Multiscale drainage dynamics with Haines jumps monitored by stroboscopic 4D X-ray microscopy.

Slow multiphase flow in porous media is intriguing because its underlying dynamics is almost deterministic, yet depends on a hierarchy of spatiotemporal processes. There has been great progress in the experimental study of such multiphase flows, but three-dimensional (3D) microscopy methods probing the pore-scale fluid dynamics with millisecond resolution have been lacking. Yet, it is precisely at these length and time scales that the crucial pore-filling events known as Haines jumps take place. Here, we report four-dimensional (4D) (3D + time) observations of multiphase flow in a consolidated porous medium as captured in situ by stroboscopic X-ray micro-tomography. With a total duration of 6.5 s and 2 kHz frame rate, our experiments provide unprecedented access to the multiscale liquid dynamics. Our tomography strategy relies on the fact that Haines jumps, although irregularly spaced in time, are almost deterministic, and therefore repeatable during imbibition-drainage cycling. We studied the time-dependent flow pattern in a porous medium consisting of sintered glass shards. Exploiting the repeatability, we could combine the radiographic projections recorded under different angles during successive cycles into a 3D movie, allowing us to reconstruct pore-scale events, such as Haines jumps, with a spatiotemporal resolution that is two orders of magnitude higher than was hitherto possible. This high resolution allows us to explore the detailed interfacial dynamics during drainage, including fluid-front displacements and velocities. Our experimental approach opens the way to the study of fast, yet deterministic mesoscopic processes also other than flow in porous media.

High-resolution polarization-sensitive Fourier ptychography microscopy using a high numerical aperture dome illuminator.

Polarization-sensitive Fourier-ptychography microscopy (pFPM) allows for high resolution imaging while maintaining a large field of view, and without mechanical movements of optical-setup components. In contrast to ordinary light microscopes, pFPM provides quantitative absorption and phase information, for complex and birefringent specimens, with high resolution across a wide field of view. Using a semi-spherical home-built LED illumination array, a single polarizer, and a 10x /0.28NA objective, we experimentally demonstrate high performance pFPM with a synthesized NA of 1.1. Applying the standard quantitative method, a measured half-pitch resolution of 244 nm is achieved for the 1951 USAF resolution test target. As application examples, the polarimetric properties of a herbaceous flowering plant and the metastatic carcinoma of human liver cells are analyzed and quantitatively imaged.

In situ coherent X-ray diffraction imaging of radiation-induced mass loss in metal-polymer composite spheres.

A major limitation to the use of coherent X-ray diffraction imaging (CXDI) for imaging soft materials like polymers and biological tissue is that the radiation can cause extensive damage to the sample under investigation. In this study, CXDI has been used to monitor radiation-induced structural changes in metal-coated poly(methyl methacrylate) microspheres. Using a coherent undulator X-ray beam with 8.10 keV photon energy, 14 tomograms at a resolution of ∼30 nm were measured consecutively, which resulted in an accumulated dose of 30 GGy. The three-dimensional images confirmed that the polymer core was strongly affected by the absorbed dose, giving pronounced mass loss. Specifically, as the metal-polymer composite was exposed to the X-ray beam, a bubble-like region of reduced density grew within the composite, almost filling the entire volume within the thin metallic shell in the last tomogram. The bubble seemed to have its initiation point at a hole in the metal coating, emphasizing that the free polymer surface plays an important role in the degradation process. The irradiation of an uncoated polystyrene microsphere gave further evidence for mass loss at the free surface as the radius decreased with increased dose. The CXDI study was complemented by X-ray photon correlation spectroscopy, which proved efficient in establishing exposure dose limits. Our results demonstrate that radiation-induced structural changes at the tens of nanometer scale in soft materials can be followed as a function of dose, which is important for the further development of soft-matter technology.

Coexistence of helical morphologies in columnar stacks of star-shaped discotic hydrazones.

