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[Display omitted] Soft, waterborne polyurethane dispersions are indispensable components in many state-of-the-art materials, with applications ranging from binders for coatings and adhesives to matrixes for flexible devices. While the static bulk nanostructure of such systems is widely studied, the influence that environmental conditions such as relative humidity and airflow have on their film formation and phase segregation behavior in supported films is unknown. Here, we elucidate the nanostructure evolution occurring during drying of an industrially relevant, soft polyurethane, utilizing real-time, non-destructive grazing incidence X-ray scattering analysis. Using an environmental-controlled casting cell, we highlight the differences between the drying mechanism under different conditions generated by tuning the airflow and the relative humidity. Our results show how the environment's relative humidity strongly influences chain aggregation and chain interdiffusion due to extended plasticization of the hard segment at high humidities, while accelerated air flows are responsible for the occurrence of (partial) skinning. Interestingly, despite changes in the chain aggregation behavior and occurrence of skinning and skin breakup during drying resulting in higher roughness at the film surface, minor influence is registered on the bulk tensile properties of the films, revealing the resilient nature towards environmental conditions of these soft weakly phase segregating polyurethane systems. [ABSTRACT FROM AUTHOR]

The annealing process is one of the most common methods used to study the thermal stability of multilayers. To study the effect of the annealing process on the microstructural variation in NiV/B4C multilayers, different annealing experiments were performed on NiV/B4C multilayers with a d-spacing of 8 nm. This work provides a foundation for the fabrication of non-periodic NiV/B4C multilayers. The NiV/B4C multilayers were investigated by grazing-incidence X-ray reflectometry (GIXR), X-ray diffuse scattering (XRS), atomic force microscopy (AFM), X-ray diffraction (XRD), grazing-incidence small-angle X-ray scattering (GISAXS) and transmission electron microscopy (TEM). The temperature-dependent experiments showed that annealing at 70–290 °C slightly increased the period thickness and interface width. Annealing at higher temperatures resulted in significant structural changes and thickness ratio (Г = dNiV/d) changes from 0.4 to 1/3 at 340 °C. The time-dependent results showed that the microstructural variations primarily occurred after 60 min. The XRD, XRS, GISAXS and TEM were further used to study microstructural changes. It was found that the NiV/B4C multilayers exhibited a microcrystal structure after annealing, and that enhanced crystallinity and an increase in interface roughness were the main reasons for the microstructural changes. [ABSTRACT FROM AUTHOR]

The impact of additives on the nanoscale structures of spin‐cast polymer composite films, particularly in polymer solar cells, is a topic of significant interest. This study focuses on the blend film comprising poly(thieno[3,4‐b]thiophene‐alt‐benzodithiophene) (PTB7) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM), exploring how additives like 1,8‐diiodooctane (DIO) influence the film structures spin‐cast from chlorobenzene solution. Combined results of specular X‐ray and neutron reflectivity, grazing‐incidence small‐ and wide‐angle X‐ray scattering (GISAXS and GIWAXS), and X‐ray photoelectron spectroscopy indicate that DIO could significantly enhance the dispersion of PC71BM and reduce composition inhomogeneity in the film. Time‐resolved GISAXS–GIWAXS with 100 ms resolution further captures a rapid spinodal decomposition of the mixture within 1 s in the constant‐evaporation stage of spin‐casting. Further combined with parallel analysis of time‐resolved UV–Vis reflectance, these findings reveal that DIO mitigates the spinodal decomposition process by accelerating solvent evaporation, which, in turn, decelerates phase segregation, leading to a nucleation‐driven process. These observations provide mechanistic insights into the role of additives in controlling the nanostructural evolution of spin‐cast films by altering the kinetics of solvent evaporation and phase separation during the spin‐coating process. [ABSTRACT FROM AUTHOR]

A multi‐technique analysis was used to investigate how the orientation of single‐crystal Si wafer surfaces affects the size, shape and orientation of NiSi2 nanocrystals grown within the wafers through the thermal diffusion of Ni atoms from a nickel‐doped thin film deposited on the surface. Nickel‐doped thin films were prepared on silicon wafers with three distinct crystallographic orientations, [001], [110] and [111]. Three sets of samples were then annealed at 500, 600 and 700°C for 2 h. Regardless of crystallographic orientation or annealing temperature, NiSi2 nanoplates with a nearly hexagonal shape grew close to the external surface of the wafers, aligning their larger surfaces parallel to one of the planes of the Si{111} crystallographic form. The crystallographic orientation and annealing temperature in the 500–700°C range did not significantly affect the final values of the average diameter and thickness of the nanoplates. However, significant differences were noted in the number of nanoplates formed in Si wafers with different crystallographic orientations. The results indicate that these observed differences are correlated with the number of pre‐existing defects in the wafers that influence the heterogeneous nucleation process. In addition, the average size and size dispersion were determined for pores at the surface of the Si wafers formed due to the etching process used for native oxide removal. [ABSTRACT FROM AUTHOR]

Electrode materials for application in lithium‐ion batteries are commonly probed by X‐ray diffraction (XRD) to investigate their crystalline structure. Grazing incidence wide‐angle X‐ray scattering (GIWAXS) is an extension to XRD since in‐plane structures are also accessible. Additionally, with grazing incidence small‐angle X‐ray scattering (GISAXS), morphological information on the nanoscale can be revealed. In this work, the nanostructure of battery electrodes, which consist of lithium iron phosphate (LiFePO4) as active material, carbon black (CB) as conducting agent, and the polymeric binders polyvinylidenefluoride (PVDF) and poly((trifluoromethane) sulfonimide lithium styrene) (PSTFSILi) is studied by performing GISAXS and GIWAXS. The chemical nature of the binder is tuned by blending PVDF and PSTFSILi. Specifically, a series of LiFePO4 electrodes with polymer blends of the common, non‐conducting PVDF and the single‐ion conducting PSTFSILi with different weight ratios as binders is investigated to understand the influence of the binder on the structure of the electrode in detail. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) complement these studies to correlate the morphology and structure with the electrochemical behavior. It is found that LiFePO4 crystallites do not exhibit any preferred orientation with respect to the substrate, irrespective of the binder composition, but their size depends on the binder composition. [ABSTRACT FROM AUTHOR]

