X-ray Reflectivity Profiles Research Articles

Influence of substructure inhomogeneity on the anisotropy of physical properties of textured materials

Calculation of the physical properties anisotropy is based on single crystal properties and information about material texture, i.e. orientation distribution function (ODF). At the same time, the grains of different orientations are known to have different substructure parameters including the lattice distortion and microstrains. Determination of these parameters is possible with the X-ray method of Generalized Pole Figures (GPF), which consists of registration of the whole X-ray reflection profile under the pole figure recording. As a result, one can obtain the FWHMs of X-ray line profiles and microstrains distributed on the stereographic projection. Despite the observable equilibrium of tensile and compressive microstrains of differently oriented grains within the studied material volume, they can affect the product properties anisotropy. In this study the calculation method for elastic properties and thermal expansion coefficients taking into account substructure inhomogeneity is offered on the basis of elastic energy minimization. Its efficiency is demonstrated for the samples of zirconium alloys.

Potential Dependent Ion Arrangement Near the Electrode/Electrolyte Interface

The electric double layer (EDL) is the ion arrangement evolving at electrolyte interfaces. Despite its importance in many applications such as super-capacitors, lithium ion batteries (LIB), water purification, and stabilization of nanoparticles in solution, the structural motifs of the EDL are still under debate.In LIB, the molecular scale ion arrangement near the interface or EDL controls solvation and hence mass/charge transfer across the interface. Additionally, the interfacial speciation governs the reductive and oxidative processes at the interface. Thus, it has a great impact on the stability of the electrolyte. Hence, the near-interface structure plays a vital role in the solid electrolyte interphase (SEI) formation which is still poorly understood. The SEI protects the electrolyte from further decomposition and its stability, low electrical conductance, and good Li-ion transport properties are crucial for the cycling ability and long-term stability of the cell. Therefore, an atomic level elucidation of the electrolyte/electrode interface and its rearrangement dynamics due to potential changes is of utmost importance for understanding the behaviors of LIBs, and will ultimately lead to the minimization of ion transport resistance and improved long-term stability.We present an in-situ X-ray reflectivity (XR) study on the single crystalline boron-doped diamond – electrolyte interface. The metal-like electric conductivity and wide electrochemical window of the single crystalline boron-doped diamond allow us to apply a potential across the interface. We obtain structural information by modeling the potential dependent EDL to reproduce our experimental data. First proof-of-concept results on 1m CsCl(aq) show a clear trend of the XR profile on the applied potential of -1.2V – 1.2V vs AgCl. The length scale of π/qz = 4Å of the observed minima at qz = 0.75 Å−1 corresponds well to the expected length-scale of the inner-Helmholtz layer of the EDL. Our analysis suggests that the population of the inner-Helmholtz layer decreases with increasing potential.Our efforts allow to challenge the current theoretical models and simulations and will ultimately help to understand the mechanisms involved in the SEI formation and lead to the minimization of ion transport resistance as well as to an improvement of the LIB cycling ability. Figure 1

Estimation of Forces on Actin Filaments in Living Muscle from X-ray Diffraction Patterns and Mechanical Data.

Many biological processes are triggered or driven by mechanical forces in the cytoskeletal network, but these transducing forces have rarely been assessed. Striated muscle, with its well-organized structure provides an opportunity to assess intracellular forces using small-angle X-ray fiber diffraction. We present a new methodology using Monte Carlo simulations of muscle contraction in an explicit 3D sarcomere lattice to predict the fiber deformations and length changes along thin filaments during contraction. Comparison of predicted diffraction patterns to experimental meridional X-ray reflection profiles allows assessment of the stepwise changes in intermonomer spacings and forces in the myofilaments within living muscle cells. These changes along the filament length reflect the effect of forces from randomly attached crossbridges. This approach enables correlation of the molecular events, such as the current number of attached crossbridges and the distributions of crossbridge forces to macroscopic measurements of force and length changes during muscle contraction. In addition, assessments of fluctuations in local forces in the myofilaments may reveal how variations in the filament forces acting on signaling proteins in the sarcomere M-bands and Z-discs modulate gene expression, protein synthesis and degradation, and as well to mechanisms of adaptation of muscle in response to changes in mechanical loading.