Discotic hydrazone molecules are of particular interest as they form discotic phases where the discs are rigidified by intramolecular hydrogen bonds. Here, we investigate the thermotropic behavior and solid-state organizations of three discotic hydrazone derivatives with dendritic groups attached to their outer peripheries, containing six, eight, and ten carbons of linear alkoxy chains. On the basis of two-dimensional wide angle X-ray scattering (2DWAXS), the elevated temperature liquid crystalline (LC) phases were assigned to a hexagonal columnar (Colh) organization with nontilted hydrazone discs for all three compounds. With WAXS, advanced solid-state nuclear magnetic resonance (SSNMR) techniques, and ab initio computations, the compounds with six and ten carbons of achiral alkoxy side chains were further subjected to studies at 25 °C, revealing complex crystalline phases with rigid columns and flexible side chains. This combined approach led to models of coexisting helical columnar stacking morphologies for both systems with two different tilt/pitch angles between successive hydrazone molecules. The differences in tilt/pitch angles between the two compounds illustrate that the columns with short alkoxy chains (six carbons) are more influenced by the presence of other stacks in their vicinity, while those with long side chains are less tilted due to a larger alkoxy (ten carbons) buffer zone. The formation of different packing morphologies in the crystalline phase of a columnar LC has rarely been reported so far, which suggests the possibility of complex stacking structures of similar organic LC systems, utilizing small molecules as potential materials for applications in organic electronics.

Tuning and Tracking of Coherent Shear Waves in Molecular Films.

We have determined the time-dependent displacement fields in molecular sub-micrometer thin films as response to femtosecond and picosecond laser pulse heating by time-resolved X-ray diffraction. This method allows a direct absolute determination of the molecular displacements induced by electron-phonon interactions, which are crucial for, for example, charge transport in organic electronic devices. We demonstrate that two different modes of coherent shear motion can be photoexcited in a thin film of organic molecules by careful tuning of the laser penetration depth relative to the thickness of the film. The measured response of the organic film to impulse heating is explained by a thermoelastic model and reveals the spatially resolved displacement in the film. Thereby, information about the profile of the energy deposition in the film as well as about the mechanical interaction with the substrate material is obtained.

X-Ray Nanoscopy of a Bulk Heterojunction.

Optimizing the morphology of bulk heterojunctions is known to significantly improve the photovoltaic performance of organic solar cells, but available quantitative imaging techniques are few and have severe limitations. We demonstrate X-ray ptychographic coherent diffractive imaging applied to all-organic blends. Specifically, the phase-separated morphology in bulk heterojunction photoactive layers for organic solar cells, prepared from a 50:50 blend of poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) and thermally treated for different annealing times is imaged to high resolution. Moreover, using a fast-scanning calorimetry chip setup, the nano-morphological changes caused by repeated thermal annealing applied to the same sample could be monitored. X-ray ptychography resolves to better than 100 nm the phase-segregated domains of electron donor and electron acceptor materials over a large field of view within the active layers. The quantitative phase contrast images further allow us to estimate the local volume fraction of PCBM across the photovoltaically active layers. The volume fraction gradient for different regions provides insight on the PCBM diffusion across the depletion zone surrounding PCBM aggregates. Phase contrast X-ray microscopy is under rapid development, and the results presented here are promising for future studies of organic-organic blends, also under in situ conditions, e.g., for monitoring the structural stability during UV-Vis irradiation.

Laser recrystallization and inscription of compositional microstructures in crystalline SiGe-core fibres.

Glass fibres with silicon cores have emerged as a versatile platform for all-optical processing, sensing and microscale optoelectronic devices. Using SiGe in the core extends the accessible wavelength range and potential optical functionality because the bandgap and optical properties can be tuned by changing the composition. However, silicon and germanium segregate unevenly during non-equilibrium solidification, presenting new fabrication challenges, and requiring detailed studies of the alloy crystallization dynamics in the fibre geometry. We report the fabrication of SiGe-core optical fibres, and the use of CO2 laser irradiation to heat the glass cladding and recrystallize the core, improving optical transmission. We observe the ramifications of the classic models of solidification at the microscale, and demonstrate suppression of constitutional undercooling at high solidification velocities. Tailoring the recrystallization conditions allows formation of long single crystals with uniform composition, as well as fabrication of compositional microstructures, such as gratings, within the fibre core.

Field-effect transistors based on self-organized molecular nanostripes.

Charge transport properties in organic semiconductors depend strongly on molecular order. Here we demonstrate field-effect transistors where drain current flows through a precisely defined array of nanostripes made of crystalline and highly ordered molecules. The molecular stripes are fabricated across the channel of the transistor by a stamp-assisted deposition of the molecular semiconductors from a solution. As the solvent evaporates, the capillary forces drive the solution to form menisci under the stamp protrusions. The solute precipitates only in the regions where the solution is confined by the menisci once the critical concentration is reached and self-organizes into molecularly ordered stripes 100-200 nm wide and a few monolayers high. The charge mobility measured along the stripes is 2 orders of magnitude larger than the values measured for spin-coated thin films.