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The first report of sub-4 nm mapping of donor : acceptor nanoparticle composition in eco-friendly colloidal dispersions for organic electronics.

Crystalline organic semiconducting thin films from the benchmark molecule C8-BTBT-C8 were obtained using physical vapor deposition and various solution-based methods. Utilizing atomic force microscopy and X-ray spectromicroscopy, we illustrate the influence of the underlying growth mechanism and determine the highly preparation-dependent orientation of the thiophene backbone. We observe a continuous trend for crystalline C8-BTBT-C8 thin film domains to extend into the square millimeter-range under near-equilibrium growth conditions. For such well-defined systems, electron diffraction tomography allows us to precisely determine the unit cell directly after film deposition and to reveal an 8° molecular tilt angle with respect to the surface normal. This finding is in almost perfect accordance with the values derived from near-edge X-ray absorption fine structure linear dichroism. Within this work, we shine a light on both the successes and challenges connected to the realization of potent, thiophene-based semiconducting films, paving the way toward square centimeter-sized ultrathin organic crystals and their application in organic circuitry.

Many European sculptures and altarpieces from the Middle Ages were decorated with Zwischgold, a bilayer metal leaf with an ultra-thin gold face backed by silver. Zwischgold corrodes quickly when exposed to air, causing the surface of the artefact to darken and lose gloss. The conservation of such Zwischgold applied artefacts has been an obstinate problem. We have acquired quantitative, 3D nanoscale images of Zwischgold samples from 15th century artefacts and modern materials using ptychographic X-ray computed tomography (PXCT), a recently developed coherent diffractive imaging technique, to investigate the leaf structure and chemical state of Zwischgold. The measurements clearly demonstrate decreasing density (increasing porosity) of the leaf materials and their corrosion products, as well as delamination of the leaves from their substrate. Each of these effects speak to typically observed issues in the conservation of such Zwischgold applied artefacts. Further, a rare variant of Zwischgold that contains extremely thin multiple gold layers and an overlapping phenomenon of Zwischgold with other metal leaves are observed through PXCT. As supportive data, scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray analysis (EDX) were performed on the medieval samples.

While the strategy of blending commodity insulating polymers with conjugated polymers has been previously applied to modify the properties of organic field-effect transistors (OFETs), comprehensive...

Through Monte Carlo simulations, we investigate how various experimental parameters can influence the quality of time-resolved scanning transmission X-ray microscopy images. In particular, the effect of the X-ray photon flux, of the thickness of the investigated samples, and of the frequency of the dynamical process under investigation on the resulting time-resolved image are investigated. The ideal sample and imaging conditions that allow for an optimal image quality are then identifed.

The absorption of extreme ultraviolet (EUV) radiation by a photoresist strongly depends on its atomic composition. Consequently, elements with a high EUV absorption cross section can assist in meeting the demand for higher photon absorbance by the photoresist to improve the sensitivity and reduce the photon shot noise induced roughness. In this work, we enhanced the EUV absorption of the methacrylic acid ligands of Zn oxoclusters by introducing fluorine atoms. We evaluated the lithography performance of this fluorine-rich material as a negative tone EUV photoresist along with extensive spectroscopic and microscopic studies, providing deep insights into the underlying mechanism. UV-vis spectroscopy studies demonstrate that the presence of fluorine in the oxocluster enhances its stability in the thin films to the ambient atmosphere. However, the EUV photoresist sensitivity (D50) of the fluorine-rich oxocluster is decreased compared to its previously studied methacrylic acid analogue. Scanning transmission X-ray microscopy and in situ X-ray photoelectron spectroscopy in combination with FTIR and UV-vis spectroscopy were used to gain insights into the chemical changes in the material responsible for the solubility switch. The results support decarboxylation of the ligands and subsequent radical-induced polymerization reactions in the thin film upon EUV irradiation. The rupture of carbon-fluorine bonds via dissociative electron attachment offers a parallel way of generating radicals. The mechanistic insights obtained here will be applicable to other hybrid materials and potentially pave the way for the development of EUV materials with better performance.

