Exploring fingerprints of ultrafast structural dynamics in molecular solutions with an X-ray laser.

We apply ultrashort X-ray laser pulses to track optically excited structural dynamics of [Ir2(dimen)4]2+ molecules in solution. In our exploratory study we determine angular correlations in the scattered X-rays, which comprise a complex fingerprint of the ultrafast dynamics. Model-assisted analysis of the experimental correlation data allows us to elucidate various aspects of the photoinduced changes in the excited molecular ensembles. We unambiguously identify that in our experiment the photoinduced transition dipole moments in [Ir2(dimen)4]2+ molecules are oriented perpendicular to the Ir-Ir bond. The analysis also shows that the ground state conformer of [Ir2(dimen)4]2+ with a larger Ir-Ir distance is mostly responsible for the formation of the excited state. We also reveal that the ensemble of solute molecules can be characterized with a substantial structural heterogeneity due to solvent influence. The proposed X-ray correlation approach offers an alternative path for studies of ultrafast structural dynamics of molecular ensembles in the liquid and gas phases.

Angular X-ray cross-correlation analysis applied to the scattering data in 3D reciprocal space from a single crystal.

An application of angular X-ray cross-correlation analysis (AXCCA) to the scattered intensity distribution measured in 3D reciprocal space from a single-crystalline sample is proposed in this work. Contrary to the conventional application of AXCCA, when averaging over many 2D diffraction patterns collected from different randomly oriented samples is required, the proposed approach provides an insight into the structure of a single specimen. This is particularly useful in studies of defect-rich samples that are unlikely to have the same structure. The application of the method is shown on an example of a qualitative structure determination of a colloidal crystal from simulated as well as experimentally measured 3D scattered intensity distributions.

Spatially resolved fluorescence of caesium lead halide perovskite supercrystals reveals quasi-atomic behavior of nanocrystals.

We correlate spatially resolved fluorescence (-lifetime) measurements with X-ray nanodiffraction to reveal surface defects in supercrystals of self-assembled cesium lead halide perovskite nanocrystals and study their effect on the fluorescence properties. Upon comparison with density functional modeling, we show that a loss in structural coherence, an increasing atomic misalignment between adjacent nanocrystals, and growing compressive strain near the surface of the supercrystal are responsible for the observed fluorescence blueshift and decreased fluorescence lifetimes. Such surface defect-related optical properties extend the frequently assumed analogy between atoms and nanocrystals as so-called quasi-atoms. Our results emphasize the importance of minimizing strain during the self-assembly of perovskite nanocrystals into supercrystals for lighting application such as superfluorescent emitters.

In situ characterization of crystallization and melting of soft, thermoresponsive microgels by small-angle X-ray scattering.

Depending on the volume fraction and interparticle interactions, colloidal suspensions can form different phases, ranging from fluids, crystals, and glasses to gels. For soft microgels that are made from thermoresponsive polymers, the volume fraction can be tuned by temperature, making them excellent systems to experimentally study phase transitions in dense colloidal suspensions. However, investigations of phase transitions at high particle concentration and across the volume phase transition temperature in particular, are challenging due to the deformability and possibility for interpenetration between microgels. Here, we investigate the dense phases of composite core-shell microgels that have a small gold core and a thermoresponsive microgel shell. Employing Ultra Small-Angle X-ray Scattering, we make use of the strong scattering signal from the gold cores with respect to the almost negligible signal from the shells. By changing the temperature we study the freezing and melting transitions of the system in situ. Using Bragg peak analysis and the Williamson-Hall method, we characterize the phase transitions in detail. We show that the system crystallizes into an rhcp structure with different degrees of in-plane and out-of-plane stacking disorder that increase upon particle swelling. We further find that the melting process is distinctly different, where the system separates into two different crystal phases with different melting temperatures and interparticle interactions.

High spatial coherence and short pulse duration revealed by the Hanbury Brown and Twiss interferometry at the European XFEL.

Second-order intensity interferometry was employed to study the spatial and temporal properties of the European X-ray Free-Electron Laser (EuXFEL). Measurements were performed at the soft x-ray Self-Amplified Spontaneous Emission (SASE3) undulator beamline at a photon energy of 1.2 keV in the Self-Amplified Spontaneous Emission (SASE) mode. Two high-power regimes of the SASE3 undulator settings, i.e., linear and quadratic undulator tapering at saturation, were studied in detail and compared with the linear gain regime. The statistical analysis showed an exceptionally high degree of spatial coherence up to 90% for the linear undulator tapering. Analysis of the measured data in spectral and spatial domains provided an average pulse duration of about 10 fs in our measurements. The obtained results will be valuable for the experiments requiring and exploiting short pulse duration and utilizing high coherence properties of the EuXFEL.

