X-ray Reflectivity Research Articles

Mesoscale self-organization of polydisperse magnetic nanoparticles at the water surface.

In this study, we investigated the self-ordering process in Langmuir films of polydisperse iron oxide nanoparticles on a water surface, employing in situ x-ray scattering, surface pressure-area isotherm analysis, and Brewster angle microscopy. X-ray reflectometry confirmed the formation of a monolayer, while grazing incidence small-angle x-ray scattering revealed short-range lateral correlations with a characteristic length equal to the mean particle size. Remarkably, our findings indicated that at zero surface pressure, the particles organized into submicrometer clusters, merging upon compression to form a homogeneous layer. These layers were subsequently transferred to a solid substrate using the Langmuir-Schaefer technique and further characterized via scanning electron microscopy and polarized neutron reflectometry. Notably, our measurements revealed a second characteristic length in the lateral correlations, orders of magnitude longer than the mean particle diameter, with polydisperse particles forming circular clusters densely packed in a hexagonal lattice. Furthermore, our evidence suggests that the lattice constant of this mesocrystal depends on the characteristics of the particle size distribution, specifically the mean particle size and the width of the size distribution. In addition, we observed internal size separation within these clusters, where larger particles were positioned closer to the center of the cluster. Finally, polarized neutron reflectometry measurements provided valuable insights into the magnetization profile across the layer.

Tripling of the scattering vector range of X-ray reflectivity on liquid surfaces using a double-crystal deflector.

The maximum range of perpendicular momentum transfer (q z) has been tripled for X-ray scattering from liquid surfaces when using a double-crystal deflector setup to tilt the incident X-ray beam. This is achieved by employing a higher-energy X-ray beam to access Miller indices of reflecting crystal atomic planes that are three times higher than usual. The deviation from the exact Bragg angle condition induced by misalignment between the X-ray beam axis and the main rotation axis of the double-crystal deflector is calculated, and a fast and straightforward procedure to align them is deduced. An experimental method of measuring scattering intensity along the q z direction on liquid surfaces up to q z = 7 Å-1 is presented, with liquid copper serving as a reference system for benchmarking purposes.

Combined Scanned Macro X-Ray Fluorescence and Reflectance Spectroscopy Mapping on Corroded Ancient Bronzes

Bronze is an alloy composed primarily of copper and tin and since its discovery is widespread in the whole world. This alloy can thus be found in many archaeological sites and its study can give information about the technology of production, the trading routes, or the warfare within a region. However, bronze artefacts can undergo severe alteration processes, and the formation of corrosion layers of different copper minerals can prevent the readability of the artefact or even destroy it, as in the case of the ‘bronze disease’. Their preservation is crucial for maintaining a connection to our cultural heritage. In this paper, we present the study of some corroded bronze artefacts found in different burying conditions. They have been analysed through a scanner system that combines two non-invasive techniques, macro XRF (MA-XRF) and visible, near infrared, short wave infrared (VIS-NIR-SWIR) reflectance, to unravel information about the metal and the patina composition, thickness, and distribution. As the corrosion of bronze depends on the burying conditions and the alloy composition, these data are of the utmost importance to understanding the alteration processes occurring in the archaeological site and to ensure the artefacts’ optimal preservation.

Synthesis of WS2 Ultrathin Films by Magnetron Sputtering Followed by Sulfurization in a Confined Space

In the quest for advanced materials suitable for next-generation electronic and optoelectronic applications, tungsten disulfide (WS2) ultrathin films have emerged as promising candidates due to their unique properties. However, obtaining WS2 directly on the desired substrate, eliminating the need for transfer, which produces additional defects, poses many challenges. This paper aims to explore the synthesis of WS2 ultrathin films via physical vapor deposition (PVD) followed by sulfurization in a confined space, addressing the challenge of film formation for practical applications. Precursor layers of tungsten and WS2 were deposited by RF magnetron sputtering. Subsequent sulfurization treatments were conducted in a small, closed, graphite box to produce WS2 films. The physical and chemical properties of these precursor and sulfurized layers were thoroughly characterized using techniques such as X-ray reflectometry (XRR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The findings reveal notable distinctions in film thickness, structural orientation, and chemical composition, attributable to the different precursor used. Particularly, the sulfurized layers from the tungsten precursor exhibited a preferred orientation of WS2 crystallites with their (00L) planes parallel to the substrate surface, along with a deviation from parallelism in a small angular range. This study highlights the necessity of precise control over deposition and sulfurization parameters to tailor the properties of WS2 films for specific technological applications.