Organic-inorganic hybrid compounds are arising as promising resist materials for extreme-ultraviolet (EUV) lithography, a new technique introduced in the semiconductor industry for the fabrication of integrated circuits of sub-10 nm feature size. In this work, we show that the sensitivity to EUV radiation of zirconium oxo clusters with methacrylate ligands is substantially enhanced when a small fraction of the ligands are replaced by trifluoromethylacrylates. We studied the details of the chemical changes that occur in thin films of the precursor and the partially fluorinated materials using scanning transmission X-ray microscopy (STXM) and X-ray photoelectron spectroscopy (XPS). Evidence is presented for radical chain polymerization as a mechanism for the solubility switch. Yet, XPS results also indicate that Zr-F bonds are formed during the exposure to EUV light in the fluorinated material, dissociative electron attachment being likely involved. Our observations show that, while fluorinated ligands enhance EUV absorption, their effect on the reactivity of the material might be more critical, thereby contributing to an increase in the sensitivity of the resist in both ways.

Precipitation is mostly formed via the ice phase in mixed phase clouds, and ice clouds are very relevant for Earths’ climate. Freezing or prevention of freezing is common to everyday life, e.g. for food and drug storage, icing and de-icing, etc. However, the ice nucleation process is not well understood, since it occurs on the size scale of clusters of molecules and time scales of molecular fluctuations. In this study, we have taken a step toward nanoscale observation of particles that nucleate ice by developing a new ice nucleation instrument, referred as the INXcell, which couples an ice nucleation environmental cell to the scanning transmission X-ray microscope (STXM) at the Swiss Light Source. We employ near-edge X-ray absorption fine-structure spectroscopy (NEXAFS) to map in situ chemical composition of ice nucleating particles with 35 × 35 nm2 spatial resolution. The main technical challenge was control of temperature, T, and thus relative humidity, RH, while maintaining X-ray transparency. In the INXcell, X-rays are focused onto a sample through a temperature-controlled aperture, which was modified to host a jet of nitrogen cooled down to 170 K. The cold jet impinges on the back surface of a sample exposed to water vapor to control sample temperature and thus RH. We used our unique spectroscopic and ice nucleation capability and investigated the heterogeneous freezing ability of ferrihydrite particles with and without coatings of citric acid. Ferrihydrite is an amorphous or poorly crystalline iron oxyhydroxide abundant in mineral dust and is difficult to identify with conventional XRD analysis. We confirmed that ferrihydrite could nucleate ice via immersion freezing and deposition ice nucleation, depending on whether or not the particles first take up water, respectively. When coating ferrihydrite with citric acid, mimicking organic coatings that aerosol particles obtain throughout their atmospheric lifetime, we observed a reduction in the efficiency to nucleate ice following freezing point depression. Spectroscopic identification of the coated ferrihydrite structure emplyed the iron and carbon X-ray absorption L-edges and K-edge, respectively. We also investigated feldspar particles coated with xanthan gum, a surrogate for a highly ice active mineral with a highly viscous organic coating. We observed that deposition ice nucleation occurred only below the RH dependent glass transition of xanthan gum. Using a newly developed stochastic freezing model (SFM) based on solution water activity, we reproduced average conditions and data scatter of the RH and T at which ice formed. Additionally, we ran our model with atmospheric idealized air parcel trajectories and found overall that deposition ice nucleation was the dominant heterogeneous freezing mechanism. Homogeneous ice nucleation subsequent to water uptake out-performed immersion freezing.

Ice nucleation is one of the most uncertain microphysical processes, as it occurs in various ways and on many types of particles. To overcome this challenge, we present a heterogeneous ice nucleation study on deposition ice nucleation and immersion freezing in a novel cryogenic X-ray experiment with the capability to spectroscopically probe individual ice nucleating and non-ice nucleating particles. Mineral dust type particles composed of either ferrihydrite or feldspar were used and mixed with organic matter of either citric acid or xanthan gum. We observed in situ ice nucleation using scanning transmission X-ray microscopy (STXM) and identified unique organic carbon functionalities and iron oxidation state using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the new in situ environmental ice cell, termed the ice nucleation X-ray cell (INXCell). Deposition ice nucleation of ferrihydrite occurred at a relative humidity with respect to ice, RHi, between ∼120–138% and temperatures, T ∼ 232 K. However, we also observed water uptake on ferrihydrite at the same T when deposition ice nucleation did not occur. Although, immersion freezing of ferrihydrite both in pure water droplets and in aqueous citric acid occurred at or slightly below conditions for homogeneous freezing, i.e. the effect of ferrihydrite particles acting as a heterogeneous ice nucleus for immersion freezing was small. Microcline K-rich feldspar mixed with xanthan gum was also used in INXCell experiments. Deposition ice nucleation occurred at conditions when xanthan gum was expected to be highly viscous (glassy). At less viscous conditions, immersion freezing was observed. We extended a model for heterogeneous and homogeneous ice nucleation, named the stochastic freezing model (SFM). It was used to quantify heterogeneous ice nucleation rate coefficients, mimic the competition between homogeneous ice nucleation; water uptake; deposition ice nucleation and immersion freezing, and predict the T and RHi at which ice was observed. The importance of ferrihydrite to act as a heterogeneous ice nucleating particle in the atmosphere using the SFM is discussed., Environmental Science: Atmospheres, 2 (3), ISSN:2634-3606