Grazing incidence small angle X-ray scattering (GISAXS) was used to study the structure and interparticle spacing of monolayers of organic ligand-stabilized iron oxide nanocrystals floating at the air–water interface on a Langmuir trough, and after transfer to a solid support via the Langmuir–Blodgett technique. GISAXS measurements of the nanocrystal arrangement at the air–water interface showed that lateral compression decreased the interparticle spacing of continuous films. GISAXS also revealed that Langmuir–Blodgett transfer of the nanocrystal layers to a silicon substrate led to a stretching of the film, with a significant increase in interparticle spacing. [ABSTRACT FROM AUTHOR]

Ionomers are important to electrode function in energy conversion devices, such as fuel cells and electrolyzers, as the catalyst‐binding nanometer‐thick films under confinement, which compromises mass transport of species. Mitigating confinement effects is necessary for improved performance of polymer electrolyte fuel cells. Studies on perfluorosulfonic acid (PFSA) ionomers provided insights into origins of transport resistances, but limited improvements by current strategies necessitate a need for alternative chemistries to enhance film function. This work investigates new ionomers based on sidechain modifications of PFSA to tune local acidity and structure. Their application‐relevant properties (hydration, thermal‐transition) and nanomorphology are systematically characterized using environmental ellipsometry and grazing‐incidence X‐ray scattering, respectively, to develop chemistry‐structure‐property relationships in thin‐film motif (≤100 nm). Introducing acid sites to sidechains improves hydration and nano‐phase‐separation but reduce chain mobility. Replacing the hydrophilic end‐groups with hydrophobic perfluoro‐groups enhances mobility but disrupts phase‐separation. Although modifying sidechain functional groups alters ionomer‐substrate interactions (Pt/C), chemistry has greater influence on structure‐properties. Proton conductivity correlates with hydration, regardless of chemistry. This work improves the fundamental understanding of chemistry‐function relationships of ionomers by providing a novel means to independently control their side‐chain vs. end‐group and observe resulting effects on interfacial properties to modulate electrode function in electrochemical technologies. [ABSTRACT FROM AUTHOR]

The colloidal layer formation on porous materials is a crucial step for printing and applying functional coatings, which can be used to fabricate anticounterfeiting paper. The deposition of colloidal layers and subsequent thermal treatment allows for modifying the hydrophilicity of the surface of a material. In the present work, wood-based colloidal inks are applied by spray deposition on spray-deposited porous cellulose nanofibrils (CNF) films. The surface modification by thermal annealing of the fabricated colloid-cellulose hybrid thin films is investigated in terms of layering and hydrophobicity. The polymer colloids in the inks are core–shell nanoparticles with different sizes and glass transition temperatures (Tg), thus enabling different and low thermal treatment temperatures. The ratio between the core polymers, poly-(sobrerol methacrylate) (PSobMA), and poly-(-butyl methacrylate) (PBMA) determines the Tg and hence allows for tailoring of the Tg. The layer formation of the colloidal inks on the porous CNF layer depends on the imbibition properties of the CNF layer which is determined by their morphology. The water adhesion of the CNF layer decreases due to the deposition of the colloids and thermal treatment except for the colloids with a size smaller than the void size of the porous CNF film. In this case, the colloids are imbibed into the CNF layer when Tg of the colloids is reached and the polymer chains transit in a mobile phase. Tailored aggregate and nanoscale-embedded hybrid structures are achieved depending on the colloid properties. The imbibition of these colloids into the porous CNF films is verified with grazing incidence small-angle X-ray scattering. This study shows a route for tuning the nanoscale structure and macroscopic physicochemical properties useful for anticounterfeiting paper. [ABSTRACT FROM AUTHOR]

Electrode materials for application in lithium‐ion batteries are commonly probed by X‐ray diffraction (XRD) to investigate their crystalline structure. Grazing incidence wide‐angle X‐ray scattering (GIWAXS) is an extension to XRD since in‐plane structures are also accessible. Additionally, with grazing incidence small‐angle X‐ray scattering (GISAXS), morphological information on the nanoscale can be revealed. In this work, the nanostructure of battery electrodes, which consist of lithium iron phosphate (LiFePO4) as active material, carbon black (CB) as conducting agent, and the polymeric binders polyvinylidenefluoride (PVDF) and poly((trifluoromethane) sulfonimide lithium styrene) (PSTFSILi) is studied by performing GISAXS and GIWAXS. The chemical nature of the binder is tuned by blending PVDF and PSTFSILi. Specifically, a series of LiFePO4 electrodes with polymer blends of the common, non‐conducting PVDF and the single‐ion conducting PSTFSILi with different weight ratios as binders is investigated to understand the influence of the binder on the structure of the electrode in detail. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) complement these studies to correlate the morphology and structure with the electrochemical behavior. It is found that LiFePO4 crystallites do not exhibit any preferred orientation with respect to the substrate, irrespective of the binder composition, but their size depends on the binder composition.