A computational approach to predict and enhance the sensitivity of X-ray resonant magnetic reflectometry to the magnetic behavior of deeply buried interfaces

In the present work a computational approach is applied to model and predict the results of X-ray resonant magnetic reflectometry – a non-destructive synchrotron-based technique to probe chemical composition, crystallographic environment and magnetization in multilayer epitaxial heterostructures with nanoscale depth resolution. The discussed 2D mapping approach is a step forward with respect to conventional resonant X-ray reflectometry and consists of collecting a fine step array of reflected intensity as a function of grazing angle and photon energy across the absorption edge of a particular chemical element. With the use of circularly polarized photons the method can be extended to magnetic systems to produce a map of dichroic reflectance directly related to the magnetization profile of the heterostructure. Studying the magnetic field dependence of dichroic reflectance maps can provide valuable information on the magnetization reversal of individual sublayers of a multilayer heterostructure. In the present paper modeling is performed for a bilayer system mimicking the behavior of a 30 nm ɛ-Fe2O3 thin film that is known to exhibit a pronounced two-component magnetic hysteresis. A technique to find optimal energy/angle combinations in order to sense magnetization of individual sublayers is proposed. Also discussed is the advantage of heavy-element capping, which leads to a substantial increase of the dichroic intensity oscillation contrast in the pre-edge region where the sensitivity to the magnetic behavior of the deeply buried interfaces is most pronounced.

A versatile beamline for soft x-ray reflectivity, absorption, and fluorescence measurements at Indus-2 synchrotron source.

A versatile beamline for performing reflectivity, fluorescence, and absorption experiments in the soft x-ray region of 100-1500eV is commissioned on a bending magnet port of the Indus-2 synchrotron source. A high vacuum 2-axis reflectometer with x, y, and z sample scanning stages is installed. This reflectometer is used to measure the reflectivity of large samples up to 300mm in length and 5kg in weight. This feature is useful for characterizing x-ray optical elements, such as mirrors, gratings, and multilayers. A flange mounted silicon drift detector is installed in the downstream of the reflectometer for soft x-ray fluorescence measurements. The soft x-ray absorption measurements are carried out in the total electron yield and partial fluorescence yield modes. Integration of three different experimental techniques in the experimental station makes the beamline versatile for materials science applications as it provides structural, chemical, and electronic state information by performing the required experiments in an identical environment. The beamline uses a varied line spacing plane grating monochromator and gives a high flux (∼109 to 1011 photon/s) with a moderate resolution (λ/Δλ ~1000-5000). A three-mirror-based higher harmonic setup is incorporated to get rid of harmonics and to get a high spectral purity monochromatic beam with less than 0.1% harmonic content. In the present article, the beamline optical scheme, mechanical configuration, and details of the experimental setups are presented, along with a few representative results of each experimental mode.

Interfacial structure changes between amorphous silicon anode/liquid electrolyte using a highly dense and flat model electrode

AbstractChanges in the interfacial structures of the amorphous silicon (a-Si) anode/organic electrolyte interfaces in lithium-ion batteries were investigated using highly dense a-Si films fabricated by cathodic arc plasma deposition as a model electrode. Raman spectroscopy, transmission electron microscopy (TEM), and X-ray reflectivity revealed that the Si films were grown in an amorphous state with an atomically flat surface. The a-Si films exhibited lithium alloying and de-alloying reactions, with a large irreversible capacity during the first cycle. The irreversible capacity was derived from the formation of a solid electrolyte interphase (SEI) along with an incompletely de-alloyed Li-Si phase, as confirmed by ex situ TEM and X-ray photoelectron spectroscopy observations. The discharge and charge capacities of the Si films gradually decreased in the subsequent cycles, despite the fact that no further SEI formation or cracking of the Si layer occurred. Scanning electron microscopy observations combined with energy-dispersive X-ray spectroscopy revealed the miniaturization of the a-Si film in the surface region to generate domains measuring less than a few hundred nanometers. These results suggest that delamination and miniaturization of the a-Si nanodomains from the electrode surface are partly responsible for degradation of the a-Si anode.

