X-ray beam diagnostics at the MID instrument of the European X-ray Free-Electron Laser Facility.

The Materials Imaging and Dynamics (MID) instrument at the European X-ray Free-Electron Laser Facility (EuXFEL) is equipped with a multipurpose diagnostic end-station (DES) at the end of the instrument. The imager unit in DES is a key tool for aligning the beam to a standard trajectory and for adjusting optical elements such as focusing lenses or the split-and-delay line. Furthermore, the DES features a bent-diamond-crystal spectrometer to disperse the spectrum of the direct beam to a line detector. This enables pulse-resolved characterization of the EuXFEL spectrum to provide X-ray energy calibration, and the spectrometer is particularly useful in commissioning special modes of the accelerator. Together with diamond-based intensity monitors, the imager and spectrometer form the DES unit which also contains a heavy-duty beamstop at the end of the MID instrument. Here, we describe the setup in detail and provide exemplary beam diagnostic results.

Crystal Nucleation in Supercooled Atomic Liquids.

The liquid-to-solid phase transition is a complex process that is difficult to investigate experimentally with sufficient spatial and temporal resolution. A key aspect of the transition is the formation of a critical seed of the crystalline phase in a supercooled liquid, that is, a liquid in a metastable state below the melting temperature. This stochastic process is commonly described within the framework of classical nucleation theory, but accurate tests of the theory in atomic and molecular liquids are challenging. Here, we employ femtosecond x-ray diffraction from microscopic liquid jets to study crystal nucleation in supercooled liquids of the rare gases argon and krypton. Our results provide stringent limits to the validity of classical nucleation theory in atomic liquids, and offer the long-sought possibility of testing nonclassical extensions of the theory.

Imaging via Correlation of X-Ray Fluorescence Photons.

We demonstrate that x-ray fluorescence emission, which cannot maintain a stationary interference pattern, can be used to obtain images of structures by recording photon-photon correlations in the manner of the stellar intensity interferometry of Hanbury Brown and Twiss. This is achieved utilizing femtosecond-duration pulses of a hard x-ray free-electron laser to generate the emission in exposures comparable to the coherence time of the fluorescence. Iterative phasing of the photon correlation map generated a model-free real-space image of the structure of the emitters. Since fluorescence can dominate coherent scattering, this may enable imaging uncrystallised macromolecules.

Single-pulse phase-contrast imaging at free-electron lasers in the hard X-ray regime.

X-ray free-electron lasers (XFELs) have opened up unprecedented opportunities for time-resolved nano-scale imaging with X-rays. Near-field propagation-based imaging, and in particular near-field holography (NFH) in its high-resolution implementation in cone-beam geometry, can offer full-field views of a specimen's dynamics captured by single XFEL pulses. To exploit this capability, for example in optical-pump/X-ray-probe imaging schemes, the stochastic nature of the self-amplified spontaneous emission pulses, i.e. the dynamics of the beam itself, presents a major challenge. In this work, a concept is presented to address the fluctuating illumination wavefronts by sampling the configuration space of SASE pulses before an actual recording, followed by a principal component analysis. This scheme is implemented at the MID (Materials Imaging and Dynamics) instrument of the European XFEL and time-resolved NFH is performed using aberration-corrected nano-focusing compound refractive lenses. Specifically, the dynamics of a micro-fluidic water-jet, which is commonly used as sample delivery system at XFELs, is imaged. The jet exhibits rich dynamics of droplet formation in the break-up regime. Moreover, pump-probe imaging is demonstrated using an infrared pulsed laser to induce cavitation and explosion of the jet.

Nanosecond timing and synchronization scheme for holographic pump-probe studies at the MID instrument at European XFEL.

Single-pulse holographic imaging at XFEL sources with 1012 photons delivered in pulses shorter than 100 fs reveal new quantitative insights into fast phenomena. Here, a timing and synchronization scheme for stroboscopic imaging and quantitative analysis of fast phenomena on time scales (sub-ns) and length-scales (≲100 nm) inaccessible by visible light is reported. A fully electronic delay-and-trigger system has been implemented at the MID station at the European XFEL, and applied to the study of emerging laser-driven cavitation bubbles in water. Synchronization and timing precision have been characterized to be better than 1 ns.