Microstructure, Surface Plasmon, Magneto-Optic Surface Plasmon, and Sensitivity Properties of Magneto-Plasmonic Co/Au Multilayers

Microstructure properties of Co/Au multilayers prepared using dc-magnetron sputtering is reported using X-ray reflectivity (XRR) and X-ray diffraction (XRD) analysis. XRR profiles of these multilayers showed excellent bilayer periodicity. The XRD spectra displayed Co layer thickness-dependent properties. However, annealing increased lateral tensile strain decreased compressive strain along the normal substrate direction. While surface roughness, crystallite grain size, and strain are affected by Co layer thickness, microstructure and periodicity are dominated by fcc-Au (111). Surface plasmon resonance (SPR) and magneto-optic SPR study of an optimized Co/Au multilayer in Kretschmann configuration for air-He and water-Methanol media showed an enhanced sensitivity by over 4 times when excited at the wavelength of 785 nm as compared to the conventional SPR configuration when excited at the wavelength of 632.8 nm. This enhancement in MOSPR sensitivity means the detection limit of this class of transducers can be substantially improved by tuning Co/Au layer thickness, wavelength, and incident angle of optical radiation.

Data-reduction procedure for correction of geometric factors in the analysis of specular X-ray reflectivity of small samples

For small samples, the modification of the X-ray reflectivity (XRR) profile by the geometric factors due to the profile and size of the beam and the size of the sample is significant. These geometric factors extend the spill-over angle, which is often greater than the critical angle for small samples. To separate the geometric factors, it is necessary to know the spill-over angle. Since the geometric factors are smoothly varying functions and extend beyond the critical angle, it is impossible to determine the spill-over angle from the XRR profile of small samples. It is shown that the spill-over angle can be determined by comparing the normal XRR profile of a small sample with the XRR profile taken with a surface-contact knife edge on the same sample. Thus, a procedure has been developed for data reduction for small samples and validated with suitable experiments. Unlike the methods used hitherto, which have drawbacks, this is a self-consistent method for data reduction.

Isotropic, nematic, and lamellar phases in colloidal suspensions of nanosheets

The phase diagram of colloidal suspensions of electrically charged nanosheets, such as clays, despite their many industrial uses, is not yet understood either experimentally or theoretically. When the nanosheet diameter is very large (∼100 nm to 1 µm), it is quite challenging to distinguish the lamellar liquid-crystalline phase from a nematic phase with strong stacking local order, often called "columnar" nematic. We show here that newly upgraded small-angle X-ray scattering beamlines at synchrotron radiation facilities provide high-resolution measurements which allow us to identify both phases unambiguously, provided that single domains can be obtained. We investigated dilute aqueous suspensions of synthetic Sb3P2O143- nanosheets that self-organize into two distinct liquid-crystalline phases, sometimes coexisting in the same sample. Close examination of their X-ray reflection profiles in the directions perpendicular to the director demonstrates that these two mesophases are a columnar nematic and a lamellar phase. In the latter, the domain size reaches up to ∼20 µm, which means that each layer is made of >600 nanosheets. Because the lamellar phase was only rarely predicted in suspensions of charged disks, our results show that these systems should be revisited by theory or simulations. The unexpected stability of the lamellar phase also suggests that the rims and faces of Sb3P2O143- nanosheets may have different properties, giving them a patchy particle character.

