Metasurface-Enabled Holographic Lithography for Impact-Absorbing Nanoarchitected Sheets.

Nanoarchitected materials represent a class of structural meta-materials that utilze nanoscale features to achieve unconventional material properties such as ultralow density and high energy absorption. A dearth of fabrication methods capable of producing architected materials with sub-micrometer resolution over large areas in a scalable manner exists. A fabrication technique is presented that employs holographic patterns generated by laser exposure of phase metasurface masks in negative-tone photoresists to produce 30-40 µm-thick nanoarchitected sheets with 2.1 × 2.4 cm2 lateral dimensions and ≈500 nm-wide struts organized in layered 3D brick-and-mortar-like patterns to result in ≈50-70% porosity. Nanoindentation arrays over the entire sample area reveal the out-of-plane elastic modulus to vary between 300 MPa and 4 GPa, with irrecoverable post-elastic material deformation commencing via individual nanostrut buckling, densification within layers, shearing along perturbation perimeter, and tensile cracking. Laser induced particle impact tests (LIPIT) indicate specific inelastic energy dissipation of 0.51-2.61 MJ kg-1 , which is comparable to other high impact energy absorbing composites and nanomaterials, such as Kevlar/poly(vinyl butyral) (PVB) composite, polystyrene, and pyrolized carbon nanolattices with 23% relative density. These results demonstrate that holographic lithography offers a promising platform for scalable manufacturing of nanoarchitected materials with impact resistant capabilities.

Exploration of the X-ray Dark-Field Signal in Mineral Building Materials.

Mineral building materials suffer from weathering processes such as salt efflorescence, freeze-thaw cycling, and microbial colonization. All of these processes are linked to water (liquid and vapor) in the pore space. The degree of damage following these processes is heavily influenced by pore space properties such as porosity, pore size distribution, and pore connectivity. X-ray computed micro-tomography (µCT) has proven to be a valuable tool to non-destructively investigate the pore space of stone samples in 3D. However, a trade-off between the resolution and field-of-view often impedes reliable conclusions on the material's properties. X-ray dark-field imaging (DFI) is based on the scattering of X-rays by sub-voxel-sized features, and as such, provides information on the sample complementary to that obtained using conventional µCT. In this manuscript, we apply X-ray dark-field tomography for the first time on four mineral building materials (quartzite, fired clay brick, fired clay roof tile, and carbonated mineral building material), and investigate which information the dark-field signal entails on the sub-resolution space of the sample. Dark-field tomography at multiple length scale sensitivities was performed at the TOMCAT beamline of the Swiss Light Source (Villigen, Switzerland) using a Talbot grating interferometer. The complementary information of the dark-field modality is most clear in the fired clay brick and roof tile; quartz grains that are almost indistinguishable in the conventional µCT scan are clearly visible in the dark-field owing to their low dark-field signal (homogenous sub-voxel structure), whereas the microporous bulk mass has a high dark-field signal. Large (resolved) pores on the other hand, which are clearly visible in the absorption dataset, are almost invisible in the dark-field modality because they are overprinted with dark-field signal originating from the bulk mass. The experiments also showed how the dark-field signal from a feature depends on the length scale sensitivity, which is set by moving the sample with respect to the grating interferometer.

Fast acquisition protocol for X-ray scattering tensor tomography.

Microstructural information over an entire sample is important to understand the macroscopic behaviour of materials. X-ray scattering tensor tomography facilitates the investigation of the microstructural organisation in statistically large sample volumes. However, established acquisition protocols based on scanning small-angle X-ray scattering and X-ray grating interferometry inherently require long scan times even with highly brilliant X-ray sources. Recent developments in X-ray diffractive optics towards circular pattern arrays enable fast single-shot acquisition of the sample scattering properties with 2D omnidirectional sensitivity. X-ray scattering tensor tomography with the use of this circular grating array has been demonstrated. We propose here simple yet inherently rapid acquisition protocols for X-ray scattering tensor tomography leveraging on these new optical elements. Results from both simulation and experimental data, supported by a null space analysis, suggest that the proposed acquisition protocols are not only rapid but also corroborate that sufficient information for the accurate volumetric reconstruction of the scattering properties is provided. The proposed acquisition protocols will build the basis for rapid inspection and/or time-resolved tensor tomography of the microstructural organisation over an extended field of view.

