X‐Ray Multibeam Ptychography at up to 20 keV: Nano‐Lithography Enhances X‐Ray Nano‐Imaging

Hard X-rays are needed for non-destructive nano-imaging of solid matter. Synchrotron radiation facilities (SRF) provide the highest-quality images with single-digit nm resolution using advanced techniques such as X-ray ptychography. However, the resolution or field of view is ultimately constrained by the available coherent flux. To address this, the beam\u27s incoherent fraction can be exploited using multiple parallel beams in an X-ray multibeam ptychography (MBP) approach. This expands the domain of X-ray ptychography to larger samples or more rapid measurements. Both qualities favor the study of complex composite or functional samples, such as catalysts, energy materials, or electronic devices. The challenge of performing ptychography at high energy and with many parallel beams must be overcome to extract the full advantages for extended samples while minimizing beam attenuation. Here, that challenge is overcome by creating a lens array using cutting-edge laser printing technology and applying it to perform scanning with MBP with up to 12 beams and at photon energies of 13 and 20 keV. This exceeds the measurement limits of conventional hard X-ray ptychography without compromising image quality for various samples: Siemens star test pattern, Ni/Al$_2$O$_3$ catalyst, microchip, and gold nano-crystal clusters

Tomographic reconstruction with a generative adversarial network

This paper presents a deep learning algorithm for tomographic reconstruction (GANrec). The algorithm uses a generative adversarial network (GAN) to solve the inverse of the Radon transform directly. It works for independent sinograms without additional training steps. The GAN has been developed to fit the input sinogram with the model sinogram generated from the predicted reconstruction. Good quality reconstructions can be obtained during the minimization of the fitting errors. The reconstruction is a self-training procedure based on the physics model, instead of on training data. The algorithm showed significant improvements in the reconstruction accuracy, especially for missing-wedge tomography acquired at less than 180° rotational range. It was also validated by reconstructing a missing-wedge X-ray ptychographic tomography (PXCT) data set of a macroporous zeolite particle, for which only 51 projections over 70° could be collected. The GANrec recovered the 3D pore structure with reasonable quality for further analysis. This reconstruction concept can work universally for most of the ill-posed inverse problems if the forward model is well defined, such as phase retrieval of in-line phase-contrast imaging

X-ray multibeam ptychography at up to 20 keV: nano-lithography enhances X-ray nano-imaging

Non-destructive nano-imaging of the internal structure of solid matter is only feasible using hard X-rays due to their high penetration. The highest resolution images are achieved at synchrotron radiation sources (SRF), offering superior spectral brightness and enabling methods such as X-ray ptychography delivering single-digit nm resolution. However the resolution or field of view is ultimately constrained by the available coherent flux. To address this, the beam's incoherent fraction can be exploited using multiple parallel beams in an approach known as X-ray multibeam ptychography (MBP). This expands the domain of X-ray ptychography to larger samples or more rapid measurements. Both qualities favor the study of complex composite or functional samples, such as catalysts, energy materials, or electronic devices. The challenges of performing ptychography at high energy and with many parallel beams must be overcome to extract the full advantages for extended samples while minimizing beam attenuation. Here, we report the application of MBP with up to 12 beams and at photon energies of 13 and 20 keV. We demonstrate performance for various samples: a Siemens star test pattern, a porous Ni/\ce{Al2O3} catalyst, a microchip, and gold nano-crystal clusters, exceeding the measurement limits of conventional hard X-ray ptychography without compromising image quality

Restructuring of Ag catalysts for methanol to formaldehyde conversion studied using in situ X-ray ptychography and electron microscopy

Dynamic restructuring of silver catalysts during the industrial conversion of methanol to formaldehyde leads to surface faceting and pinhole formation. Subsequent sintering under reaction conditions, followed by increased pressure drop and decreased catalyst activity requires catalyst bed replacement after several months of operation. This necessitates a comprehensive understanding of the bulk catalyst restructuring under exposure to different gas environments. In this work, Ag restructuring was studied at elevated temperatures under different reactive and inert gas environments. Bubble formation within catalysts of 5-8 µm thickness was visualized in real-time using in situ X-ray ptychography. Stepwise heating up to 650 °C in combination with imaging was used to determine the effect of temperature on silver restructuring. Dynamic changes within the catalyst were further quantified in terms of relative changes in mass on selected regions at a constant temperature of 500 °C. Quantitative assessment of dynamic changes in the catalyst resulting from bubble growth and movement revealed the influence of temperature, time, and gas environment on the degree of restructuring. Post-mortem scanning electron microscopy with energy-dispersive X-ray spectroscopy mapping confirmed the redistribution of material as a consequence of bubble rupture and collapse. The formation of pores and cavities under reaction environments was additionally confirmed using a fixed bed reactor, and subsequent examination using focused-ion beam milling, providing detailed analysis of the surface structure.This study demonstrates the unique advantage of correlative hard X-ray and electron microscopy for quantitative morphological studies of industrial catalysts

Evolution of Hierarchically Porous Nickel Alumina Catalysts Studied by X‐Ray Ptychography