Ionomer thin-films (i.e., 20–100 nm) on supports serve as model systems to understand ionomer-catalyst interfacial behavior as well as the confinement-driven deviation in properties from bulk membranes. While ionomer thin-films have been examined for proton exchange ionomers, the thin-film properties of anion exchange ionomers (AEIs) remain largely unexplored. More importantly, delineating the convoluted impact of chemistry and confinement on thin-film morphology and hydration is of interest to advancing the field on functional ionic interfaces. In this work, these aspects are studied by using AEIs of different backbones (perfluorinated, aliphatic, and aromatic) and side chains (various lengths, and single versus dual functional groups). Quartz-crystal microbalance and spectroscopic ellipsometry are used to analyze density and coupled with calculated free volume fraction of thin-films to provide insights on their gas transport properties. AEI side-chain's chemical character plays a key role in how confinement modulates hydration (in thin-film versus bulk). The results elucidate the effects of backbone, side-chain chemistry versus anion/cation type in the confinement-driven changes in thin-film morphology and swelling. This study also provides new insights for tuning AEI transport functionalities at interfaces via chemistry, which can benefit the design and development of electrode-ionomers for alkaline membrane-based energy systems.

Grazing incidence small angle X-ray scattering (GISAXS) was used to study the structure and interparticle spacing of monolayers of organic ligand-stabilized iron oxide nanocrystals floating at the air–water interface on a Langmuir trough, and after transfer to a solid support via the Langmuir–Blodgett technique. GISAXS measurements of the nanocrystal arrangement at the air–water interface showed that lateral compression decreased the interparticle spacing of continuous films. GISAXS also revealed that Langmuir–Blodgett transfer of the nanocrystal layers to a silicon substrate led to a stretching of the film, with a significant increase in interparticle spacing.

The evolution of the tungsten microstructure and properties under helium irradiation could cause problems for both operational and safety reasons in fusion reactors. In particular, the presence of helium bubbles, formed mainly in the subsurface area, modifies the mechanical and retention properties of radioactive elements. In that context we have investigated the shape of helium bubbles in tungsten induced by helium irradiation under well-defined experimental conditions. We have used single crystals with controlled bombardment energy, flux, fluence and post-irradiation annealing at high temperature under ultra-high vacuum in order to get closer to the thermodynamic equilibrium of the helium bubbles. The bubble shape has been characterized by a combination of TEM and 3D reciprocal space map by in-situ GISAXS. We have shown the presence of facetted bubbles exposing {110} and {100} facets of similar size. Using Wulff theorem and experimental results from both techniques, we derive a surface energy ratio of γ100γ110= 1.03 ± 0.03.

Grazing-incidence small-angle X-ray scattering (GISAXS) is a widely used method for the characterization of the nanostructure of supported thin films and enables time-resolved in situ measurements. The 2D scattering patterns contain detailed information about the nanostructures within the film and at its surface. However, this information is distorted not only by the reflection of the X-ray beam at the substrate-film interface and its refraction at the film surface but also by scattering of the substrate, the sample holder and other types of parasitic background scattering. In this work, a new, efficient strategy to simulate and fit 2D GISAXS patterns that explicitly includes these effects is introduced and demonstrated for (i) a model case nanostructured thin film on a substrate and (ii) experimental data from a microphase-separated block copolymer thin film. To make the protocol efficient, characteristic linecuts through the 2D GISAXS patterns, where the different contributions dominate, are analysed. The contributions of the substrate and the parasitic background scattering - which ideally are measured separately - are determined first and are used in the analysis of the 2D GISAXS patterns of the nanostructured, supported film. The nanostructures at the film surface and within the film are added step by step to the real-space model of the simulation, and their structural parameters are determined by minimizing the difference between simulated and experimental scattering patterns in the selected linecuts. Although in the present work the strategy is adapted for and tested with BornAgain, it can be easily used with other types of simulation software. The strategy is also applicable to grazingincidence small-angle neutron scattering. [ABSTRACT FROM AUTHOR]

In times of climate change and resource scarcity, researchers are aiming to find sustainable alternatives to synthetic polymers for the fabrication of biodegradable, eco-friendly, and, at the same time, high-performance materials. Nanocomposites have the ability to combine several favorable properties of different materials in a single device. Here, we evaluate the suitability of two kinds of inks containing silver nanowires for the fast, facile, and industrial-relevant fabrication of two different types of cellulose-based silver nanowire electrodes via layer-by-layer spray deposition only. The Type I electrode has a layered structure, which is composed of a network of silver nanowires sprayed on top of a cellulose nanofibrils layer, while the Type II electrode consists of a homogeneous mixture of silver nanowires and cellulose nanofibrils. A correlation between the surface structure, conductivity, and transparency of both types of electrodes is established. We use the Haacke figure of merit for transparent electrode materials to demonstrate the favorable influence of cellulose nanofibrils in the spray ink by identifying Type II as the electrode with the lowest sheet resistance (minimum 5 ± 0.04 Ω/sq), while at the same time having a lower surface roughness and shorter fabrication time than Type I. Finally, we prove the mechanical stability of the Type II electrode by bending tests and its long-time stability under ambient conditions. The results demonstrate that the mixed spray ink of silver nanowires and cellulose nanofibrils is perfectly suitable for the fast fabrication of highly conductive organic nanoelectronics on an industrial scale. [ABSTRACT FROM AUTHOR]

GaN nanowires (NWs) grown by molecular beam epitaxy on Ti films sputtered on Al2O3 are studied by X‐ray diffraction (XRD) and grazing‐incidence small‐angle X‐ray scattering (GISAXS). XRD, performed both in symmetric Bragg reflection mode and at grazing incidence, reveals Ti, TiN, Ti3O, Ti3Al and Ga2O3 crystallites with in‐plane and out‐of‐plane lattice parameters intermediate between those of Al2O3 and GaN. These topotaxial crystallites in the Ti film, formed as a result of interfacial reactions and N exposure, possess little misorientation with respect to Al2O3. As a result, GaN NWs grow on the top TiN layer, possessing a high degree of epitaxial orientation with respect to the substrate. The measured GISAXS intensity distributions are modelled by the Monte Carlo method, taking into account the orientational distributions of NWs, the variety of their cross‐sectional shapes and sizes, and the roughness of their side facets. The cross‐sectional size distributions of the NWs and the relative fractions of the {1100} and {1120} side facets are determined. [ABSTRACT FROM AUTHOR]