Tunable X-ray dark-field imaging for sub-resolution feature size quantification in porous media.

X-ray computed micro-tomography typically involves a trade-off between sample size and resolution, complicating the study at a micrometer scale of representative volumes of materials with broad feature size distributions (e.g. natural stones). X-ray dark-field tomography exploits scattering to probe sub-resolution features, promising to overcome this trade-off. In this work, we present a quantification method for sub-resolution feature sizes using dark-field tomograms obtained by tuning the autocorrelation length of a Talbot grating interferometer. Alumina particles with different nominal pore sizes (50 nm and 150 nm) were mixed and imaged at the TOMCAT beamline of the SLS synchrotron (PSI) at eighteen correlation lengths, covering the pore size range. The different particles cannot be distinguished by traditional absorption µCT due to their very similar density and the pores being unresolved at typical image resolutions. Nevertheless, by exploiting the scattering behavior of the samples, the proposed analysis method allowed to quantify the nominal pore sizes of individual particles. The robustness of this quantification was proven by reproducing the experiment with solid samples of alumina, and alumina particles that were kept separated. Our findings demonstrate the possibility to calibrate dark-field image analysis to quantify sub-resolution feature sizes, allowing multi-scale analyses of heterogeneous materials without subsampling.

Fabrication of X-ray Gratings for Interferometric Imaging by Conformal Seedless Gold Electroplating.

We present a method to produce small pitch gratings for X-ray interferometric imaging applications, allowing the phase sensitivity to be increased and/or the length of the laboratory setup to be minimized. The method is based on fabrication of high aspect ratio silicon microstructures using deep reactive ion etching (Bosch technique) of dense grating arrays and followed by conformal electroplating of Au. We demonstrated that low resistivity Si substrates (<0.01 Ohm·cm) enable the metal seeding layer deposition step to be avoided, which is normally required to initiate the electroplating process. Etching conditions were optimized to realize Si recess structures with a slight bottom tapering, which ensured the void-free Au filling of the trenches. Vapor HF was used to remove the native oxide layer from the Si grating surface prior to electroplating in the cyanide-based Au electrolyte. Fabrication of Au gratings with pitch in the range 1.2-3.0 µm was successfully realized. A substantial improved aspect ratio of 45:1 for a pitch size of 1.2 µm was achieved with respect to the prior art on 4-inch wafer-based technology. The fabricated Au gratings were tested with X-ray interferometers in Talbot-Laue configuration with measured visibility of 13% at an X-ray design energy of 26 keV.

Modeling of beam hardening effects in a dual-phase X-ray grating interferometer for quantitative dark-field imaging.

X-ray grating interferometry (XGI) can provide access to unresolved sub-pixel information by utilizing the so-called dark-field or visibility reduction contrast. A recently developed variant of conventional XGI named dual-phase grating interferometer, based only on phase-shifting structures, has allowed for straightforward micro-structural investigations over multiple length scales with conventional X-ray sources. Nonetheless, the theoretical framework of the image formation for the dark-field signal has not been fully developed yet, thus hindering the quantification of unresolved micro-structures. In this work, we expand the current theoretical formulation of dual-phase grating interferometers taking into account polychromatic sources and beam hardening effects. We propose a model that considers the contribution of beam hardening to the visibility reduction and accounts for it. Finally, the method is applied to previously acquired and new experimental data showing that discrimination between actual micro-structures and beam hardening effects can be achieved.

Metal assisted chemical etching of silicon in the gas phase: a nanofabrication platform for X-ray optics.