While the general effects of experimental conditions such as photon flux and sample thickness on the quality of data acquired by scanning transmission X-ray microscopy (STXM) are widely known at a basic level, the specific details are rarely discussed. This leaves the community open to forming misconceptions that can lead to poor decisions in the design and execution of STXM measurements. A formal treatment of the uncertainty and distortions of transmission signals (due to dark counts, higher-order photons and poor spatial or spectral resolution) is presented here to provide a rational basis for the pursuit of maximizing data quality in STXM experiments. While we find an optimum sample optical density of 2.2 in ideal conditions, the distortions considered tend to have a stronger effect for thicker samples and so ∼1 optical density at the analytical energy is recommended, or perhaps even thinner if significant distortion effects are expected (e.g. lots of higher-order light is present in the instrument). (Note that X-ray absorption calculations based on simple elemental composition do not include near-edge resonances and so cannot accurately represent the spectral resonances typically employed for contrast in STXM.) Further, we present a method for objectively assessing the merits of higher-order suppression in terms of its impact on the quality of transmission measurements that should be useful for the design of synchrotron beamlines.

Nanoplastics (NP) are of environmental and human health concern. We tested a novel NP extraction method and scanning transmission X-ray spectro-microscopy (STXM) in combination with near-edge X-ray absorption fine-structure spectroscopy (NEXAFS) to image and identify individual NP in environmental and food matrices. We 1) discussed the potential of STXM compared to other methods potentially suitable for NP analysis, 2) applied the method on NP suspensions of eight of the most common polymers, 3) analyzed environmental water and soil samples spiked with NP and 4) characterized NP in tea water infused in plastic teabags and unspiked soil samples. Here we show that STXM has methodological advantages and that polymers give characteristic spectra, which allows NP identification in environmental and food matrices. For soils we deliver a visual and spectroscopic characterization of NP, proving their presence and highlighting their diversity. Thus, STXM, can be used for the detection and characterisation of NP in different types of matrices.

The penetration of topically applied tacrolimus formulated in micelles into murine skin is reported, measured by X-ray microscopy. Tacrolimus and micelles are probed for the first time by this high spatial resolution technique by element-selective excitation in the C 1s- and O 1s-regimes. This method allows selective detection of the distribution and penetration depth of drugs and carrier molecules into biologic tissues. It is observed that small, but distinct quantities of the drug and micelles, acting as a drug carrier, penetrate the stratum corneum. A comparison is made with the paraffin-based commercial tacrolimus ointment Protopic®, where local drug concentrations show to be low. A slight increase in local drug concentration in the stratum corneum is observed, if tacrolimus is formulated in micelles, as compared to Protopic®. This underscores the importance of the drug formulations for effective drug delivery. Time-resolved penetration shows presence of drug in the stratum corneum 100 min after formulation application, with penetration to deeper skin layers at 1000 min. High resolution micrographs give indications for a penetration pathway along the lipid membranes between corneocytes, but also suggest that the compound may penetrate corneocytes.

Dwindling supplies of natural concrete aggregates, the cost of landfilling construction waste, and interest in sustainable design have increased the demand for recycled concrete aggregates (RCA) in new portland cement concrete mixtures. RCA repurposes waste material to provide useful ingredients for new construction applications. However, RCA can reduce the performance of the concrete. This study investigated the effectiveness of ternary blended binders, mixtures containing portland cement and two different supplementary cementitious materials, at mitigating performance losses of concrete mixtures with RCA materials. Concrete mixtures with different ternary binder combinations were batched with four recycled concrete aggregate materials. For the materials used, the study found that a blend of portland cement, Class C fly ash, and blast furnace slag produced the highest strength of ternary binder. At 50% replacement of virgin aggregates and ternary blended binder, some specimens showed comparable mechanical performance to a control mix of only portland cement as a binder and no RCA substitution. This study demonstrates that even at 50% RCA replacement, using the appropriate ternary binder can create a concrete mixture that performs similarly to a plain portland cement concrete without RCA, with the added benefit of being environmentally beneficial.