Here, an experimental grazing‐incidence small‐angle X‐ray scattering (GISAXS) study of the nanostructure of a sample composed of a Si(001) wafer covered by a Ni‐doped SiO2 thin film and thermally treated at high temperature is described. Previous studies indicated that this type of composite contains Ni nanocrystals mainly inside the thin film and NiSi2 nanoplates buried in the Si wafer. To achieve accurate determinations of low‐resolution structural parameters of the nanoparticles derived from the experimental results (shape, volume and size), two GISAXS patterns were recorded. The first pattern was produced by the Si wafer covered by a nanoporous Ni‐doped SiO2 thin film and the second pattern was recorded after removal of the SiO2 thin film by chemical etching. By using the procedure of best fitting of a modeled isotropic GISAXS intensity to a set of 1D GISAXS patterns recorded before thin‐film removal, the average radius and radius dispersion of a size polydisperse set of spherical Ni nanocrystals were determined. The GISAXS pattern recorded after removal of the SiO2 thin film was almost completely due to the scattering intensity produced by oriented NiSi2 nanoplates located inside the Si wafer. By fitting a theoretical function for the X‐ray scattering intensity produced by oriented nanoplates to a set of experimental 1D GISAXS patterns, the maximum diameters and average thickness of the hexagonal NiSi2 nanoplates were determined. The GISAXS intensity pattern produced by the sample after thin‐film removal is essentially anisotropic (with only a weak isotropic contribution from Ni nanocrystals), thus allowing for precise quantitative determinations of the relevant sizes of the NiSi2 nanoplates. [ABSTRACT FROM AUTHOR]

Grazing-incidence small-angle x-ray scattering (GISAXS) and thermal desorption spectroscopy (TDS) were used to study the thermal evolution of helium (He) bubbles in tungsten (W). W samples were exposed to a low ion energy (∼20 eV, sheath accelerated) He plasma at two sample temperatures: 573 K (low-temperature) and 1050 K (high-temperature). They were then annealed to temperatures of 773 K, 873 K and 998 K. GISAXS analysis showed an increase in the median bubble radius of the high-temperature samples from 6.42 Å to 12.87 Å as a result of annealing to 998 K. No changes in the bubble radii distributions were observed for the low-temperature samples and the median radius remained at ∼4 Å even after annealing. TDS showed that the desorption behaviour of He in W has a dependence on the sample temperature during plasma irradiation. The higher-temperature sample experienced a maximum desorption rate that is an order of magnitude larger than the low-temperature sample. The desorption profile of the high-temperature sample spanned a wider temperature range, 500 K - 1500 K, than the low-temperature sample, 500 K - 750 K. The formation and thermal evolution of He bubbles in W have a clear dependence on sample temperature during plasma exposure. The differences in annealing behaviour observed in this work agree with prior in-situ TEM annealing experiments and help explain macroscopic plasma-material interaction effects such as recrystallisation suppression. • Annealing causes growth in He bubbles in W exposed to plasma at 1050 K. • No growth in He bubbles after annealing W exposed to He plasma at 573 K. • He desorption by annealing is higher in W exposed at 1050 K than at 573 K. • He desorption in W exposed to 1050 K is a symptom of the bubble growth mechanism. • GISAXS trends agree with prior in-situ TEM annealing experiments. [ABSTRACT FROM AUTHOR]

Xi-cam is an extensible platform for data management, analysis and visualization. Xi-cam aims to provide a flexible and extensible approach to synchrotron data treatment as a solution to rising demands for high-volume/high-throughput processing pipelines. The core of Xi-cam is an extensible plugin-based graphical user interface platform which provides users with an interactive interface to processing algorithms. Plugins are available for SAXS/WAXS/GISAXS/GIWAXS, tomography and NEXAFS data. With Xi-cam's `advanced' mode, data processing steps are designed as a graph-based workflow, which can be executed live, locally or remotely. Remote execution utilizes high-performance computing or de-localized resources, allowing for the effective reduction of high-throughput data. Xi-cam's plugin-based architecture targets cross-facility and cross-technique collaborative development, in support of multi-modal analysis. Xi-cam is open-source and cross-platform, and available for download on GitHub.

Ternary hybrid thin films composed of a diblock copolymer templating two types of nanoparticles (NPs) expand the functionality of binary systems, which renders them interesting for magnetic sensing or magnetic data storage applications. Herein, one-pot slot-die printed hybrid polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) thin films are prepared with iron oxide (magnetite, Fe 3 O 4 , d = 20 nm) and nickel NPs (Ni, d = 46 nm) in one step by the advanced slot-die coating technique, which facilitates upscaling of fabrication. The evolution of the hybrid film morphology is probed with in situ grazing-incidence small-angle X-ray scattering and compared to that of a PS- b -PMMA thin film without NPs. Additionally, scanning electron microscopy and atomic force microscopy are used to analyze the surface morphology of hybrid films with an increasing NP content after deposition. It is found that different from the pure PS- b -PMMA thin film drying kinetics with five stages, the ternary hybrid film formation can be divided into four stages that are attributed first to the wet film, solvent evaporation, a subsequent rapid coalescence and microphase separation, and finally the dry film. The magnetic properties of the hybrid thin films are investigated with a superconducting quantum interference device magnetometer. All hybrid films are ferrimagnetic and with increasing nickel weight percent in the hybrid film, while the iron oxide weight percent is kept constant, the magnetic properties of the film are modulated accordingly.