Evaluation of spontaneous superlattice ordering in MOCVD grown AlxGa1-xAs epilayer on GaAs (100) using X-ray reflectivity and rocking curve analysis

Spontaneous superlattice structure in few monolayer length scale has been observed very recently in AlxGa1-xAs epilayer on (001) GaAs substrate grown by Metal Organic Chemical Vapor Deposition. Here we have reported a detailed study of this structure using high resolution x-ray reflectivity (XRR) and rocking curve (XRC) analysis and tried to extract composition modulation in the superlattice. A model-independent Distorted Wave Born Approximation (DWBA) has been applied to the XRR results to successfully obtain the electron density profile of the structure from which the compositional information could be extracted. The XRR profile of the AlxGa1-xAs sample (x = 0.17) showed sharp equidistant peaks giving clear evidence of superlattice ordering in the epilayer. Simulation of the XRR results showed a bilayer segregation with alternating Al composition of 0.1 and 0.4 of thickness 20 and 8 Å, respectively with interfacial thicknesses of 12 Å on both sides, giving a periodicity of 52 Å. The cross-sectional transmission electron microscopic (XTEM) image also showed similar length scale. A kinematical model was then used successfully to fit the sharp peaks observed in the XRC using the characteristic length and compositional parameters obtained from the XRR simulation. These results also showed that the individual bilayers were of single crystalline zinc blende structures. Both the simulation techniques were first applied to a test structure of AlAs/GaAs multilayer of known thickness before applying the same to the spontaneous superlattice to validate the model.

Structural, electrical and magnetic characteristics of Ni/Ti modified BiFeO3 lead free multiferroic material

Recently, scientists and researcher are focussing on multiferroic materials which are widely used in various multifunctional devices. In this communication, synthesis and characterisation of nickel and titanium modified bismuth ferrite have been reported. A lead-free multiferroic compound, Bi(Ni0.40Ti0.40Fe0.20)O3, has been synthesized using solvent-free solid-state reaction route at 1073 K in an air atmosphere. The formation of a single-phase with orthorhombic symmetry and the substitution/concentration of Ni/Ti at the Fe-site of BiFeO3 were confirmed by X-ray diffraction and energy dispersive X-ray microanalysis spectroscopy techniques respectively. Based on X-ray reflection profiles, the average particle size was estimated to be around 30 nm. Study of surface morphology of the compound by field emission scanning electron microscope has shown nearly uniform distribution of grains of different dimension with some voids. The density (measured by Archimedes method) of as-synthesized pellets was found to be nearly 92.8% of the theoretical density. A significant effect of substitution of multiple elements at the Fe site on dielectric constant and tangent loss of BiFeO3 has been observed. Detailed analysis of dielectric and impedance data, collected in a wide range of frequency (1–1000 kHz) and temperature (298–773 K), has provided many important results on structure-properties relationship and dielectric relaxation of modified bismuth ferrite. Magnetic field dependent magnetisation, measured by vibrating sample magnetometer (VSM at room temperature), shows a significant enhancement in the value of remnant magnetization of Ni/Ti modified bismuth ferrite.

Correlation Between Optical, Morphological, and Compositional Properties of Aluminum Nitride Thin Films by Pulsed Laser Deposition

Aluminum nitride (AlN) thin films were grown in a N2 atmosphere onto a Si/Si3N4 substrate by pulsed laser ablation. We have varied the substrate temperature for the thin film growth, using X-ray reflectometry analysis, we have characterized the thickness and density of the thin layer and the interface roughness from the X-ray reflectivity profiles. Experimental data showed that the root-mean-square roughness was in the range of 0.3 nm. The X-ray photoelectron spectroscopy (XPS) was employed to characterize the chemical composition of the films. These measurements detected carbon and oxygen contamination at the surface. In the high-resolution XPS Al2p data, binding energies for Al–N and Al–O species were identified but no Al–Al species were present. In the N1s data, N–O species were not detected, but chemically bonded O was present in the films as Al–O species. Furthermore, the value of optical energy gap, $E_{g}$ was $\sim 5.3$ (±0.1) eV. The composition varied with process conditions, and the nitrogen content decreased in AlN films processed above 500 °C.