A special gilding material called Zwischgold has been frequently observed in medieval gilded artefacts. As a bilayer metal leaf made from gold and silver, it exhibits similar but slightly paler golden colour tone compared to pure gold. Zwischgold surface can be darkened quickly due to the corrosion of its silver base. Despite its frequent mentions in medieval guild statutes, the production of Zwischgold and its important technological parameters have been under a veil of secrecy since the Middle Ages. Here, we examine the thicknesses and materials proportions of medieval Zwischgold, through high-resolution scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) on a large number of samples taken from late medieval gilded sculptures. We observe that medieval Zwischgold contains ultra-thin gold layers in a thickness range of ca. 20–50 nm, indicating the employment of high-precision technologies in manufacturing of delicate art materials in the late medieval period. It further clarifies some ambiguity in gilding history, regarding the colour appearance of medieval Zwischgold. As supportive data, Rutherford backscattering spectrometry (RBS) and scanning transmission electron microscopy (STEM) were applied, in order to confirm the precision and accuracy of the sample preparation and the SEM analysis., Journal of Cultural Heritage, 49

Ultrashort optical pulses can trigger a variety of non-equilibrium processes in magnetic thin films affecting electrons and spins on femtosecond timescales. In order to probe the charge and magnetic degrees of freedom simultaneously, we developed an X-ray streaking technique that has the advantage of providing a jitter-free picture of absorption cross-section changes. In this paper, we present an experiment based on this approach, which we performed using five photon probing energies at the Ni M2,3-edges. This allowed us to retrieve the absorption and magnetic circular dichroism time traces, yielding detailed information on transient modifications of electron and spin populations close to the Fermi level. Our findings suggest that the observed absorption and magnetic circular dichroism dynamics both depend on the extreme ultraviolet (XUV) probing wavelength, and can be described, at least qualitatively, by assuming ultrafast energy shifts of the electronic and magnetic elemental absorption resonances, as reported in recent work. However, our analysis also hints at more complex changes, highlighting the need for further experimental and theoretical studies in order to gain a thorough understanding of the interplay of electronic and spin degrees of freedom in optically excited magnetic thin films.

The three-dimensional (3D) dual-energy focal stacks (FS) imaging method has been developed to quickly obtain the spatial distribution of an element of interest in a sample; it is a combination of the 3D FS imaging method and two-dimensional (2D) dual-energy contrast imaging based on scanning transmission soft X-ray microscopy (STXM). A simulation was firstly performed to verify the feasibility of the 3D elemental reconstruction method. Then, a sample of composite nanofibers, polystyrene doped with ferric acetylacetonate [Fe(acac)3], was further investigated to quickly reveal the spatial distribution of Fe(acac)3 in the sample. Furthermore, the data acquisition time was less than that for STXM nanotomography under similar resolution conditions and did not require any complicated sample preparation. The novel approach of 3D dual-energy FS imaging, which allows fast 3D elemental mapping, is expected to provide invaluable information for biomedicine and materials science.

In the history of medieval gilding, a common view has been circulated for centuries that the substrate colour can influence the visual appearance of a gilded surface. In order to fully understand the correlation between the gilding substrate and the colour appearance of the gold leaf laid above, in this paper (Part I) analytical techniques such as colorimetry and interferometric microscopy are implemented on models made from modern gold leaves. This study demonstrates that the substrate colour is not perceptible for gold leaf of at least 100 nm thickness, however the surface burnishing can greatly alter the visual appearance of a gold surface, and the quality of the burnishing is dependent on the substrate materials. Additionally, surface roughness and texture of the substrate can play supplementary roles, which can be visually observed through digital microscopy and quantified through interferometric microscopy. The findings in this paper will form the basis for the study of gold leaf samples taken from medieval European gilded sculptures in Part II.