Responsive nanostructured films from food-grade lipids can be valuable for food, pharmaceutical, and biotechnological science. Lyotropic liquid crystalline structures that respond to enzymes in their environment can, for instance, be innovated as drug delivery platforms or biosensors. However, the structural changes that such films undergo during enzymatic reactions with lipase are not yet understood. This work demonstrates the preparation of mesostructured lipid films from the food-grade lipids glycerol monooleate (GMO) and triolein on silicon wafers and their digestion with pancreatic lipase using time-resolved synchrotron grazing incidence small-angle X-ray scattering (GISAXS). The film structure is compared with the corresponding GMO/triolein bulk phases in excess water. Increasing the GMO/triolein ratio in the film makes it possible to modulate the structure of the films from oil coatings to inverse hexagonal and inverse bicontinuous cubic films. Pancreatic lipase triggered swelling of the internal film nanostructure and eventually structural transformation inside the film. Orientation and reorientation of the internal film structure relative to the silicon wafer surface were observed during the preparation of the films and their digestion. The findings contribute to the understanding of self-assembly in thin films and guide the development of enzyme-responsive coatings for the functional modification of various substrates.

Featured Application: This paper presents the open software platform GisaxStudio for analysis of GISAXS maps from 3D lattices of nanoparticles. Grazing-incidence small-angle X-ray scattering (GISAXS) is a powerful method for the structural analysis of ordered arrays of nanoparticles, quantum dots, or similar objects. However, for the correct interpretation of the measured GISAXS intensity distributions, a proper data analysis, including a suitable model, is required. Here, we demonstrate a software platform, GisaxStudio, aimed at the analysis and simulation of 2D GISAXS intensity distributions from ordered lattices of different nanoparticles. It contains several models that satisfactorily describe the GISAXS from 3D lattices or crystals of nanoparticles prepared by the self-assembly processes, pre-pattering, or ion-beam interaction with the material within their tracks. It also supports different shapes of nanoparticles, including core-shell structure with the center of core possibly displaced from the center of the shell. The software is very useful for fast and accurate GISAXS data analysis. [ABSTRACT FROM AUTHOR]

The properties of semiconductor materials can be strongly affected by the addition of metallic nanoparticles. Here we investigate the properties of SiC + Au and Si3N4 + Au thin films prepared by magnetron sputtering deposition followed by thermal annealing. The influence of gold addition on the optical and electrical properties is explored. We show the formation of self-assembled Au nanoparticles in SiC and Si3N4, with the size and arrangement properties determined by the deposition and annealing conditions. Both SiC- and Si3N4-based films show an increase in the overall absorption with increasing Au content, and its decrease with increasing annealing temperature. All films show the presence of surface plasmon resonance, whose peaks shift toward larger wavelengths with increasing Au nanoparticle size. The resistivity significantly drops with the Au content increase for both types of matrices, although the resistivity of Si3N4-based films is much higher. The incorporated quantity of Au in the host matrix was chosen in such a way to demonstrate that a huge range of optical and electrical characteristics is achievable. The materials are very interesting for application in opto-electronic devices. [ABSTRACT FROM AUTHOR]

[Display omitted] • Comparison of biased DCMS, HiPIMS and bipolar HiPIMS silver deposition. • HiPIMS offers additional control of early growth stage on SiO 2 and PS. • Ion acceleration limits surface diffusion thus increasing surface coverage. • Bipolar HiPIMS results in earliest percolation and lowest resistance. The integration of silver thin films into optoelectronic devices has gained much interest due to their exceptional properties in terms of conductivity and compatibility with flexible substrates. For this type of application, ultra-thin layers are desirable, because of their optical transparency. Standard direct current magnetron sputtering (DCMS) is known to lead to undesirable formation of islands at low effective film thicknesses on typical substrates like SiO 2 or polystyrene (PS). Therefore, in this study, we explore high-power impulse magnetron sputtering (HiPIMS) with optional further acceleration of metal ions by biasing the substrate or an additional positive pulse (bipolar HiPIMS) for the fabrication of ultra-thin silver layers. The morphology and electrical properties of ultra-thin silver layers with selected effective thicknesses are characterized on SiO 2 and PS substrates. The growth evolution of characteristic parameters is further investigated by in-situ grazing-incidence small-angle X-ray scattering (GISAXS). The results show that HiPIMS deposition yields films with a higher density of clusters than DCMS leading to a percolation threshold at lower effective film thicknesses. This effect is amplified by further ion acceleration. Thus, we suggest HiPIMS as a promising technique for fabricating ultra-thin, conductive layers on organic and oxide substrates. [ABSTRACT FROM AUTHOR]

The rapid growth of digital information in the world necessitates a big leap in improving the existing technologies for magnetic recording. For the best modern perpendicular recording, the highest coercivity materials with minimal volume are required. We present a study of a facile technology for establishing mono- and multilayer surfaces from various single-domain flat magnetic nanoparticles that exhibit a strong perpendicular-oriented magnetic moment on solid and flexible substrates. Surfactant-free, hard ferromagnetic, and single-domain anisotropic strontium hexaferrite SrFe12O19 nanoparticles with a perpendicular magnetic moment orientation and two different aspect ratios are self-ordered into magnetic thin nanofilms, exploiting the templating effect of cellulose nanofibrils and magnetic fields. Uniform magnetic coatings obtained by the scalable layer-by-layer spray deposition from a monolayer coverage up to thicknesses of a few tens of nanometers show a preferred in-plane orientation of the hard-magnetic nanoparticles. High coercivities of the films of up to 5 kOe and a high perpendicular anisotropy of Mr⊥/Ms > 80% are found. The application of the magnetic field during film deposition ensures additional improvement in perpendicular magnetic anisotropy and the appearance of residual magnetization in the film of up to 0.6Ms. For low-aspect-ratio nanoparticles stacked in periodic planar structures, the signs of the photonic band gap are revealed. The ability to create scalable, thin magnetic structures based on nanosized particles/building blocks opens great opportunities for their application in a wide variety of optoelectronic and magnetic storage devices. [ABSTRACT FROM AUTHOR]