Structure of n-Alkyltrichlorosilane Monolayers on Si(100)/SiO2.

The structure of n-alkyltrichlorosilane self-assembled monolayers (SAMs) of alkyl chain lengths n = 12, 14, 18, and 22 formed on the amorphous native oxide of silicon (100) has been investigated via angstrom-resolution surface X-ray scattering techniques, with particular focus on the proliferation of lateral order along the molecules' long axis. Grazing incidence diffraction shows that the monolayer is composed of hexagonally packed crystalline-like domains for n = 14, 18, and 22 with a lateral size of about 60 Å. However, Bragg rod analysis shows that ∼12 of the CH2 units are not included in the crystalline-like domains. We assign this, and the limited lateral crystallites' size, to strain induced by the size mismatch between the optimal chain-chain and headgroup-headgroup spacings. Analysis of X-ray reflectivity profiles for n = 12, 14, and 22 shows that the density profile used to successfully model n = 18 provides an excellent fit where the analysis-derived parameters provide complementary structural information to the grazing incidence results.

Nanostructure and salt effect of zwitterionic carboxybetaine brush at the air/water interface.

Zwitterionic amphiphilic diblock copolymer, poly(ethylhexyl acrylate)-b-poly(carboxybetaine) (PEHA-b-PGLBT), was synthesized by the reversible addition-fragmentation chain transfer (RAFT) method with precise control of block length and polydispersity. The polymers thus obtained were spread onto the water surface to form a polymer monolayer. The fundamental property and nanostructure of the block copolymer monolayer were systematically studied by the surface pressure-molecular area (π-A) isotherm, Brewster angle microscopy (BAM), and X-ray reflectivity (XR) techniques. The π values of the monolayer increased by compression in relatively larger A regions. After showing a large plateau region by compression, the π value sharply increased at very small A regions, suggesting the formation of poly(GLBT) brush formation just beneath the water surface. The domain structure of μm size was observed by BAM in the plateau region. XR profiles for the monolayer at higher surface pressure regions clearly showed the PGLBT brush formation in addition to PGLBT carpet layer formation under the hydrophobic PEHA layer on the water surface, as was observed for both anionic and cationic brush layer in the water surface monolayer studied previously. The critical brush density, where the PGLBT brush is formed, was estimated to be about 0.30 chains/nm(2) for the (EHA)45-b-(GLBT)60 monolayer, which is relatively large compared to other ionic brushes. This observation is consistent with the fact that the origin of brush formation is mainly steric hindrance between brush chains. The brush thickness increased by compression and also by salt addition, unlike the normal ionic brush (anionic and cationic), whose thickness tended to decrease, i.e., shrink, by salt addition. This might be a character unique to the zwitterionic brush, and its origin is thought to be transition to an ionic nature from the almost nonionic inner salt caused by salt addition since both the cation and anion of the GLBT chain obtained counterions by the addition of salt. This stretching nature of the PGLBT brush depends on the ion species of the salt added, and it followed the Hofmeister series, i.e., more stretching in the order of Li(+) > Na(+) > K(+). However, it was rather insensitive to the anion species (Cl(-), Br(-), SCN(-)), which suggests that the carboxylic anion has a more dominant effect than the quaternized cation in GLBT although the former is a weak acid and the latter is believed to be a strong base.

Comparative study of the X-ray reflectivity and in-depth profile of a-C, B4C and Ni coatings at 0.1–2 keV

The use of soft X-rays near the carbon edge of absorption (270-300 eV) greatly enhances studies in various branches of science. However, the choice of reflecting coatings for mirrors operating in free-electron and X-ray free-electron laser (FEL and XFEL) beamlines in this spectral range is not so evident and experimental justifications of the mirror efficiency are rather limited. In the present paper it is demonstrated experimentally that the reflectivity of B4C- and Ni-coated grazing-incidence mirrors is high enough for their operation in FEL or XFEL beamlines near the carbon K-edge of absorption. The minimal reflectivity of both mirrors proves to exceed 80% near the carbon absorption edge at a grazing angle of 0.6°. An in-depth profile of the chemical elements composing the reflecting coatings is reconstructed based on analysis of a set of reflectivity curves measured versus the grazing angle at different photon energies in the soft X-ray spectral region. This allows us to predict correctly the mirror reflectivity at any X-ray energy and any grazing angle.