High aspect ratio nanostructuring requires high precision pattern transfer with highly directional etching. In this work, we demonstrate the fabrication of structures with ultra-high aspect ratios (up to 10 000 : 1) in the nanoscale regime (down to 10 nm) by platinum assisted chemical etching of silicon in the gas phase. The etching gas is created by a vapour of water diluted hydrofluoric acid and a continuous air flow, which works both as an oxidizer and as a gas carrier for reactive species. The high reactivity of platinum as a catalyst and the formation of platinum silicide to improve the stability of the catalyst pattern allow a controlled etching. The method has been successfully applied to produce straight nanowires with section size in the range of 10-100 nm and length of hundreds of micrometres, and X-ray optical elements with feature sizes down to 10 nm and etching depth in the range of tens of micrometres. This work opens the possibility of a low cost etching method for stiction-sensitive nanostructures and a large range of applications where silicon high aspect ratio nanostructures and high precision of pattern transfer are required.

Diffractive small angle X-ray scattering imaging for anisotropic structures.

Insights into the micro- and nano-architecture of materials is crucial for understanding and predicting their macroscopic behaviour. In particular, for emerging applications such as meta-materials, the micrometer scale becomes highly relevant. The micro-architecture of such materials can be tailored to exhibit specific mechanical, optical or electromagnetic behaviours. Consequently, quality control at micrometer scale must be guaranteed over extended areas. Mesoscale investigations over millimetre sized areas can be performed by scanning small angle X-ray scattering methods (SAXS). However, due to their long measurement times, real time or operando investigations are hindered. Here we present a method based on X-ray diffractive optics that enables the acquisition of SAXS signals in a single shot (few milliseconds) over extended areas. This method is applicable to a wide range of X-ray sources with varying levels of spatial coherence and monochromaticity, as demonstrated from the experimental results. This enables a scalable solution of spatially resolved SAXS.

Interpretation and Utility of the Moments of Small-Angle X-Ray Scattering Distributions.

Small angle x-ray scattering has been proven to be a valuable method for accessing structural information below the spatial resolution limit implied by direct imaging. Here, we theoretically derive the relation that links the subpixel differential phase signal provided by the sample to the moments of scattering distributions accessible by refraction sensitive x-ray imaging techniques. As an important special case we explain the scatter or dark-field contrast in terms of the sample's phase signal. Further, we establish that, for binary phase objects, the nth moment scales with the difference of the refractive index decrement to the power of n. Finally, we experimentally demonstrate the utility of the moments by quantitatively determining the particle sizes of a range of powders with a laboratory-based setup.

Anisotropic hydrodynamic function of dense confined colloids.

Dense colloidal dispersions exhibit complex wave-vector-dependent diffusion, which is controlled by both direct particle interactions and indirect nonadditive hydrodynamic interactions mediated by the solvent. In bulk the hydrodynamic interactions are probed routinely, but in confined geometries their studies have been hitherto hindered by additional complications due to confining walls. Here we solve this issue by combining high-energy x-ray photon correlation spectroscopy and small-angle x-ray-scattering experiments on colloid-filled microfluidic channels to yield the confined fluid's hydrodynamic function in the short-time limit. Most importantly, we find the confined fluid to exhibit a strongly anisotropic hydrodynamic function, similar to its anisotropic structure factor. This observation is important in order to guide future theoretical research.

Sub-pixel correlation length neutron imaging: Spatially resolved scattering information of microstructures on a macroscopic scale.

Neutron imaging and scattering give data of significantly different nature and traditional methods leave a gap of accessible structure sizes at around 10 micrometers. Only in recent years overlap in the probed size ranges could be achieved by independent application of high resolution scattering and imaging methods, however without providing full structural information when microstructures vary on a macroscopic scale. In this study we show how quantitative neutron dark-field imaging with a novel experimental approach provides both sub-pixel resolution with respect to microscopic correlation lengths and imaging of macroscopic variations of the microstructure. Thus it provides combined information on multiple length scales. A dispersion of micrometer sized polystyrene colloids was chosen as a model system to study gravity induced crystallisation of microspheres on a macro scale, including the identification of ordered as well as unordered phases. Our results pave the way to study heterogeneous systems locally in a previously impossible manner.