Fluorine-doped tin oxide thin films (SnO2:F) are widely used as transparent conductive oxide electrodes in thin-film solar cells because of their appropriate electrical and optical properties. The surface morphology of these films influences their optical properties and therefore plays an important role in the overall efficiencies of the solar cells in which they are implemented. At rough surfaces light is diffusely scattered, extending the optical path of light inside the active layer of the solar cell, which in term improves light absorption and solar cell conversion efficiency. In this work, we investigated the surface morphology of undoped and doped SnO2 thin films and their influence on the optical properties of the films. We have compared and analysed the results obtained by several complementary methods for thin-film surface morphology investigation: atomic force microscopy (AFM), transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS). Based on the AFM and TEM results we propose a theoretical model that reproduces well the GISAXS scattering patterns. [ABSTRACT FROM AUTHOR]

Non‐fullerene acceptor (NFA)‐based organic solar cells have made tremendous progress in recent years. For the neat NFA system PBDB‐T:ITIC, the film morphology and crystallinity are tailored by the choice of the solvent used for spin coating the active layers. Three different chlorinated solvents, chlorobenzene (CB), chloroform, and dichlorobenzene, are compared and the obtained active layer morphology is correlated with the optoelectronic properties and the device performance. The small domain sizes in the case of CB are most beneficial for the device performance, whereas the largest number or size of face‐on PBDB‐T crystallites is not causing the highest power conversion efficiencies (PCEs). In addition, when using CB, the number of edge‐on crystallites is highest and the distances between neighboring domains are small. The smoothest blend films are realized with CB, which exhibit correlated roughness with their substrates and no large aggregates have formed in these blend films. Thus, CB offers the best way to balance the aggregation and crystallization kinetics in the active layer and enables the highest PCE values. [ABSTRACT FROM AUTHOR]

Although amphiphilic diblock copolymer templating of inorganic materials such as TiO2 is already well investigated, sol–gel synthesis routines for porous silicon and germanium are relatively rare. Therefore, especially in the field of Li-ion batteries, novel synthesis routines with the possibility to tune the silicon and germanium ratio and the morphology in the nanometer regime are of high interest. Here, we demonstrate a synthesis method that allows a change of morphology and elemental composition with minimal effort. We evidence a morphological transformation in the nanometer regime with real space (scanning electron microscopy) and complementary reciprocal space analysis methods (grazing-incidence small-angle X-ray scattering). Although energy-dispersive X-ray spectroscopy (EDS) reveals a considerable amount of oxygen in the thin film, crystalline Ge in the bulk is detected with powder X-ray diffraction (PXRD) and Raman spectroscopy. Due to the system's simplicity, chemical mass production options such as roll-to-roll or slot-die printing can also be considered high-yield methods compared to standard synthesis routines. [ABSTRACT FROM AUTHOR]

Grazing-incidence small-angle X-ray scattering (GISAXS) is an important technique in the characterization of samples at the nanometre scale. A key aspect of GISAXS data analysis is the accurate simulation of samples to match the measurement. The distorted-wave Born approximation (DWBA) is a widely used model for the simulation of GISAXS patterns. For certain classes of sample such as nanostructures embedded in thin films, where the electric field intensity variation is significant relative to the size of the structures, a multi-slice DWBA theory is more accurate than the conventional DWBA method. However, simulating complex structures in the multi-slice setting is challenging and the algorithms typically used are designed on a case-by-case basis depending on the structure to be simulated. In this paper, an accurate algorithm for GISAXS simulations based on the multi-slice DWBA theory is presented. In particular, fundamental properties of the Fourier transform have been utilized to develop an algorithm that accurately computes the average refractive index profile as a function of depth and the Fourier transform of the portion of the sample within a given slice, which are key quantities required for the multi-slice DWBA simulation. The results from this method are compared with the traditionally used approximations, demonstrating that the proposed algorithm can produce more accurate results. Furthermore, this algorithm is general with respect to the sample structure, and does not require any sample-specific approximations to perform the simulations. This paper presents an accurate numerical algorithm for simulating grazing-incidence small-angle X-ray scattering patterns of nanostructures using the multi-slice distorted-wave Born approximation. The method overcomes the typical challenge of requiring the users to manually specify a way to approximate their samples by utilizing properties of Fourier transforms to automate the computation.

Self-assembly of diblock copolymers (BCP) into periodic arrays is a promising route to generate templates for the fabrication of nanoscopic elements, when one block is selectively removed. In cylindrical morphology polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymer (BCP) films, the efficiency of different processes for removing the PMMA from cylinders is studied using grazing incidence small angle X-ray scattering (GISAXS), x-ray reflectivity and critical dimension scanning electron microscopy. The detailed analysis of the GISAXS patterns leads to the determination of the depth of cylindrical holes left by removal of the PMMA. It is found that the combination of a preliminary UV exposure followed by a wet treatment allows to remove totally the PMMA blocks. Furthermore, the optimization of both UV exposition time and solvent allows to preserve the PS matrix and interestingly for nanolithographic applications to decrease the process costs.