Non-uniform nanosecond gate-delay of hybrid pixel detectors.

A simple experiment to characterize the gating properties of X-ray area detectors using pulsed X-ray sources is presented. For a number of time-resolved experiments the gating uniformity of area detectors is important. Relative gating delays between individual modules and readout chips of PILATUS2 series area X-ray detectors have been observed. For three modules of a PILATUS 300K-W unit the maximum gating offset between the modules is found to be as large as 30 ns. On average, the first photosensor module is found to be triggered 15 ns and 30 ns later than the second and the third modules, respectively.

Ultrafast switching of hard X-rays.

A new concept for shortening hard X-ray pulses emitted from a third-generation synchrotron source down to few picoseconds is presented. The device, called the PicoSwitch, exploits the dynamics of coherent acoustic phonons in a photo-excited thin film. A characterization of the structure demonstrates switching times of ≤ 5 ps and a peak reflectivity of ∼10(-3). The device is tested in a real synchrotron-based pump-probe experiment and reveals features of coherent phonon propagation in a second thin film sample, thus demonstrating the potential to significantly improve the temporal resolution at existing synchrotron facilities.

Real-time swelling-collapse kinetics of nanogels driven by XFEL pulses.

Stimuli-responsive polymers are an important class of materials with many applications in nanotechnology and drug delivery. The most prominent one is poly-N-isopropylacrylamide (PNIPAm). The characterization of the kinetics of its change after a temperature jump is still a lively research topic, especially at nanometer-length scales where it is not possible to rely on conventional microscopic techniques. Here, we measured in real time the collapse of a PNIPAm shell on silica nanoparticles with megahertz x-ray photon correlation spectroscopy at the European XFEL. We characterize the changes of the particles diffusion constant as a function of time and consequently local temperature on sub-microsecond timescales. We developed a phenomenological model to describe the observed data and extract the characteristic times associated to the swelling and collapse processes. Different from previous studies tracking the turbidity of PNIPAm dispersions and using laser heating, we find collapse times below microsecond timescales and two to three orders of magnitude slower swelling times.

Jetting bubbles observed by x-ray holography at a free-electron laser: internal structure and the effect of non-axisymmetric boundary conditions.

In this work, we study the jetting dynamics of individual cavitation bubbles using x-ray holographic imaging and high-speed optical shadowgraphy. The bubbles are induced by a focused infrared laser pulse in water near the surface of a flat, circular glass plate, and later probed with ultrashort x-ray pulses produced by an x-ray free-electron laser (XFEL). The holographic imaging can reveal essential information of the bubble interior that would otherwise not be accessible in the optical regime due to obscuration or diffraction. The influence of asymmetric boundary conditions on the jet's characteristics is analysed for cases where the axial symmetry is perturbed and curved liquid filaments can form inside the cavity. The x-ray images demonstrate that when oblique jets impact the rigid boundary, they produce a non-axisymmetric splash which grows from a moving stagnation point. Additionally, the images reveal the formation of complex gas/liquid structures inside the jetting bubbles that are invisible to standard optical microscopy. The experimental results are analysed with the assistance of full three-dimensional numerical simulations of the Navier-Stokes equations in their compressible formulation, which allow a deeper understanding of the distinctive features observed in the x-ray holographic images. In particular, the effects of varying the dimensionless stand-off distances measured from the initial bubble location to the surface of the solid plate and also to its nearest edge are addressed using both experiments and simulations. A relation between the jet tilting angle and the dimensionless bubble position asymmetry is derived. The present study provides new insights into bubble jetting and demonstrates the potential of x-ray holography for future investigations in this field. Supplementary Information: The online version contains supplementary material available at 10.1007/s00348-023-03759-9.

Ultrafast orbital tomography of a pentacene film using time-resolved momentum microscopy at a FEL.