Semitransparent Organic Photovoltaic Devices: Interface/Bulk Properties and Stability Issues

In the present work, an insight on the morpho/structural properties of semitransparent organic devices for buildings’ integrated photovoltaics is presented, and issues related to interface and bulk stability are addressed. The organic photovoltaic (OPV) cells under investigation are characterized by a blend of PM6:Y6 as a photo-active layer, a ZnO ETL (electron transporting layer), a HTL (hole transporting layer) of HTL-X and a transparent electrode composed by Ag nanowires (AgNWs). The devices’ active nanomaterials, processed as thin films, and their mutual nanoscale interfaces are investigated by a combination of in situ Energy Dispersive X-ray Reflectometry (EDXR) and ex situ Atomic Force Microscopy (AFM), X-ray Diffraction (XRD) and micro-Raman spectroscopy. In order to discriminate among diverse concomitant aging pathways potentially occurring upon working conditions, the effects of different stress factors were investigated: light and temperature. Evidence is gained of an essential structural stability, although an increased roughness at the ZnO/PM6:Y6 interface is deduced by EDXR measurements. On the contrary, an overall stability of the system subjected to thermal stress in the dark was observed, which is a clear indication of the photo-induced origin of the observed degradation phenomenon. Micro-Raman spectroscopy brings light on the origin of such effect, evidencing a photo-oxidation process of the active material in the device, using hygroscopic organic HTL, during continuous illumination in ambient moisture conditions. The process may be also triggered by a photocatalytic role of the ZnO layer. Therefore, an alternative configuration is proposed, where the hygroscopic HTL-X is replaced by the inorganic compound MoOx. The results show that such alternative configuration is stable under light stress (solar simulator), suggesting that the use of Molybdenum Oxide, limiting the photo-oxidation of the bulk PM6:Y6 active material, can prevent the cell from degradation.

Sc/SiC/Al Multilayer Optimization for Li K Spectroscopy

This paper presents an X-ray reflectivity study of a Sc/SiC/Al periodic multilayer deposited via magnetron sputtering and its possible adaptation to be used as a dispersive element in the crystal spectrometers equipping scanning electron microscopes and electron probe microanalyzers. This multilayer is designed for the spectral range of 45–60 eV. The results reveal a reflectance of 40.8% at 54.1 eV for a near-normal incidence angle of 7° with a narrow bandwidth of 2.6 eV. The measured and simulated reflectivity curves are very close, suggesting that this system has smooth interfaces and low interdiffusion. Owing to the growing importance of lithium and lack of spectroscopic data, we simulate a new Sc/SiC/Al stack based on the reflectivity data and optimize it to perform spectroscopy in the range near the Li K absorption edge around 55 eV, which is in the spectral range of the Li Kα emission band. This optimization is achieved by tuning the thicknesses of the different layers and the number of periods of the multilayer using an in-house Python script. The optimization results are compared with the performances of other multilayers employed in the same energy range and at a working angle close to 30° grazing, including Be/Si/Al. This analysis indicates that the Sc/SiC/Al multilayer could be a good candidate for performing spectroscopy in the Li K range.

Stress-driven recrystallization of pentacene films via diffusion-induced ingress of MOF nanocrystals into the grain boundaries

Metal-organic frameworks (MOFs) have been identified as versatile candidates for producing functional materials for various applications. However, the growth of MOF thin film becomes challenging due to non-availability of a proper solvent that restricts the use of the materials in electronic sensor fabrication. The receptor molecules in sensors are often used to functionalize the semiconducting channel. However, integrating such molecules degrade the crystallinity of channel materials, leading to poor sensor performance. In this work, we report the growth of a MOF (CPO-27-Ni) thin film and the recrystallization of semiconducting pentacene thin films due to diffusion of the crystallites into the grain boundaries. MOF films were successfully spin coated at various revolutions per minute (rpm) on pentacene surfaces. The growth of MOF films was studied using statistical analysis of rough surfaces by utilizing scaling theory to capture the evolution of surface morphologies. The x-ray reflectivity study unveiled the diffusion-induced ingress of the MOF through the grain boundaries of pentacene films that imparts compressive stress within the grains leading to subsequent rearrangement of pentacene molecules in the thin-film phase and recrystallizes the bulk crystallographic phase, which in a way will enhance the device performance.

