In situ aggregation and early states of gelation of gold nanoparticle dispersions.

The aggregation and onset of gelation of PEGylated gold nanoparticles dispersed in a glycerol-water mixture is studied by small-angle X-ray scattering and X-ray photon correlation spectroscopy. Tracking structural dynamics with sub-ms time resolution over a total experimental time of 8 hours corresponding to a time windows larger than 108 Brownian times and varying the temperature between 298 K and 266 K we can identify three regimes. First, while cooling to 275 K the particles show Brownian motion that slows down due to the increasing viscosity. Second, upon further cooling the static structure changes significantly, indicated by a broad structure factor peak. We attribute this to the formation of aggregates while the dynamics are still dominated by single-particle diffusion. Finally, the relaxation functions become more and more stretched accompanied by an increased slow down of the dynamics. At the same time the structure changes continuously indicating the onset of gelation. Our observations further suggest that the colloidal aggregation and gelation is characterized first by structural changes with a subsequent slowing down of the systems dynamics. The analysis also reveals that the details of the gelation process and the gel structure strongly depend on the thickness of the PEG-coating of the gold nanoparticles.

Emergence of anomalous dynamics in soft matter probed at the European XFEL.

Dynamics and kinetics in soft matter physics, biology, and nanoscience frequently occur on fast (sub)microsecond but not ultrafast timescales which are difficult to probe experimentally. The European X-ray Free-Electron Laser (European XFEL), a megahertz hard X-ray Free-Electron Laser source, enables such experiments via taking series of diffraction patterns at repetition rates of up to 4.5 MHz. Here, we demonstrate X-ray photon correlation spectroscopy (XPCS) with submicrosecond time resolution of soft matter samples at the European XFEL. We show that the XFEL driven by a superconducting accelerator provides unprecedented beam stability within a pulse train. We performed microsecond sequential XPCS experiments probing equilibrium and nonequilibrium diffusion dynamics in water. We find nonlinear heating on microsecond timescales with dynamics beyond hot Brownian motion and superheated water states persisting up to 100 µs at high fluences. At short times up to 20 µs we observe that the dynamics do not obey the Stokes-Einstein predictions.

Three-step colloidal gelation revealed by time-resolved x-ray photon correlation spectroscopy.

The gelation of PEGylated gold nanoparticles dispersed in a glycerol-water mixture is probed in situ by x-ray photon correlation spectroscopy. Following the evolution of structure and dynamics over 104 s, a three-step gelation process is found. First, a simultaneous increase of the Ornstein-Zernike length ξ and slowdown of dynamics is characterized by an anomalous q-dependence of the relaxation times of τ ∝ q-6 and strongly stretched intermediate scattering functions. After the structure of the gel network has been established, evidenced by a constant ξ, the dynamics show aging during the second gelation step accompanied by a change toward ballistic dynamics with τ ∝ q-1 and compressed correlation functions. In the third step, aging continues after the arrest of particle motion. Our observations further suggest that gelation is characterized by stress release as evidenced by anisotropic dynamics once gelation sets in.

Kinetics of pressure-induced nanocrystal superlattice formation.

Colloidal nanocrystals (NC) are known to self-organize into superlattices that promise many applications ranging from medicine to optoelectronics. Recently, the formation of high-quality PEGylated gold NC was reported at high hydrostatic pressure and high salt concentrations. Here, we study the formation kinetics of these superlattices after pressure jumps beyond their crystallisation pressure by means of small-angle X-ray scattering with few ms experimental resolution. The timescale of NC formation was found to be reduced the larger the width of the pressure jump. This is connected to an increase of crystal quality, i.e., the faster the NC superlattice forms, the better the crystal quality. In contrast to the formation kinetics, the melting of the NC superlattice is approximately one order of magnitude slower and shows linear kinetics.

Dynamics and Time Scales of Higher-Order Correlations in Supercooled Colloidal Systems.

The dynamics and time scales of higher-order correlations are studied in supercooled colloidal systems. A combination of X-ray photon correlation spectroscopy (XPCS) and X-ray cross-correlation analysis (XCCA) shows the typical slowing of the dynamics of a hard sphere system when approaching the glass transition. The time scales of higher-order correlations are probed using a novel time correlation function gC, tracking the time evolution of cross-correlation function C. With an increasing volume fraction, the ratio of relaxation times of gC to the standard individual particle relaxation time obtained by XPCS increases from ∼0.4 to ∼0.9. While a value of ∼0.5 is expected for free diffusion, the increasing values suggest that the local orders within the sample are becoming more long-lived for larger volume fractions. Furthermore, the dynamics of local order is more heterogeneous than the individual particle dynamics. These results indicate that not only the presence but also the lifetime of locally favored structures increases close to the glass transition.

Nanosecond X-ray photon correlation spectroscopy using pulse time structure of a storage-ring source.

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.

Microsecond hydrodynamic interactions in dense colloidal dispersions probed at the European XFEL.

Many soft-matter systems are composed of macromolecules or nanoparticles suspended in water. The characteristic times at intrinsic length scales of a few nanometres fall therefore in the microsecond and sub-microsecond time regimes. With the development of free-electron lasers (FELs) and fourth-generation synchrotron light-sources, time-resolved experiments in such time and length ranges will become routinely accessible in the near future. In the present work we report our findings on prototypical soft-matter systems, composed of charge-stabilized silica nanoparticles dispersed in water, with radii between 12 and 15 nm and volume fractions between 0.005 and 0.2. The sample dynamics were probed by means of X-ray photon correlation spectroscopy, employing the megahertz pulse repetition rate of the European XFEL and the Adaptive Gain Integrating Pixel Detector. We show that it is possible to correctly identify the dynamical properties that determine the diffusion constant, both for stationary samples and for systems driven by XFEL pulses. Remarkably, despite the high photon density the only observable induced effect is the heating of the scattering volume, meaning that all other X-ray induced effects do not influence the structure and the dynamics on the probed timescales. This work also illustrates the potential to control such induced heating and it can be predicted with thermodynamic models.

Structural and electronic properties of ultrathin FeSe films grown on Bi2Se3(0 0 0 1) studied by STM/STS.

We report scanning tunnelling microscopy and spectroscopy (STM/STS) studies on one and two unit cell (UC) high FeSe thin films grown on Bi2Se3(0 0 0 1). In our thin films, we find the tetragonal phase of FeSe and dumb-bell shaped defects oriented along Se-Se bond directions. In addition, we observe striped moiré patterns with a periodicity of (7.3 ± 0.1) nm generated by the mismatch between the FeSe lattice and the Bi2Se3 lattice. We could not find any signature of a superconducting gap in the tunneling spectra measured on the surface of one and two UC thick islands of FeSe down to 6.5 K. The spectra rather show an asymmetric behavior across and a finite density of states at the Fermi level (E F) resembling those taken in the normal state of bulk FeSe.