In the previous paper (Part I), the colorimetry and interferometric microscopy measurements on modern gold leaf models have revealed that the visual appearance of a gilded surface, both burnished and unburnished, depends strongly on the substrate type, surface roughness and texture, but not on the colour of the substrate. In this second part, we investigate the materials compositions and technical specifications of medieval gold leaf through combining literature sources and materials analysis such as scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) on samples taken from gilded wooden sculptures. Our study shows that the late medieval gold leaf has a high purity of about 23.7 carat and has an average thickness of 160 nm (with a peak value of 138 nm), purer and thicker than the modern gold leaves studies in Part I. Supportive Rutherford backscattering spectrometry (RBS) measurements on gilded models confirms the accuracy and reliability of the SEM-EDX observations on the medieval gold leaf samples. We additionally present observations of a rarely recorded special variant of medieval gold leaf – “fine reinforced gold leaf”. Combined with the findings from Part I, we conclude that light penetrating the medieval gold leaf and reflected from the gilding substrate could not be a significant, or even perceptible contribution to the visual appearance of the gilding. We argue that the misconception surrounding the correlation between the substrate colour and the gilded surface appearance can be attributed to the historical development of gilding and polychromy technologies.

In the previous paper (Part I), the colorimetry and interferometric microscopy measurements on modern gold leaf models have revealed that the visual appearance of a gilded surface, both burnished and unburnished, depends strongly on the substrate type, surface roughness and texture, but not on the colour of the substrate. In this second part, we investigate the materials compositions and technical specifications of medieval gold leaf through combining literature sources and materials analysis such as scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) on samples taken from gilded artefacts. Our study shows that the late medieval gold leaf has a high purity of about 23.7 carat and has an average thickness of 160 nm (with a peak value of 138 nm), purer and thicker than the modern gold leaves studies in Part I. Supportive Rutherford backscattering spectrometry (RBS) measurements on gilded models confirms the accuracy and reliability of the SEM-EDX observations on the medieval gold leaf samples. We additionally present observations of a rarely recorded special variant of medieval gold leaf – “fine reinforced gold leaf”. Combined with the findings from Part I, we conclude that light penetrating the medieval gold leaf and reflected from the substrate could not be a significant, or even perceptible contribution to the visual appearance of the gilding. We argue that the misconception surrounding the correlation between the substrate colour and the gilded surface appearance can be attributed to the historical development of gilding and polychromy technologies.

Iron(III) carboxylate photochemistry plays an important role in aerosol aging, especially in the lower troposphere. These complexes can absorb light over a broad wavelength range, inducing the reduction of iron(III) and the oxidation of carboxylate ligands. In the presence of O2, ensuing radical chemistry leads to further decarboxylation, and the production of ·OH, HO2·, peroxides, and oxygenated volatile organic compounds, contributing to particle mass loss. The ·OH, HO2·, and peroxides in turn re-oxidize iron(II) back to iron(III), closing a photocatalytic cycle. This cycle is repeated resulting in continual mass loss due to the release of CO2 and other volatile compounds. In a cold and/or dry atmosphere, organic aerosol particles tend to attain highly viscous states. While the impact of reduced mobility of aerosol constituents on dark chemical reactions has received substantial attention, studies on the effect of high viscosity on photochemical processes are scarce. Here, we choose iron(III)-citrate (FeIII(Cit)) as a model light absorbing iron carboxylate complex that induces citric acid (CA) degradation to investigate how transport limitations influence photochemical processes. Three complementary experimental approaches were used to investigate kinetic transport limitations. The mass loss of single, levitated particles was measured with an electrodynamic balance, the oxidation state of deposited particles was measured with X-ray spectromicroscopy, and HO2· radical production and release into the gas phase was observed in coated wall flow tube experiments. To quantitatively compare these experiments and determine important physical and chemical parameters, a numerical multi-layered photochemical reaction and diffusion (PRAD) model that treats chemical reactions and transport of various species was developed. We observed significant photochemical degradation, with up to 80 % mass loss within 24 hours of light exposure. Interestingly, we also observed that mass loss always accelerated during irradiation, resulting in an increase of the mass loss rate by about a factor of 10. When we increased relative humidity, the observed particle mass loss rate also increased. This is consistent with strong kinetic transport limitations for highly viscous particles. The PRAD model was tuned to reproduce all experimental results and captured the essential chemistry and transport during irradiation. In particular, the photolysis rate of FeIII, the re-oxidation rate of FeII, HO2· production, and the diffusivity of O2 in aqueous FeIII(Cit)/CA system as function of relative humidity and FeIII(Cit) / CA molar ratio could be constrained. Photochemical degradation under atmospheric conditions predicted by the PRAD model shows that release of CO2 and re-partitioning of organic compounds to the gas phase may be very significant to accurately predict organic aerosol aging processes.