Tailoring of plasmon resonances is essential for applications in anticounterfeiting. This is readily achieved by tuning the composition of alloyed metal clusters; in the simplest case, binary alloys are used. Yet, one challenge is the correlation of cluster morphology and composition with the changing optoelectronic properties. Hitherto, the early stages of metal alloy nanocluster formation in immiscible binary systems such as silver and copper have been accessible by molecular dynamics (MD) simulations and transmission electron microscopy (TEM). Here, we investigate in real time the formation of supported silver, copper, and silver-copper-alloy nanoclusters during sputter deposition on poly-(methyl methacrylate) by combining in situ surface-sensitive X-ray scattering with optical spectroscopy. While following the transient growth morphologies, we quantify the early stages of phase separation at the nanoscale, follow the shifts of surface plasmon resonances, and quantify the growth kinetics of the nanogranular layers at different thresholds. We are able to extract the influence of scaling effects on the nucleation and phase selection. The internal structure of the alloy cluster shows a copper-rich core/silver-rich shell structure because the copper core yields a lower mobility and higher crystallization tendency than the silver fraction. We compare our results to MD simulation and TEM data. This demonstrates a route to tailor accurately the plasmon resonances of nanosized, polymer-supported clusters which is a crucial prerequisite for anticounterfeiting. [ABSTRACT FROM AUTHOR]

In situ synchrotron small‐angle X‐ray scattering (SAXS) is a powerful tool for studying dynamic processes during material preparation and application. The processing and analysis of large data sets generated from in situ X‐ray scattering experiments are often tedious and time consuming. However, data processing software for in situ experiments is relatively rare, especially for grazing‐incidence small‐angle X‐ray scattering (GISAXS). This article presents an open‐source software suite (SGTools) to perform data processing and analysis for SAXS and GISAXS experiments. The processing modules in this software include (i) raw data calibration and background correction; (ii) data reduction by multiple methods; (iii) animation generation and intensity mapping for in situ X‐ray scattering experiments; and (iv) further data analysis for the sample with an order degree and interface correlation. This article provides the main features and framework of SGTools. The workflow of the software is also elucidated to allow users to develop new features. Three examples are demonstrated to illustrate the use of SGTools for dealing with SAXS and GISAXS data. Finally, the limitations and future features of the software are also discussed. [ABSTRACT FROM AUTHOR]

Gas bubbles are a necessary byproduct of water electrolysis whereby hydrogen and oxygen are produced from water. These attached gases reduce the electrode's active area, which necessitates a deep understanding of the bubble life cycle starting from nanobubbles. Synchronized with the electrochemistry, the time evolution of the surface nanobubble size and coverage is resolved using grazing incidence small-angle X-ray scattering (GISAXS) and correlated with optical microscopy and theoretical calculations to show that a significant portion of the surface is covered in nanobubbles after larger micron-sized bubbles are observed. These nanobubbles increase in number and decrease in size, toward 2 nm diameter, with the charge passed. The trend in size and number is consistent with an increase in supersaturation, which reduces the nascent bubble size. Altogether, this study suggests a significant portion of the surface contains nanobubbles and that strategies to reduce the dissolved hydrogen would be effective at reducing the nanobubble surface coverage.

PbS quantum dots (QDs) are promising for short-wave infrared (SWIR) photodetection and imaging. Solid-state ligand exchange (SSLE) is a low-fabrication-threshold QD solid fabrication method. However, QD treatment by SSLE remains challenging in seeking refined surface passivation to achieve the desired device performance. This work investigates using NaAc in the ligand exchange process to enhance the film morphology and electronic coupling configuration of QD solids. By implementing various film and photodetector device characterization studies, we confirm that adding NaAc with a prominent adding ratio of 20 wt % NaAc with tetrabutylammonium iodide (TBAI) in the SSLE leads to an improved film morphology, reduced surface roughness, and decreased trap states in the QD solid films. Moreover, compared to the devices without NaAc treatment, those fabricated with NaAc-treated QD solids exhibit an enhanced performance, including lower dark current density (<100 nA/cm 2 ), faster response speed, higher responsivity, detectivity, and external quantum efficiency (EQE reaching 25%). The discoveries can be insightful in developing efficient, low-cost, and low-fabrication-threshold QD SWIR detection and imager applications.

Ionic liquid (IL) post‐treatment of poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films with ethyl‐3‐methylimidazolium dicyanamide (EMIM DCA), allyl‐3‐methylimidazolium dicyanamide (AMIM DCA), and 1‐ethyl‐3‐methylimidazolium tetracyanoborate (EMIM TCB) is compared. Doping level modifications of PEDOT are characterized using UV–Vis spectroscopy and directly correlate with the observed Seebeck coefficient enhancement. With conductive atomic force microscopy (c‐AFM) the authors investigate changes in the topographic‐current features of the PEDOT:PSS thin film surface due to IL treatment. Grazing incidence small‐angle X‐ray scattering (GISAXS) demonstrates the morphological rearrangement towards an optimized PEDOT domain distribution upon IL post‐treatment, directly facilitating the interconductivity and causing an increased film conductivity. Based on these improvements in Seebeck coefficient and conductivity, the power factor is increased up to 236 µW m−1K−2. Subsequently, a model is developed indicating that ILs, which contain small, sterically unhindered ions with a strong localized charge, appear beneficial to boost the thermoelectric performance of post‐treated PEDOT:PSS films. [ABSTRACT FROM AUTHOR]

Here, we report on adding an important dimension to the fundamental understanding of the evolution of the thin film micro structure evolution. Thin films have gained broad attention in their applications for electro-optical devices, solar-cell technology, as well storage devices. Deep insights into fundamental functionalities can be realized via studying crystallization microstructure and formation processes of polycrystalline or epitaxial thin films. Besides the fundamental aspects, it is industrially important to minimize cost which intrinsically requires lower energy consumption at increasing performance which requires new approaches to thin film growth in general. Here, we present a state of the art sputtering technique that allows for time-resolved in situ studies of such thin film growth with a special focus on the crystallization via small angle scattering and X-ray diffraction. Focusing on the crystallization of the example material of BaTiO 3 , we demonstrate how a prototypical thin film forms and how detailed all phases of the structural evolution can be identified. The technique is shaped to enable a versatile approach for understanding and ultimately controlling a broad variety of growth processes, and more over it demonstrate how to in situ investigate the influence of single high temperature sputtering parameters on the film quality. It is shown that the whole evolution from nucleation, diffusion adsorption and grain growth to the crystallization can be observed during all stages of thin film growth as well as quantitatively as qualitatively. This can be used to optimize thin-film quality, efficiency and performance. [ABSTRACT FROM AUTHOR]