Correction: Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging.

Correction for 'Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging' by Jerome Carnis et al., Nanoscale, 2021, DOI: 10.1039/D1NR01806J.

Exploring the 3D structure and defects of a self-assembled gold mesocrystal by coherent X-ray diffraction imaging.

Mesocrystals are nanostructured materials consisting of individual nanocrystals having a preferred crystallographic orientation. On mesoscopic length scales, the properties of mesocrystals are strongly affected by structural heterogeneity. Here, we report the detailed structural characterization of a faceted mesocrystal grain self-assembled from 60 nm sized gold nanocubes. Using coherent X-ray diffraction imaging, we determined the structure of the mesocrystal with the resolution sufficient to resolve each gold nanoparticle. The reconstructed electron density of the gold mesocrystal reveals its intrinsic structural heterogeneity, including local deviations of lattice parameters, and the presence of internal defects. The strain distribution shows that the average superlattice obtained by angular X-ray cross-correlation analysis and the real, "multidomain" structure of a mesocrystal are very close to each other, with a deviation less than 10%. These results will provide an important impact to understanding the fundamental principles of structuring and self-assembly including ensuing properties of mesocrystals.

Structure-Transport Correlation Reveals Anisotropic Charge Transport in Coupled PbS Nanocrystal Superlattices.

The assembly of colloidal semiconductive nanocrystals into highly ordered superlattices predicts novel structure-related properties by design. However, those structure-property relationships, such as charge transport depending on the structure or even directions of the superlattice, have remained unrevealed so far. Here, electric transport measurements and X-ray nanodiffraction are performed on self-assembled lead sulfide nanocrystal superlattices to investigate direction-dependent charge carrier transport in microscopic domains of these materials. By angular X-ray cross-correlation analysis, the structure and orientation of individual superlattices is determined, which are directly correlated with the electronic properties of the same microdomains. By that, strong evidence for the effect of superlattice crystallinity on the electric conductivity is found. Further, anisotropic charge transport in highly ordered monocrystalline domains is revealed, which is attributed to the dominant effect of shortest interparticle distance. This implies that transport anisotropy should be a general feature of weakly coupled nanocrystal superlattices.

Revealing Grain Boundaries and Defect Formation in Nanocrystal Superlattices by Nanodiffraction.

X-ray nanodiffraction is applied to study the formation and correlation of domain boundaries in mesocrystalline superlattices of PbS nanocrystals with face-centered cubic structure. Each domain of the superlattice can be described with one of two mesocrystalline polymorphs with different orientational orders. Close to a grain boundary, the lattice constant decreases and the superlattice undergoes an out-of-plane rotation, while the orientation of the nanocrystals with respect to the superlattice remains unchanged. These findings are explained with the release of stress on the expense of specific nanocrystal-substrate interactions. The fact that correlations between adjacent nanocrystals are found to survive the structural changes at most grain boundaries implies that the key to nanocrystal superlattices with macroscopic domain sizes are strengthened interactions with the substrate.

Parylene Based Memristive Devices with Multilevel Resistive Switching for Neuromorphic Applications.

In this paper, the resistive switching and neuromorphic behaviour of memristive devices based on parylene, a polymer both low-cost and safe for the human body, is comprehensively studied. The Metal/Parylene/ITO sandwich structures were prepared by means of the standard gas phase surface polymerization method with different top active metal electrodes (Ag, Al, Cu or Ti of ~500 nm thickness). These organic memristive devices exhibit excellent performance: low switching voltage (down to 1 V), large OFF/ON resistance ratio (up to 104), retention (≥104 s) and high multilevel resistance switching (at least 16 stable resistive states in the case of Cu electrodes). We have experimentally shown that parylene-based memristive elements can be trained by a biologically inspired spike-timing-dependent plasticity (STDP) mechanism. The obtained results have been used to implement a simple neuromorphic network model of classical conditioning. The described advantages allow considering parylene-based organic memristors as prospective devices for hardware realization of spiking artificial neuron networks capable of supervised and unsupervised learning and suitable for biomedical applications.

Planar and 3D fibrous polyaniline-based materials for memristive elements.

The memristive elements constructed using polymers - polyaniline (PANI) and polyethyleneoxide (PEO) - could be assembled on planar thin films or on 3D fibrous materials. Planar conductive PANI-based materials were made using the Langmuir-Schaefer (LS) method, and the 3D materials - using the electrospinning method which is a scalable technique. We have analyzed the influence of PANI molar mass, natures of solvent and subphase on the crystalline structure, thickness and conductivity of planar LS films, and the influence of PANI molar mass and the PANI-PEO ratio on the morphological and structural characteristics of 3D fibrous materials.