International audience; We present and fully characterize a flow cell dedicated to imaging in liquid at the nanoscale. Its use as a routine sample environment for soft X-ray spectromicroscopy is demonstrated, in particular through the spectral analysis of inorganic particles in water. The care taken in delineating the fluidic pathways and the precision associated with pressure actuation ensure the efficiency of fluid renewal under the beam, which in turn guarantees a successful utilization of this microfluidic tool for in situ kinetic studies. The assembly of the described flow cell necessitates no sophisticated microfabrication and can be easily implemented in any laboratory. Furthermore, the design principles we relied on are transposable to all microscopies involving strongly absorbed radiations (e.g. X-ray, electron), as well as to all kinds of X-ray diffraction/scattering techniques.

The Cr/SiO2 Phillips catalyst has taken a central role in ethylene polymerization since its invention in 1953. The uniqueness of this catalyst is related to its ability to produce broad molecular weight distribution (MWD) PE materials as well as that no co‐catalysts are required to attain activity. Nonetheless, co‐catalysts in the form of metal‐alkyls can be added for scavenging poisons, enhancing catalyst activity, reducing the induction period, and tailoring polymer characteristics. The activation mechanism and related polymerization mechanism remain elusive, despite extensive industrial and academic research. Here, we show that by varying the type and amount of metal‐alkyl co‐catalyst, we can tailor polymer properties around a single Cr/SiO2 Phillips catalyst formulation. Furthermore, we show that these different polymer properties exist in the early stages of polymerization. We have used conventional polymer characterization techniques, such as size exclusion chromatography (SEC) and 13C NMR, for studying the metal‐alkyl co‐catalyst effect on short‐chain branching (SCB), long‐chain branching (LCB) and molecular weight distribution (MWD) at the bulk scale. In addition, scanning transmission X‐ray microscopy (STXM) was used as a synchrotron technique to study the PE formation in the early stages: allowing us to investigate the produced type of early‐stage PE within one particle cross‐section with high energy resolution and nanometer scale spatial resolution., Tailoring polymerization processes: The addition of the proper type and amount of co‐catalyst in a Cr/SiO2 Phillips‐type ethylene polymerization system tailors the molecular weight distribution and degree of short chain branching. We have now used scanning transmission X‐ray microscopy for investigating how these properties affect the polyethylene crystallinity in the early stages of ethylene polymerization.

Scanning transmission X-ray microscopy (STXM) produces images in which each pixel value is related to the measured attenuation of an X-ray beam. In practice, the location of the illuminated region does not exactly match the desired uniform pixel grid. This error can be measured using an interferometer. In this paper, we propose a spline-based reconstruction method for STXM which takes these position errors into account. We achieve this by formulating the reconstruction problem as a continuous-domain inverse problem in a spline basis, and by using Hessian nuclear-norm regularization. We solve this problem using the standard ADMM algorithm, and we demonstrate the pertinence of our approach on both simulated and real STXM data.

X-ray tomography has become an indispensable tool for studying complex 3D interior structures with high spatial resolution. Three-dimensional imaging using soft X-rays offers powerful contrast mechanisms but has seen limited success with tomography due to the restrictions imposed by the much lower energy of the probe beam. The generalized geometry of laminography, characterized by a tilted axis of rotation, provides nm-scale 3D resolution for the investigation of extended (mm range) but thin (μm to nm) samples that are well suited to soft X-ray studies. This work reports on the implementation of soft X-ray laminography (SoXL) at the scanning transmission X-ray spectromicroscope of the PolLux beamline at the Swiss Light Source, Paul Scherrer Institut, which enables 3D imaging of extended specimens from 270 to 1500 eV. Soft X-ray imaging provides contrast mechanisms for both chemical sensitivity to molecular bonds and oxidation states and magnetic dichroism due to the much stronger attenuation of X-rays in this energy range. The presented examples of applications range from functionalized nanomaterials to biological photonic crystals and sophisticated nanoscaled magnetic domain patterns, thus illustrating the wide fields of research that can benefit from SoXL.