Spin‐wave based technologies that use collective oscillation of electrons termed magnons have been proposed for future computing landscapes due to their low energy consumption and high data transfer speeds. Magnonic crystals, materials with magnetic properties periodically varied in space, are central to such technologies. However, they are currently limited by the lithography techniques used for the magnetic patterning. To address this issue, bottom‐up self‐assembly using polymer templates to order magnetic cargo is presented. In this work, block copolymer micelles are used as templates to direct the organization of polyoxometalate (POM) molecules into organized assemblies. The structural organization of these assemblies is evaluated using microscopy and scattering techniques. The organized POM assemblies are demonstrated to modulate spin‐waves excited in permalloy thin films. This work demonstrates the first use of a bottom‐up approach to realize the fabrication of a magnonic assembly at the nanoscale. It further paves the way to achieve magnon‐mediated self‐assembled computing architectures. [ABSTRACT FROM AUTHOR]

The properties of semiconductor materials can be strongly affected by the addition of metallic nanoparticles. Here we investigate the properties of SiC + Au and Si3N4 + Au thin films prepared by magnetron sputtering deposition followed by thermal annealing. The influence of gold addition on the optical and electrical properties is explored. We show the formation of self-assembled Au nanoparticles in SiC and Si3N4, with the size and arrangement properties determined by the deposition and annealing conditions. Both SiC- and Si3N4-based films show an increase in the overall absorption with increasing Au content, and its decrease with increasing annealing temperature. All films show the presence of surface plasmon resonance, whose peaks shift toward larger wavelengths with increasing Au nanoparticle size. The resistivity significantly drops with the Au content increase for both types of matrices, although the resistivity of Si3N4-based films is much higher. The incorporated quantity of Au in the host matrix was chosen in such a way to demonstrate that a huge range of optical and electrical characteristics is achievable. The materials are very interesting for application in opto-electronic devices.

Grazing-incidence small-angle X-ray scattering (GISAXS) is a powerful method for the structural analysis of ordered arrays of nanoparticles, quantum dots, or similar objects. However, for the correct interpretation of the measured GISAXS intensity distributions, a proper data analysis, including a suitable model, is required. Here, we demonstrate a software platform, GisaxStudio, aimed at the analysis and simulation of 2D GISAXS intensity distributions from ordered lattices of different nanoparticles. It contains several models that satisfactorily describe the GISAXS from 3D lattices or crystals of nanoparticles prepared by the self-assembly processes, pre-pattering, or ion-beam interaction with the material within their tracks. It also supports different shapes of nanoparticles, including core-shell structure with the center of core possibly displaced from the center of the shell. The software is very useful for fast and accurate GISAXS data analysis.

Mesoporous α‐Fe2O3 thin films with large area homogeneity demonstrate tremendous potential in multiple applications. In the present work, the synthesis of morphology‐controlled α‐Fe2O3 thin films is realized with polystyrene‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) diblock copolymer assisted sol‐gel chemistry. The solvent category (DMF and 1,4‐dioxane) and polymer‐to‐FeCl3 ratio used for the solution preparation are systematically varied to tune the morphology of the thin films. For both solvents, DMF and 1,4‐dioxane, nanocluster structures are obtained with low PS‐b‐P4VP concentration. When the concentration of PS‐b‐P4VP reaches the critical micelle concentration, spherical and wormlike porous structures are specifically formed in the DMF and 1,4‐dioxane solvent system, respectively. Further increasing the polymer‐to‐FeCl3 ratios leads to the enlargement of the spherical pore sizes in the DMF system, whereas the center‐to‐center distances of the wormlike structures in the 1,4‐dioxane system decrease. Moreover, DMF/1,4‐dioxane solvent mixtures with different volume ratios are applied for the sol–gel solution preparation to gain more insight into how the solvent selectivity affects the thin film morphology. By adjusting the preferential affinity of the solvent mixture to the polymer blocks, a spherical to wormlike pore shape transition is observed with a critical Δχ value of around 0.77. [ABSTRACT FROM AUTHOR]

Polymer–metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics (OPVs). The polymer components used in these devices are mostly nanostructured conductive polymers with conjugated π-electron systems. Enhanced OPV's power conversion efficiencies or sensor sensitivity can be achieved by selective metal deposition on or into polymer templates. In this study, we exploit time-resolved grazing-incidence X-ray scattering to observe the metal–polymer interface formation and the cluster crystallite size in situ during silver (Ag) sputter deposition on a poly-(3-hexylthiophene-2,5-diyl)-b-poly-(methyl methacrylate) (PMMA-b-P3HT) template. We compare the arising nanoscale morphologies with electronic properties, determine Ag growth regimes, and quantify the selective Ag growth for the diblock copolymer (DBC) template using the corresponding homopolymer thin films (P3HT and PMMA) as a reference. Hence, we are able to describe the influence of the respective polymer blocks and substrate effects on the Ag cluster percolation: the percolation threshold is correlated with the insulator-to-metal transition measured in situ with resistance measurements during the sputter deposition. The Ag cluster percolation on PMMA-b-P3HT starts already on the network of the hexagonal P3HT domain before a complete metal film covers the polymer surface, which is complemented by microscopic measurements. In general, this study demonstrates a possible method for the selective Ag growth as a scaffold for electrode preparation in nanoelectronics and for energy harvesting applications. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO 2 ) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO 2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO 2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO 2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO 2 surface. The in situ GISAXS measurements under an N 2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.