3D and Multimodal X-Ray Microscopy Reveals the Impact of Voids in CIGS Solar Cells.

Small voids in the absorber layer of thin-film solar cells are generally suspected to impair photovoltaic performance. They have been studied on Cu(In,Ga)Se2 cells with conventional laboratory techniques, albeit limited to surface characterization and often affected by sample-preparation artifacts. Here, synchrotron imaging is performed on a fully operational as-deposited solar cell containing a few tens of voids. By measuring operando current and X-ray excited optical luminescence, the local electrical and optical performance in the proximity of the voids are estimated, and via ptychographic tomography, the depth in the absorber of the voids is quantified. Besides, the complex network of material-deficit structures between the absorber and the top electrode is highlighted. Despite certain local impairments, the massive presence of voids in the absorber suggests they only have a limited detrimental impact on performance.

Cadmium and Zn hyperaccumulation provide efficient constitutive defense against Turnip yellow mosaic virus infection in Noccaea caerulescens.

To understand the role of Zn and Cd in anti-viral defence, Zn/Cd hyperaccumulator Noccaea caerulescens plants grown with deficient (0.3 µM), replete (10 µM) and excess (100 µM) Zn2+ and Cd (10 µM Zn2+ + 1 µM Cd2+) were infected with Turnip yellow mosaic virus (TYMV). Gas exchange and chlorophyll fluorescence kinetics analyses demonstrated direct TYMV effects on photosynthetic light reactions but N. caerulescens was more resistant against TYMV than the previously studied non-hyperaccumulator N. ochroleucum. Virus abundance and photosynthesis inhibition were the lowest in the high Zn and Cd treatments. RNAseq analysis of 10 µM Zn2+ plants revealed TYMV-induced upregulation of Ca transporters, chloroplastic ZTP29 and defence genes, but none of those that are known to be strongly involved in hyperaccumulation. Synchrotron µ-XRF tomography, however, showed that Zn hyperaccumulation remained strongest in vacuoles of epidermal storage cells regardless of infection. This was in contrast to N. ochroleucum, where apoplastic Zn drastically increased in response to TYMV. These results suggest that the antiviral response of N. caerulescens is less induced by the onset of this biotic stress, but it is rather a permanent resistant state of the plant. Real-time qPCR revealed upregulation of ferritin in Zn10 infected plants, suggesting Fe deprivation as a virus defence strategy under suboptimal Zn supply.

Multimodal imaging of cubic Cu2O@Au nanocage formation via galvanic replacement using X-ray ptychography and nano diffraction.

Being able to observe the formation of multi-material nanostructures in situ, simultaneously from a morphological and crystallographic perspective, is a challenging task. Yet, this is essential for the fabrication of nanomaterials with well-controlled composition exposing the most active crystallographic surfaces, as required for highly active catalysts in energy applications. To demonstrate how X-ray ptychography can be combined with scanning nanoprobe diffraction to realize multimodal imaging, we study growing Cu2O nanocubes and their transformation into Au nanocages. During the growth of nanocubes at a temperature of 138 °C, we measure the crystal structure of an individual nanoparticle and determine the presence of (100) crystallographic facets at its surface. We subsequently visualize the transformation of Cu2O into Au nanocages by galvanic replacement. The nanocubes interior homogeneously dissolves while smaller Au particles grow on their surface and later coalesce to form porous nanocages. We finally determine the amount of radiation damage making use of the quantitative phase images. We find that both the total surface dose as well as the dose rate imparted by the X-ray beam trigger additional deposition of Au onto the nanocages. Our multimodal approach can benefit in-solution imaging of multi-material nanostructures in many related fields.

Sublethal and lethal Cd toxicity in soybean roots specifically affects the metabolome, Cd binding to proteins and cellular distribution of Cd.

Soybean (Glycine max (L.) Merr.) plants were exposed to various Cd concentrations from background and low non-toxic (0.5-50 nM) via sublethally toxic (< 550 nM) to highly, ultimately lethally toxic (3 µM) concentrations. Plants were cultivated hydroponically for 10 weeks until pod development stage of the control plants. The threshold and mechanism of sublethal Cd toxicity was investigated by metabolomics and metalloproteomics (HPLC-ICP-MS) measuring metal binding to proteins in the harvested roots. Spatial distribution of Cd was revealed by µXRF-CT. Specific binding of Cd to proteins already at 50 nM Cd revealed the likely high-affinity protein binding targets in roots, identified by protein purification from natural abundance. This revealed allantoinase, aquaporins, peroxidases and protein disulfide isomerase as the most likely high-affinity targets of Cd binding. Cd was deposited in cortex cell vacuoles at sublethal and bound to the cell walls of the outer cortex and the vascular bundle at lethal Cd. Cd binding to proteins likely inhibits them, and possibly induces detoxification mechanisms, as verified by metabolomics: allantoic acid and allantoate increased due to sublethal Cd toxicity. Changes of the Cd binding pattern indicated a detoxification strategy at lower Cd, but saturated binding sites at higher Cd concentrations.

Ptychographic reconstruction with object initialization.

X-ray ptychography is a cutting edge imaging technique providing ultra-high spatial resolutions. In ptychography, phase retrieval, i.e., the recovery of a complex valued signal from intensity-only measurements, is enabled by exploiting a redundancy of information contained in diffraction patterns measured with overlapping illuminations. For samples that are considerably larger than the probe we show that during the iteration the bulk information has to propagate from the sample edges to the center. This constitutes an inherent limitation of reconstruction speed for algorithms that use a flat initialization. Here, we experimentally demonstrate that a considerable improvement of computational speed can be achieved by utilizing a low resolution sample wavefront retrieved from measured diffraction patterns as object initialization. In addition, we show that this approach avoids phase artifacts associated with large phase gradients and may alleviate the requirements on phase structure within the probe. Object initialization is computationally fast, potentially beneficial for bulky sample and compatible with flat samples. Therefore, the presented approach is readily adaptable with established ptychographic reconstruction algorithms implying a wide spread use.

