Significance: We successfully achieve unprecedentedly deep levels of supersaturation ( S ∼ 4.1) with KH ₂ PO ₄ (KDP) solutions by using a newly developed device that combines electrostatic levitation with Raman and X-ray scattering. Our study reveals two interesting phenomena. One is an existence of two different solution states, that is, low-concentration KDP solution (LCS) and high-concentration KDP solution (HCS). The other is an emergence of different crystallization paths that depend on the degree of supersaturation: ( i ) LCS to stable KDP crystal (tetrahedral structure), ( ii ) LCS to HCS to a metastable KDP crystal (monoclinic structure) to stable KDP crystal. This is a direct in situ observation of multiple pathways of nucleation in aqueous solution.

For over two decades, NaCl nucleation from a supersaturated aqueous solution has been predicted to occur via a two-step nucleation (TSN) mechanism, i.e., two sequential events, the formation of locally dense liquid regions followed by structural ordering. However, the formation of dense liquid regions in the very early stage of TSN has never been experimentally observed. By using a state-of-the-art technique, a combination of electrostatic levitation (ESL) and in situ synchrotron X-ray and Raman scatterings, we find experimental evidence that indicates the formation of dense liquid regions in NaCl bulk solution at an unprecedentedly high level of supersaturation (S = 2.31). As supersaturation increases, evolution of ion clusters leads to chemical ordering, but no topological ordering, which is a precursor for forming the dense disordered regions of ion clusters at the early stage of TSN. Moreover, as the ion clusters proceed to evolve under highly supersaturated conditions, we observe the breakage of the water hydration structure indicating the stability limit of the dense liquid regions, and thus leading to nucleation. The evolution of solute clusters and breakage of hydration in highly supersaturated NaCl bulk solution will provide new insights into the detailed mechanism of TSN for many other aqueous solutions.

X-ray photon correlation spectroscopy (XPCS) is a routine technique to study slow dynamics in complex systems at storage-ring sources. Achieving nanosecond time resolution with the conventional XPCS technique is, however, still an experimentally challenging task requiring fast detectors and sufficient photon flux. Here, the result of a nanosecond XPCS study of fast colloidal dynamics is shown by employing an adaptive gain integrating pixel detector (AGIPD) operated at frame rates of the intrinsic pulse structure of the storage ring. Correlation functions from single-pulse speckle patterns with the shortest correlation time of 192 ns have been calculated. These studies provide an important step towards routine fast XPCS studies at storage rings.

We characterize the spatial and temporal coherence properties of hard X-ray pulses from the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL, Pohang, Korea). The measurement of the single-shot speckle contrast, together with the introduction of corrections considering experimental conditions, allows obtaining an intrinsic degree of transverse coherence of 0.85 ± 0.06. In the Self-Amplified Spontaneous Emission regime, the analysis of the intensity distribution of X-ray pulses also provides an estimate for the number of longitudinal modes. For monochromatic and pink (i.e. natural bandwidth provided by the first harmonic of the undulator) beams, we observe that the number of temporal modes is 6.0 ± 0.4 and 90.0 ± 7.2, respectively. Assuming a coherence time of 2.06 fs and 0.14 fs for the monochromatic and pink beam respectively, we estimate an average X-ray pulse duration of 12.6 ± 1.0 fs.

We report on the first integrated apparatus for measuring surface and thermophysical properties and bulk structures of a highly supersaturated solution by combining electrostatic levitation with real-time laser/x-ray scattering. Even today, a proper characterization of supersaturated solutions far above their solubility limits is extremely challenging because heterogeneous nucleation sites such as container walls or impurities readily initiate crystallization before the measurements can be performed. In this work, we demonstrate simultaneous measurements of drying kinetics and surface tension of a potassium dihydrogen phosphate (KH₂PO₄) aqueous solution droplet and its bulk structural evolution beyond the metastable zone width limit. Our experimental finding shows that the noticeable changes of the surface properties are accompanied by polymerizations of hydrated monomer clusters. The novel electrostatic levitation apparatus presented here provides an effective means for studying a wide range of highly concentrated solutions and liquids in deep metastable states.

We investigate the effect of free carrier dynamics on heat transport in bulk crystalline Silicon following femtosecond optical excitation of varying fluences. By taking advantage of the dense 500 MHz standard fill pattern in the PLS-II storage ring, we perform high angular-resolution X-ray diffraction measurements on nanosecond-to-microsecond time-scales with femtometer spatial sensitivity. We find noticeably slowed lattice recovery at increasingly high excitation intensities. Modeling the temporal evolution of lattice displacements due to the migration of the near surface generated heat into the bulk requires reduced thermal diffusion coefficients. We attribute this pump-fluence dependent thermal transport behavior to two separate effects: first, the enhanced nonradiative recombination of free carriers, and, second, reduced size of the effective heat source in the material. These results demonstrate the capability of time-resolved X-ray scattering as an effective means to explore the connection between charge carrier dynamics and macroscopic transport properties.