Probing the Electronic Structure of Prussian Blue and Analog Films by Photoemission and Electron Energy Loss Spectroscopies.

X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS) were employed to characterize the electronic properties of Prussian blue (PB) and its analogs when electrodeposited over metal-decorated carbon nanotubes (CNTs). Through an investigation of the influence of carbon nanotubes (CNTs) and preparation conditions on the electronic structure, valuable insights were obtained regarding their effects on electrochemical properties. XPS analysis enabled the probing of the chemical composition and oxidation states of the film materials, unveiling synthesis-driven variations in their electronic properties. REELS provided information on energy loss and electronic transitions, enabling further characterization of the changes in the electronic structure induced by different preparation methods. Such findings emphasize the importance of surface characterization to understand how the unique electronic properties of such materials can be harnessed to enhance their performance and functionality.

Studies on the structural and magnetic properties of PMMA/Ni nanocomposite system prepared by embedding Ni nanoparticles in the PMMA films

PMMA/Ni nanocomposite films have been prepared by embedding Ni nanoparticles and maintaining their different thickness (5–50 nm) in PMMA (polymethylmethacrylate) film matrix by using ion beam sputtering (IBS) technique. Grazing incidence x-ray diffraction (GIXRD) results reveal Ni is present in metallic form in the FCC phase. X-ray reflectivity (XRR) is used to measure the nominal thickness of the Ni nanoparticle layer. Surface morphology was studied using atomic force microscopes (AFM). SXAS (soft x-ray absorption spectroscopy) studies on PMMA/Ni nanocomposites were done using synchrotron radiation to understand the electronic structure of these films which reveals that Ni is present in metallic state confirming that PMMA as host matrix protects the magnetic Ni nanoparticles from external oxidation. The magneto-optical Kerr effect (MOKE) magnetometer and MOKE microscope were employed to study the magnetic properties and simultaneously record the real time evolution of magnetic domains at 0°, 45°, and 90° azimuthal angles. All films show soft ferromagnetic behaviour and all the films show isotropic behaviour except one with Ni nanoparticle layer thickness of 40 nm. MOKE micrographs witness the gradual growth of magnetic domains with increase in thickness of Ni nanoparticle layer. These PMMA/Ni nanocomposite films may be viewed as potential candidate for futuristic functional material.

Sputter-cleaning modified interfacial energetic and molecular structure of DNTT thin film on ITO substrate

The effect of natural electrode contamination on interfacial energetic, structure and morphology of π-conjugated organic molecular layers were studied by depositing dinapthothienothiophene (DNTT) thin films of varying thickness on indium-tin-oxide (ITO) substrates and by using photoelectron spectroscopy, atomic force microscopy and X-ray reflectivity techniques. The DNTT thin film on unclean-ITO surface shows a smaller threshold ionization potential (by ∼0.4 eV) compared to the film on clean-ITO one. A molecule–substrate interaction, present in the DNTT/clean-ITO system, gives rise to an interfacial dipole and charge transfer, presumably through flat-lying seed-layer at the interface. On further deposition, the interfacial coverage increases, while the molecules on top of the seed-layer take different orientation (mostly edge-on) to form highly-dewetted fibrous-islands of very high-thickness but very low-coverage. Overall, the growth of DNTT film on clean-ITO surface is layer-plus-island-like or Stranski–Krastanov-type. On the other hand, the contamination layer at the DNTT/unclean-ITO interface is found to act as a spacer layer, which reduces the intimate molecule–substrate interaction and also the roughness to give rise an edge-on ordered island-like or Volmer–Weber-type film-growth with reduced hole injection barrier (by ∼0.2 eV) and better (almost double) film-coverage to make it a more efficient hole injector compared to the clean interface one.