Developing a technology that enables oral vaccines to work efficiently remains a considerable effort since a number of difficulties must be addressed. The key objective being to ensure the safe passage through the harsh conditions within the gastrointestinal tract, promoting delivery that induces enhanced immune response. In the particular case of hepatitis B, the oral formulation in the nanostructured silica SBA-15 is a viable approach. As a result of its porous structure, low toxicity and structural stability, SBA-15 is capable to protect and release the hepatitis B surface antigen (HBsAg), used in the vaccination scheme, at the desired destination. Furthermore, when compared to the currently used injection based delivery method, better or similar antibody response has been observed. However, information about the organisation of the antigen protein remains unknown. For instance, HBsAg is too large to enter the 10 nm ordered mesopores of SBA-15 and has a tendency to agglomerate when protected by the delivery system. Here we report on the pH dependence of HBsAg aggregation in saline solution investigated using small angle X-rays scattering that resulted in an optimisation of the encapsulation conditions. Additionally, X-ray microscopy combined with neutron and X-ray tomography provided full 3D information of the HBsAg clustering (i.e. agglomeration) inside the SBA-15 macropores. This method enables the visualisation of the organisation of the antigen in the interior of the delivery system, where agglomerated HBsAg coexists with its immunological effective uniformly distributed counterpart. This new approach, to be taken into account while preparing the formulation, can greatly help in the understanding of clinical studies and advance new formulations.

The Cr/SiO2 Phillips catalyst has taken a central role in ethylene polymerization since its invention in 1953. The uniqueness of this catalyst is related to its ability to produce broad molecular weight distribution (MWD) PE materials as well as that no co-catalysts are required to attain activity. Nonetheless, co-catalysts in the form of metal-alkyls can be added for scavenging poisons, enhancing catalyst activity, reducing the induction period, and tailoring polymer characteristics. The activation mechanism and related polymerization mechanism remain elusive, despite extensive industrial and academic research. Here, we show that by varying the type and amount of metal-alkyl co-catalyst, we can tailor polymer properties around a single Cr/SiO2 Phillips catalyst formulation. Furthermore, we show that these different polymer properties exist in the early stages of polymerization. We have used conventional polymer characterization techniques, such as size exclusion chromatography (SEC) and 13 C NMR, for studying the metal-alkyl co-catalyst effect on short-chain branching (SCB), long-chain branching (LCB) and molecular weight distribution (MWD) at the bulk scale. In addition, scanning transmission X-ray microscopy (STXM) was used as a synchrotron technique to study the PE formation in the early stages: allowing us to investigate the produced type of early-stage PE within one particle cross-section with high energy resolution and nanometer scale spatial resolution.

Optica 7(11), 1602 - 1608 (2020). doi:10.1364/OPTICA.399885, The availability of intense soft x-ray beams with tunable energy and polarization has pushed the development of highlysensitive, element-specific, and noninvasive microscopy techniques to investigate condensed matter with high spatialand temporal resolution. The short wavelengths of soft x-rays promise to reach spatial resolutions in the deep single-digitnanometer regime, providing unprecedented access to magnetic phenomena at fundamental length scales. Despiteconsiderable efforts in soft x-ray microscopy techniques, a two-dimensional resolution of 10 nm has not yet been surpassedin direct imaging. Here, we report on a significant step beyond this long-standing limit by combining newlydeveloped soft x-ray Fresnel zone plate lenses with advanced precision in scanning control and careful optical design.With this approach, we achieve an image resolution of 7 nm. By combining this highly precise microscopy techniquewith the x-ray magnetic circular dichroism effect,we reveal dimensionality effects in an ensemble of interacting magneticnanoparticles. Such effects are topical in current nanomagnetism research and highlight the opportunities of highresolutionsoft x-ray microscopy in magnetism research and beyond., Published by OSA, Washington, DC

Chromium nitride thin films were prepared by magnetron sputtering using an industrial-scale commercial coating unit. One of the thin films was post-treated by N2+ ion implantation using an ion accelerator operating at 130 keV. The chemical, structural, and mechanical changes induced by ion implantation were analysed with Rutherford Backscattering Spectrometry (RBS), Transmission Electron Microscopy (TEM), Energy Dispersive X-ray (EDX) analysis, X-Ray Diffraction (XRD), Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and nanoindentation. The as-deposited sample has the hcp Cr2N lattice structure. It was found that the ion-implantation gave rise to an increased nitrogen concentration in the approximately 150 nm outer sample region. In addition, ion implantation caused an increase in the average crystalline grain size without changing the hcp Cr2N lattice structure. It is suggested that the additional nitrogen from implantation is embedded in the Cr2N lattice structure by filling up vacancies.