Time-resolved momentum microscopy provides insight into the ultrafast interplay between structural and electronic dynamics. Here we extend orbital tomography into the time domain in combination with time-resolved momentum microscopy at a free-electron laser (FEL) to follow transient photoelectron momentum maps of excited states of a bilayer pentacene film on Ag(110). We use optical pump and FEL probe pulses by keeping FEL source conditions to minimize space charge effects and radiation damage. From the momentum microscopy signal, we obtain time-dependent momentum maps of the excited-state dynamics of both pentacene layers separately. In a combined experimental and theoretical study, we interpret the observed signal for the bottom layer as resulting from the charge redistribution between the molecule and the substrate induced by excitation. We identify that the dynamics of the top pentacene layer resembles excited-state molecular dynamics.

Resolving molecular diffusion and aggregation of antibody proteins with megahertz X-ray free-electron laser pulses.

X-ray free-electron lasers (XFELs) with megahertz repetition rate can provide novel insights into structural dynamics of biological macromolecule solutions. However, very high dose rates can lead to beam-induced dynamics and structural changes due to radiation damage. Here, we probe the dynamics of dense antibody protein (Ig-PEG) solutions using megahertz X-ray photon correlation spectroscopy (MHz-XPCS) at the European XFEL. By varying the total dose and dose rate, we identify a regime for measuring the motion of proteins in their first coordination shell, quantify XFEL-induced effects such as driven motion, and map out the extent of agglomeration dynamics. The results indicate that for average dose rates below 1.06 kGy µs-1 in a time window up to 10 µs, it is possible to capture the protein dynamics before the onset of beam induced aggregation. We refer to this approach as correlation before aggregation and demonstrate that MHz-XPCS bridges an important spatio-temporal gap in measurement techniques for biological samples.

Hydrogen Solubility and Atomic Structure of Graphene Supported Pd Nanoclusters.

We investigated the atomic structure of graphene supported Pd nanoclusters and their interaction with hydrogen up to atmospheric pressures at room temperature by surface X-ray diffraction and scanning tunneling microscopy. We find that Ir seeded Pd nanocluster superlattices with 1.2 nm cluster diameters can be grown on the graphene/Ir(111) moiré template with high structural perfection. The superlattice clusters are anchored through the rehybridized graphene to the Ir support, which superimposes a 2.0% inplane compression onto the clusters. During hydrogen exposure at 10 mbar pressure and room temperature, a significant part of the clusters gets unpinned from the superlattice. The clusters in registry undergo an out-of-plane expansion only, whereas the detached clusters expand in in- and out-of-plane directions. The formation of a hydrogen rich PdHx α' phase was not observed. After exposure to 1 bar, the majority of the clusters are unpinned from superlattice sites, due to their surface interaction with hydrogen and possible spill over to the graphene support. Only minor sintering was observed, which is more pronounced for the unpinned clusters. The results give evidence that ultrasmall Pd clusters on graphene are a stable hydrogen storage system with reduced hydrogen storage hysteresis and maintain a large surface area for hydrogen chemisorption.

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.

Ultrafast lattice response of photoexcited thin films studied by X-ray diffraction.

Using ultrafast X-ray diffraction, we study the coherent picosecond lattice dynamics of photoexcited thin films in the two limiting cases, where the photoinduced stress profile decays on a length scale larger and smaller than the film thickness. We solve a unifying analytical model of the strain propagation for acoustic impedance-matched opaque films on a semi-infinite transparent substrate, showing that the lattice dynamics essentially depend on two parameters: One for the spatial profile and one for the amplitude of the strain. We illustrate the results by comparison with high-quality ultrafast X-ray diffraction data of SrRuO3 films on SrTiO3 substrates.

Kinetic optimum of volmer-weber growth.

We find that the molecular beam epitaxy of Fe3Si on GaAs(001) observed by real-time x-ray diffraction begins by the abrupt formation of 3 monolayer (ML) high islands and approaches two-dimensional layer-by-layer growth at a thickness of 7 ML. A surface energy increase is confirmed by ab initio calculations and allows us to identify the growth as a strain-free Volmer-Weber transient. Kinetic Monte Carlo simulations incorporating this energy increase correctly reproduce the characteristic x-ray intensity oscillations found in the experiment. Simulations indicate an optimum growth rate for Volmer-Weber growth in between two limits, the appearance of trenches at slow growth and surface roughening at fast growth.