The High Energy X-ray Probe (HEX-P): probing accretion onto stellar mass black holes

Accretion is a universal astrophysical process that plays a key role in cosmic history, from the epoch of reionization to galaxy and stellar formation and evolution. Accreting stellar-mass black holes in X-ray binaries are one of the best laboratories to study the accretion process and probe strong gravity—and most importantly, to measure the angular momentum, or spin, of black holes, and its role as a powering mechanism for relativistic astrophysical phenomena. Comprehensive characterization of the disk-corona system of accreting black holes, and their co-evolution, is fundamental to measurements of black hole spin. Here, we use simulated data to demonstrate how key unanswered questions in the study of accreting stellar-mass black holes will be addressed by the High Energy X-ray Probe (HEX-P). HEX-P is a probe-class mission concept that will combine high spatial resolution X-ray imaging and broad spectral coverage (0.2–80 keV) with a sensitivity superior to current facilities (including XMM-Newton and NuSTAR) to enable revolutionary new insights into a variety of important astrophysical problems. We illustrate the capability of HEX-P to: 1) measure the evolving structures of black hole binary accretion flows down to low (≲ 0.1%) Eddington-scaled luminosities via detailed X-ray reflection spectroscopy; 2) provide unprecedented spectral observations of the coronal plasma, probing its elusive geometry and energetics; 3) perform detailed broadband studies of stellar mass black holes in nearby galaxies, thus expanding the repertoire of sources we can use to study accretion physics and determine the fundamental nature of black holes; and 4) act as a complementary observatory to a range of future ground and space-based astronomical observatories, thus providing key spectral measurements of the multi-component emission from the inner accretion flows of black hole X-ray binaries.

New Insights into the Molecular Structure of Tear Film Lipids Revealed by Surface X-ray Scattering.

The tear film lipid layer (TFLL) is a unique biological membrane that serves a pivotal role in the maintenance of ocular surface health. Reaching an overarching understanding of the functional principle of the TFLL has been hampered by a lack of insights into the structural and functional roles played by individual lipid classes. To bridge this knowledge gap, we herein focus on studying films formed by principal lipid classes by surface scattering methods. Through grazing incidence X-ray diffraction and X-ray reflectivity studies, we reveal quantitative data about the lattice distances, molecular tilt angles, and mono/multilayer thickness and density profiles for central TFLL lipid classes under close to simulated physiological conditions. In addition, we discuss the correlation of the results to those obtained previously with the natural lipid composition of meibum.

A simple method for floating graphene oxide films facilitates nanoscale investigations of ion and water adsorption.

Graphene oxide (GO) is a promising material for separations. Nanoscale GO thin films at the air/water interface are excellent experimental models to understand molecular-scale interactions of ions and water with GO. However, the characteristics of GO, such as functional groups and flake size, also affect the thin film properties making it difficult to make systematic studies with GO thin films. This paper reports a simple, reliable, and quick method of preparing ultra-thin GO films, irrespective of their origin, and demonstrates the new opportunities possible with the utilization of this method. The total amount of GO used to form the thin film is significantly less compared to previous examples in the literature, minimizing the dissolved GO in the subphase. X-ray reflectivity (XR) studies show that the majority of the GO film has 1.5 nm thickness over a macroscopic area (∼100 cm2) with very small roughness. Sum frequency generation (SFG) spectroscopy measurements show that H2O and D2O interact differently with GO films, a property that was not observed before. SFG data show that functional groups vary significantly between different commercially available GO samples. The differences are also characterized with XR at high resolution. X-ray fluorescence near total reflection (XFNTR) measurements show that these differences strongly affect ion adsorption and interfacial water behavior near GO, which are vital properties in separation applications. The results pave the way for future studies to elucidate the complex separation mechanisms with GO.

Structure affinity of the Langmuir monolayer and the corresponding Langmuir-Blodgett film revealed by X-ray techniques.

