlling the morphology of laser-derived nanomaterials is dependent on developing a better understanding of the particle nucleation dynamics in the ablation plume. Here, we utilize the femtosecond-length pulses from an x-ray free electron laser to perform time-resolved grazing incidence x-ray scattering measurements on a laser-produced silicon plasma plume. At 20 ps we observe a dramatic increase in the scattering amplitude at small scattering vectors, which we attribute to incipient formation of liquid silicon droplets. These results demonstrate the utility of XFELs as a tool for characterizing the formation dynamics of nanomaterials in laser-produced plasma plumes on ultrafast timescales.

Nonlinear optical processes at soft x-ray wavelengths have remained largely unexplored due to the lack of available light sources with the requisite intensity and coherence. Here we report the observation of soft x-ray second harmonic generation near the carbon K edge (∼284  eV) in graphite thin films generated by high intensity, coherent soft x-ray pulses at the FERMI free electron laser. Our experimental results and accompanying first-principles theoretical analysis highlight the effect of resonant enhancement above the carbon K edge and show the technique to be interfacially sensitive in a centrosymmetric sample with second harmonic intensity arising primarily from the first atomic layer at the open surface. This technique and the associated theoretical framework demonstrate the ability to selectively probe interfaces, including those that are buried, with elemental specificity, providing a new tool for a range of scientific problems.