Two Dimensional Aggregation Behaviors of Quinoxaline Dendrimers.

This study focuses on the molecular behavior of two dendrimers containing a hydrophilic core group (carboxyl group) and hydrophobic branches (quinoxaline and methoxyphenyl groups), 2,3-bis(4-(2,3- bis(4-methoxyphenyl)quinoxalin-6-yloxy)phenyl)quinoxaline-6-carb-oxylic acid (G2) and 2,3-bis(4-(2,3-bis(4-(2,3-bis(4-methoxyphenyl)quinoxalin-6-yloxy)phe-nyl)quinoxalin-6-y-oxy)phenyl) quin oxaline-6-carboxylic acid (G3) at the air-water interface. To understand the mechanism of the self-assembly of these molecules, we measured the surface pressure-area (III-A) isotherm and investigated the surface morphology of Langmuir-Blodgett films transferred onto hydrophilic silicon wafers using atomic force microscopy (AFM). Upon compression, G2 molecules stand up and steadily make close-packed monolayer whereas G3 molecules form circular domains and gradually make aggregates of domains. These results were confirmed by the X-ray Reflectivity (XRR) profiles of G2 and G3 monolayers transferred onto silicon substrates.

X-ray reflectivity study of the glass transition temperature of thin films

The glass transition takes place in amorphous materials (like polymers) during heating or cooling, and can be described as reversible transition from a hard and brittle state into a rubber-like state. Although physical properties of the material change significantly during the glass transition, this is not a phase transition of the material. The temperature at which the transition between the glassy and rubbery state occurs is called the glass transition temperature, and this temperature is always lower than the melting temperature. Thermodynamically, the glass transition is associated with transfer of heat between the system and its surrounding and with an abrupt volume change. Previously it was shown that the glass transition temperature of nano-films is different from that of bulk materials [1], which signifies the importance of determining this parameter for such systems. In the current work, we use quick X-ray reflectivity (qXRR) measurements to determine the glass transition temperature of polyvinyl acetate (PVAc). PVAc is rubbery synthetic polymer with the formula (C4H6O2), a density of 1.18 g/cm3, and a glass transition temperature for bulk material of 30oC [2]. Regular X-ray reflectivity measurements are based on θ/2θ scans at grazing incidence and typically require 0.5-1.5 h for a single scan. The qXRR technique is based on simultaneous measurement of the whole angular x-ray reflectivity profile and is suitable for in-situ measurement without moving the sample and/or the x-ray optics. Thus, the qXRR technique allows for very fast measurement of the x-ray reflectivity curves (duration of each scan is typically 0.1–20 sec [3]), which permits studying the time evolution of chemical, thermal, and mechanical changes at the surface and interface of different materials. X-ray reflectivity measurements give information about both density and thickness of thin films, and are suitable for studying glass transition phenomena. Nano-thickness PVAc layers on a Si substrate were examined with the qXRR technique, with x-ray reflectivity scans (each 10-seconds in duration) being recorded while temperature was changed from 20 to 50oC (total of 331 scans over 7 hours and 46 minutes). In the current paper, the experimental setup, the data-processing, and the analysis of the results from the qXRR measurements will be presented.