Assessing Cellular Uptake of Exogenous Coenzyme Q10 into Human Skin Cells by X-ray Fluorescence Imaging.

X-ray fluorescence (XRF) imaging is a highly sensitive non-invasive imaging method for detection of small element quantities in objects, from human-sized scales down to single-cell organelles, using various X-ray beam sizes. Our aim was to investigate the cellular uptake and distribution of Q10, a highly conserved coenzyme with antioxidant and bioenergetic properties. Q10 was labeled with iodine (I2-Q10) and individual primary human skin cells were scanned with nano-focused beams. Distribution of I2-Q10 molecules taken up inside the screened individual skin cells was measured, with a clear correlation between individual Q10 uptake and cell size. Experiments revealed that labeling Q10 with iodine causes no artificial side effects as a result of the labeling procedure itself, and thus is a perfect means of investigating bioavailability and distribution of Q10 in cells. In summary, individual cellular Q10 uptake was demonstrated by XRF, opening the path towards Q10 multi-scale tracking for biodistribution studies.

Erratum: Ossig, C., et al. Four-Fold Multi-Modal X-ray Microscopy Measurements of a Cu(In, Ga)Se2 Solar Cell. Materials 2021, 14, 228.

In the original version of our article [...].

Multi-slice ptychography enables high-resolution measurements in extended chemical reactors.

Ptychographic X-ray microscopy is an ideal tool to observe chemical processes under in situ conditions. Chemical reactors, however, are often thicker than the depth of field, limiting the lateral spatial resolution in projection images. To overcome this limit and reach higher lateral spatial resolution, wave propagation within the sample environment has to be taken into account. Here, we demonstrate this effect recording a ptychographic projection of copper(I) oxide nanocubes grown on two sides of a polyimide foil. Reconstructing the nanocubes using the conventional ptychographic model shows the limitation in the achieved resolution due to the thickness of the foil. Whereas, utilizing a multi-slice approach unambiguously separates two sharper reconstructions of nanocubes on both sides of the foil. Moreover, we illustrate how ptychographic multi-slice reconstructions are crucial for high-quality imaging of chemical processes by ex situ studying copper(I) oxide nanocubes grown on the walls of a liquid cell.

Four-Fold Multi-Modal X-ray Microscopy Measurements of a Cu(In,Ga)Se2 Solar Cell.

Inhomogeneities and defects often limit the overall performance of thin-film solar cells. Therefore, sophisticated microscopy approaches are sought to characterize performance and defects at the nanoscale. Here, we demonstrate, for the first time, the simultaneous assessment of composition, structure, and performance in four-fold multi-modality. Using scanning X-ray microscopy of a Cu(In,Ga)Se2 (CIGS) solar cell, we measured the elemental distribution of the key absorber elements, the electrical and optical response, and the phase shift of the coherent X-rays with nanoscale resolution. We found structural features in the absorber layer-interpreted as voids-that correlate with poor electrical performance and point towards defects that limit the overall solar cell efficiency.

Hard X-ray wavefront correction via refractive phase plates made by additive and subtractive fabrication techniques.

Modern subtractive and additive manufacturing techniques present new avenues for X-ray optics with complex shapes and patterns. Refractive phase plates acting as glasses for X-ray optics have been fabricated, and spherical aberration in refractive X-ray lenses made from beryllium has been successfully corrected. A diamond phase plate made by femtosecond laser ablation was found to improve the Strehl ratio of a lens stack with a numerical aperture (NA) of 0.88 × 10-3 at 8.2 keV from 0.1 to 0.7. A polymer phase plate made by additive printing achieved an increase in the Strehl ratio of a lens stack at 35 keV with NA of 0.18 × 10-3 from 0.15 to 0.89, demonstrating diffraction-limited nanofocusing at high X-ray energies.

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).

Interaction Between Zn Deficiency, Toxicity and Turnip Yellow Mosaic Virus Infection in Noccaea ochroleucum.

Zinc is essential for the functioning of numerous proteins in plants. To investigate how Zn homeostasis interacts with virus infection, Zn-tolerant Noccaea ochroleucum plants exposed to deficient (Zn'0'), optimal (Zn10), and excess Zn (Zn100) concentrations, as well as Cd amendment, were infected with Turnip yellow mosaic virus (TYMV). Imaging analysis of fluorescence kinetics from the µs (OJIP) to the minutes (Kautsky effect, quenching analysis) time domain revealed strong patchiness of systemic virus-induced photosystem II (PSII) inhibition. That was more pronounced in Zn-deficient plants, while Zn excess acted synergistically with TYMV, in both cases resulting in reduced PSII reaction centers. Infected Cd-treated plants, already severely stressed, showed inhibited non-photochemical quenching and PSII activity. Quantitative in situ hybridization at the cellular level showed increased gene expression of ZNT5 and downregulation of HMA4 in infected Zn-deficient leaves. In Zn10 and Zn100 infected leaves, vacuolar sequestration of Zn increased by activation of HMA3 (mesophyll) and MTP1 (epidermis). This correlated with Zn accumulation in the mesophyll and formation of biomineralization dots in the cell wall (Zn100) visible by micro X-ray fluorescence tomography. The study reveals the importance of adequate Zn supply and distribution in the maintenance of photosynthesis under TYMV infection, achieved by tissue-targeted activation of metal transporter gene expression.

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.