The possibility of reproducing the structural organization and functional abilities of a Langmuir monolayer in a film formed from it is one of the fundamental problems of ultrathin film science. This work is devoted to the comparison of monolayer and Langmuir-Blodgett (LB) film characteristics using the example of 2D systems based on the dithia-aza-crown substituted hemicyanine dye HCS. As was shown earlier, the investigated systems are promising for the preparation of selective sensors and extractors for mercury ions in aqueous solutions with a subnanomolar sensitivity threshold. Therefore, the study of the analyte binding mechanism by such a film is of great importance. The study carried out using an ultra-highly brilliant X-ray source (ESRF) allows the application of highly sensitive techniques such as X-ray reflectometry (XRR) and X-ray standing wave (XSW). Comparison of the electron density depth profile of the HCS Langmuir monolayer at the air/water interface and the HCS film transferred to a silicon substrate shows the preservation of the film structure and its functional features. The XSW measurements in turn reveal the similarities in the fine structure of preorganized Langmuir monolayers and Langmuir-Blodgett films of HCS. The integration of X-ray techniques with molecular modeling methods allowed us to show that the crown-ether groups of HCS molecules in the pre-organized monolayer and in the corresponding LB film lie on the surface of water or silicon, and the bound mercury ion is located above the crown-ether, partially binding to the nitrogen atom. The latter loses conjugation to the chromophore group, thereby altering the UV-vis spectrum and providing a response signal. The revealed mechanism of imprinting preorganization allows the proposed approach to be extended to other crown-substituted amphiphilic dyes to significantly enhance the sensory response.

Development of a Bayesian inference method for the analysis of X-ray reflectivity data

X-ray reflectivity (XRR) is an experimental method used in various fields of materials science to investigate the physical properties of solid surfaces and the structure of interfaces. However, it is difficult to evaluate the reliability of the estimates obtained with this method. In this study, we propose a method for analyzing XRR data using Bayesian inference. Bayesian inference allows the uncertainty of the estimate to be evaluated, which also allows the measurement limit to be evaluated, and also shows that estimation is possible even in noisy situations.

Ambient formation of high pressure Ag2Si2O5 and non-stoichiometric Ag0.3Al0.7 alloy under confinement

We report results of Field Emission Scanning Electron Microscopy (FESEM), Energy Dispersive Analysis of X-rays (EDAX), X-ray Photoelectron Spectroscopy (XPS), X-ray Reflectivity (XRR), and X-ray Diffraction (XRD) and residual stress measurement studies of Ag-silica composite films on Al(001) co-deposited from precursors and spin-coated at different frequencies under ambient conditions. FESEM and EDAX show Ag nanoparticle formation, and XRD, XPS, and XRR show Ag0.3Al0.7 alloy and Ag-rich silicate Ag2Si2O5 formation in all samples. The alloy is non-stoichiometric and non-equilibrium, while the silicate forms at high oxygen pressure. XRR shows the presence of three layers, nanoparticles on top, silicate in the middle, and alloy at the bottom, on an Ag-doped Al substrate. Film thickness decreases exponentially with frequency. Individual layers increase in crystal domain size with a frequency of 3000 rpm when the silicate layer thins below unit cell thickness and the growth has a two-dimensional preference. Our results suggest total confinement by film thinning and local confinement from the Ag nanolayer. Residual stress measurements on the films deposited at 500 and 5000 rpms show a gradual increase in the tensile stress. The increase in spinning frequency reveals the formation of high pressure ambience.

Leonardo da Vinci’s London Virgin of the Rocks re-examined

The anniversary in 2019 of Leonardo’s death prompted a new investigation of the Virgin of the Rocks now in the National Gallery in London. This built on a substantial foundation of earlier research, one past milestone being the discovery through infrared reflectography of an underdrawing for a completely different composition, showing a Virgin higher up on the panel and in a different pose. This paper focuses on the latest findings associated with this first abandoned composition, discussing how the re-examination using macro X-ray fluorescence (XRF) scanning and reflectance imaging spectroscopy (RIS) in the infrared range allowed a much more complete visualisation of the initial design, found to include figures for the Christ Child and an angel. The new study also provided interesting insights into Leonardo’s underdrawing materials and methods, identifying different drawing media (which include zinc-containing iron gall inks mixed with variable amounts of carbon black), seemingly used at different stages of the creative process to develop initial ideas into a more defined composition. The findings are relevant to the long genesis of the painting and its relationship with the version in the Musée du Louvre, Paris.