Zwischgold is a two-sided metal foil made by adhering a gold leaf over a silver leaf to present a gold surface while using less gold than gold foils. Corroded Zwischgold surfaces appear dark, accompanied by gloss loss and possible mechanical stability issues. Zwischgold applied artefacts are commonly found in museums and churches across Europe and they currently face an uncertain future as conservators have little knowledge to base conservation treatments on. We present a comprehensive material analysis of Zwischgold models through advanced characterization techniques including focused ion beam coupled with scanning electron microscopy (FIB-SEM), transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM), time-of-flight secondary ion mass spectrometry (TOF-SIMS) and Rutherford backscattering spectrometry (RBS). Complementary information on the foil thickness, sharpness of the gold-silver interface, gold purity, and the formation as well as distribution of corrosion products on Zwischgold models have been obtained, representing a starting point for understanding the morphology and the long-term chemistry of Zwischgold artefacts., Journal of cultural heritage, 31, ISSN:1296-2074, ISSN:1778-3674

Moving towards significantly smaller nanostructures, direct structuring techniques such as electron beam lithography approach fundamental limitations in feature size and aspect ratios. Application of nanostructures like diffractive X-ray lenses requires feature sizes of below 10 nm to enter a new regime in high resolution X-ray microscopy. As such dimensions are difficult to obtain using conventional electron beam lithography, we pursue a line-doubling approach. We demonstrate that this method yields structure sizes as small as 6.4 nm. X-ray lenses fabricated in this way are tested for their efficiency and microscopic resolution. In addition, the line-doubling technique is successfully extended to a six-fold scheme, where each line in a template structure written by electron beam lithography evolves into six metal lines.

Recent progress in the performance of polymer electronics devices has depended heavily on detailed knowledge of the properties of the active polymer materials. While many advanced conjugated polymer materials are being synthesized, the limited quantities produced severely restrict opportunities to measure their physical properties. In particular, the absolute mass density is a basic material property that impacts on many other important properties, yet it is very difficult to measure when in limited quantity. Here, we report a method to spatially resolve the absolute mass density of polymer materials at the nanoscale and measure values for polystyrene (1028 (43) kg/m3), PMMA (1140 (26) kg/m3), PFB (727 (51) kg/m3), and F8BT (749 (26) kg/m3). We estimate that the measurement method could be applied to sample quantities less than 1 picogram.

A description is presented of the NeXus data format for X-ray and neutron scattering and muon spectroscopy., NeXus is an effort by an international group of scientists to define a common data exchange and archival format for neutron, X-ray and muon experiments. NeXus is built on top of the scientific data format HDF5 and adds domain-specific rules for organizing data within HDF5 files, in addition to a dictionary of well defined domain-specific field names. The NeXus data format has two purposes. First, it defines a format that can serve as a container for all relevant data associated with a beamline. This is a very important use case. Second, it defines standards in the form of application definitions for the exchange of data between applications. NeXus provides structures for raw experimental data as well as for processed data.

International audience; As dipyranylidenes are excellent hole carriers, applications in organic solar cells or organic light emitting diode are envisaged. In the present study, we investigate the morphology of 2,2′,6,6′-tetraphenyl-4,4′-dipyranylidene (DIPO-Ph$_4$) deposited under vacuum on a silicon nitride (Si$_3$N$_4$) substrate, a paradigmatic system for the study of molecular crystal/inorganic substrate interfaces. Samples with various coating ratios and different thermal treatments were prepared. The films were characterized by atomic force microscopy and scanning transmission X-ray microscopy to gain insight into material growth. The results show a change in orientation at a molecular level depending upon the evaporation conditions. We are now able to tailor an organic layer with a specific molecular orientation and a specific electronic behavior.

Highly crystalline thin films of organic semiconductors offer great potential for fundamental material studies as well as for realizing high-performance, low-cost flexible electronics. The fabrication of these films directly on inert substrates is typically done by meniscus-guided coating techniques. The resulting layers show morphological defects that hinder charge transport and induce large device-to-device variability. Here, a double-step method for organic semiconductor layers combining a solution-processed templating layer and a lateral homo-epitaxial growth by a thermal evaporation step is reported. The epitaxial regrowth repairs most of the morphological defects inherent to meniscus-guided coatings. The resulting film is highly crystalline and features a mobility increased by a factor of three and a relative spread in device characteristics improved by almost half an order of magnitude. This method is easily adaptable to other coating techniques and offers a route toward the fabrication of high-performance, large-area electronics based on highly crystalline thin films of organic semiconductors. ispartof: Advanced Materials vol:29 issue:44 ispartof: location:Germany status: published