The synthesis of hierarchically porous materials usually requires complex experimental procedures, often based around extensive trial and error approaches. One common synthesis strategy is the sol–gel method, although the relation between synthesis parameters, material structure and function has not been widely explored. Here, in situ 2D hard X‐ray ptychography (XRP) and 3D ptychographic X‐ray computed tomography (PXCT) are applied to monitor the development of hierarchical porosity in Ni/Al(2)O(3) and Al(2)O(3) catalysts with connected meso‐ and macropore networks. In situ XRP allows to follow textural changes of a dried gel Ni/Al(2)O(3) sample as a function of temperature during calcination, activation and CO(2) methanation reaction. Complementary PXCT studies on dried gel particles of Ni/Al(2)O(3) and Al(2)O(3) provide quantitative information on pore structure, size distribution, and shape with 3D spatial resolution approaching 50 nm, while identical particles are imaged ex situ before and after calcination. The X‐ray imaging results are correlated with N(2)‐sorption, Hg porosimetry and He pycnometry pore characterization. Hard X‐ray nanotomography is highlighted to derive fine structural details including tortuosity, branching nodes, and closed pores, which are relevant in understanding transport phenomena during chemical reactions. XRP and PXCT are enabling technologies to understand complex synthesis pathways of porous materials

X-ray in-line holography and holotomography at the NanoMAX beamline

Coherent X-ray imaging techniques, such as in-line holography, exploit the high brilliance provided by diffraction-limited storage rings to perform imaging sensitive to the electron density through contrast due to the phase shift, rather than conventional attenuation contrast. Thus, coherent X-ray imaging techniques enable high-sensitivity and low-dose imaging, especially for low-atomic-number (Z) chemical elements and materials with similar attenuation contrast. Here, the first implementation of in-line holography at the NanoMAX beamline is presented, which benefits from the exceptional focusing capabilities and the high brilliance provided by MAX IV, the first operational diffraction-limited storage ring up to approximately 300 eV. It is demonstrated that in-line holography at NanoMAX can provide 2D diffraction-limited images, where the achievable resolution is only limited by the 70 nm focal spot at 13 keV X-ray energy. Also, the 3D capabilities of this instrument are demonstrated by performing holotomography on a chalk sample at a mesoscale resolution of around 155 nm. It is foreseen that in-line holography will broaden the spectra of capabilities of MAX IV by providing fast 2D and 3D electron density images from mesoscale down to nanoscale resolution

PtyNAMi: ptychographic nano-analytical microscope

Ptychographic X-ray imaging at the highest spatial resolution requires an optimal experimental environment, providing a high coherent flux, excellent mechanical stability and a low background in the measured data. This requires, for example, a stable performance of all optical components along the entire beam path, high temperature stability, a robust sample and optics tracking system, and a scatter-free environment. This contribution summarizes the efforts along these lines to transform the nanoprobe station on beamline P06 (PETRA III) into the ptychographic nano-analytical microscope (PtyNAMi

Structure and Composition of Isolated Core-Shell(In,Ga)N/GaNRods Based on Nanofocus X-Ray Diffraction and Scanning Transmission Electron Microscopy

Nanofocus x-ray diffraction is used to investigate the structure and local strain field of an isolated ðIn; GaÞN=GaN core-shell microrod. Because the high spatial resolution of the x-ray beam is only 80 × 90 nm2, we are able to investigate several distinct volumes on one individual side facet. Here, we find a drastic increase in thickness of the outer GaN shell along the rod height. Additionally, we performed highangle annular dark-field scanning-transmission-electron-microscopy measurements on several rods from the same sample showing that (In,Ga)N double-quantum-well and GaN barrier thicknesses also increase strongly along the height. Moreover, plastic relaxation is observed in the top part of the rod. Based on the experimentally obtained structural parameters, we simulate the strain-induced deformation using the finiteelement method, which serves as the input for subsequent kinematic scattering simulations. The simulations reveal a significant increase of elastic in-plane relaxation along the rod height. However, at a certain height, the occurrence of plastic relaxation yields a decrease of the elastic strain. Because of the experimentally obtained structural input for the finite-element simulations, we can exclude unknown structural influences on the strain distribution, and we are able to translate the elastic relaxation into an indium concentration which increases by a factor of 4 from the bottom to the height where plastic relaxation occurs

Nanofocusing with aberration-corrected rotationally parabolic refractive X-ray lenses

Wavefront errors of rotationally parabolic refractive X-ray lenses made of beryllium (Be CRLs) have been recovered for various lens sets and X-ray beam configurations. Due to manufacturing via an embossing process, aberrations of individual lenses within the investigated ensemble are very similar. By deriving a mean single-lens deformation for the ensemble, aberrations of any arbitrary lens stack can be predicted from the ensemble with \bar{\sigma} = 0.034λ. Using these findings the expected focusing performance of current Be CRLs are modeled for relevant X-ray energies and bandwidths and it is shown that a correction of aberrations can be realised without prior lens characterization but simply based on the derived lens deformation. The performance of aberration-corrected Be CRLs is discussed and the applicability of aberration-correction demonstrated over wide X-ray energy ranges