Visibility simulation of realistic grating interferometers including grating geometries and energy spectra.

The performance of X-ray and neutron grating interferometers is characterised by their visibility, which is a measure for the maximum achievable contrast. In this study we show how the real grating geometry in a grating interferometer with three gratings impacts the interference and self projection that leads to visibility in the first place. We quantify the individual contributions of wavelength distributions and grating shapes in terms of visibility reduction by determining the absolute as well as relative effect of each contribution. The understanding of the impact of changed geometry and wavelength distributions on the interference of neutrons/X-rays allows us to present the first fully quantitative model of a grating interferometer setup. We demonstrate the capability of the simulation framework by building a model of the neutron grating interferometer at the ICON beamline and directly comparing simulated and measured visibility values. The general nature of the model makes it possible to extend it to any given grating interferometer for both X-rays and neutrons.

Micrometer-resolution imaging using MÖNCH: towards G2-less grating interferometry.

MÖNCH is a 25 µm-pitch charge-integrating detector aimed at exploring the limits of current hybrid silicon detector technology. The small pixel size makes it ideal for high-resolution imaging. With an electronic noise of about 110 eV r.m.s., it opens new perspectives for many synchrotron applications where currently the detector is the limiting factor, e.g. inelastic X-ray scattering, Laue diffraction and soft X-ray or high-resolution color imaging. Due to the small pixel pitch, the charge cloud generated by absorbed X-rays is shared between neighboring pixels for most of the photons. Therefore, at low photon fluxes, interpolation algorithms can be applied to determine the absorption position of each photon with a resolution of the order of 1 µm. In this work, the characterization results of one of the MÖNCH prototypes are presented under low-flux conditions. A custom interpolation algorithm is described and applied to the data to obtain high-resolution images. Images obtained in grating interferometry experiments without the use of the absorption grating G2 are shown and discussed. Perspectives for the future developments of the MÖNCH detector are also presented.

Anisotropic de Gennes Narrowing in Confined Fluids.

The collective diffusion of dense fluids in spatial confinement is studied by combining high-energy (21 keV) x-ray photon correlation spectroscopy and small-angle x-ray scattering from colloid-filled microfluidic channels. We find the structural relaxation in confinement to be slower compared to the bulk. The collective dynamics is wave vector dependent, akin to the de Gennes narrowing typically observed in bulk fluids. However, in stark contrast to the bulk, the structure factor and de Gennes narrowing in confinement are anisotropic. These experimental observations are essential in order to develop a microscopic theoretical description of collective diffusion of dense fluids in confined geometries.

2D-Omnidirectional Hard-X-Ray Scattering Sensitivity in a Single Shot.

X-ray scattering imaging can provide complementary information to conventional absorption based radiographic imaging about the unresolved microstructures of a sample. The scattering signal can be accessed with various methods based on coherent illumination, which span from self-imaging to speckle scanning. The directional sensitivity of the existing real space imaging methods is limited to a few directions on the imaging plane and requires scanning of the optical components, or the rotation of either the sample or the imaging setup, in order to cover the full range of possible scattering directions. In this Letter the authors propose a new method that allows the simultaneous acquisition of scattering images in all possible directions in a single shot. This is achieved by a specialized phase grating and a detector with sufficient spatial resolution to record the generated interference fringe. The structural length scale sensitivity of the system can be tuned by varying its geometry for a fixed grating design. Taking into account ongoing developments in the field of compact x-ray sources that allow high brightness and sufficient spatial coherence, the applicability of omnidirectional scattering imaging in industrial and medical settings is boosted significantly.

Multiple scattering tomography.

Multiple scattering represents a challenge for numerous modern tomographic imaging techniques. In this Letter, we derive an appropriate line integral that allows for the tomographic reconstruction of angular resolved scattering distributions, even in the presence of multiple scattering. The line integral is applicable to a wide range of imaging techniques utilizing various kinds of probes. Here, we use x-ray grating interferometry to experimentally validate the framework and to demonstrate additional structural sensitivity, which exemplifies the impact of multiple scattering tomography.