Microstructures of BPDA-PPD polyimide thin films with different thicknesses

The microstructures of 3,4,3′,4′-biphenyltetracarboxylic dianhydride –p-phenylene diamine (BPDA-PPD) polyimide (PI) thin films with different thicknesses were investigated by grazing incidence X-ray diffraction (GIXD) and X-ray reflectivity (XRR) at the SPring-8 synchrotron radiation facility. The film density calculated from XRR profiles increased with decreasing the film thickness. Processing of PI thin films from precursor polyamic acid (PAA) solutions involves simultaneous thermal imidization, evaporation of residual solvents and crystallization. The thickness reduction during imidization was smaller for the thinner PAA film. This implies that the much more larger amount of the residual solvent in the thinner PAA film brings high molecular mobility, which results in the higher conversion to PI at any curing temperature. The thinner BPDA-PPD film was more dense than the thicker film because of better molecular packing, which is a result of much more amount of the residual solvent for the thinner film during the thermal curing.

Precise structural investigation of symmetric diblock copolymer thin films with resonant soft X-ray reflectivity

Symmetric diblock copolymers are known to form lamellar structures in the bulk of an organic thin film. Polymer/polymer and polymer/substrate interfaces play a critical role in this application. Here, we report the investigation of multiple buried interfaces by using a novel technique resonant soft X-ray reflectivity which benefits from enhanced contrast between different polymers near the carbon K-edge. This allows us to obtain a precise interface structure. We also present an alternative method to determine optical constants of polymers by fitting X-ray reflectivity of polymers with known structural parameters at specific soft X-ray energies. This approach is compared with the way of obtaining β by NEXAFS and calculating δ via the Kramers–Kronig relationship. Finally, by using the determined index of refraction, the precise structure of a multilayer formed by a diblock copolymer is obtained by successfully fitting the resonant soft X-ray reflectivity profile.

A study of the layer structure in a calix-8-arene Langmuir–Blodgett film by reflectometry

X-ray reflectometry measurements have been made on Langmuir–Blodgett films of tertiary-octyl calix-8-arene. The samples have additional cadmium ions incorporated in the film and the typical X-ray reflectivity profile exhibits both interference fringes and a well defined Bragg peak. The total film thickness and the bilayer spacing were obtained from these. Simulations of the experimental reflectivity profile were made for three structural models, using a program based on Parratt's recursive relations. The traditional “bowl and chain” conformation and the “wheel-like” pleated loop conformation of calix-8-arene were both unable to provide an effective model for the structure of the multilayer film. In contrast, the more complex “pinched loop” molecular conformation produced a film with the correct total thickness and bilayer spacing. The reflectivity profile calculated from this model was in excellent agreement with the experimental profile. The principle features of the model are a partial interdigitation of the hydrophobic R-groups and an interpenetration of the hydrocarbon X-groups, which leads to a high value of electronic scattering length density in the plane of the incorporated cadmium ions.

Quantitative Adhesion Properties and Interfacial Behavior of SiCN Barrier Layer and Cu Film

Adhesion of the SiCN barrier layer and Cu film interface is one of the important characteristics that reflect the interfacial structure. NH3 plasma treatment of the Cu surface is a well-known way of improving adhesion. The results of X-ray reflectivity (XRR) and X-ray photoelectron spectroscopy (XPS) depth profiles indicate that the plasma treatment imparts a difference to the formation of the interface with SiCN. Adhesion properties are regarded as fracture energies measured by double cantilever beam (DCB) and 4-point bending (4PB) techniques. The influence of the NH3 plasma treatment of the Cu surface on adhesion is quantitatively discussed. The treated samples showed approximately twice the fracture energy of the non-treated samples. After 4PB and DCB measurements, fracture surfaces were investigated by XPS and atomic force microscopy (AFM). The formation of a N-Cu chemical bond on the Cu surface was enhanced as a result of removing oxygen by the plasma treatment. N-Cu chemical bonding contributes substantially to better SiCN/Cu interfacial adhesion.

Structure and dynamics of water on Li +-, Na +-, K +-, Cs +-, H 3O +-exchanged muscovite surfaces: A molecular dynamics study

The distribution and dynamics of water molecules and monovalent cations (Li +, Na +, K +, Cs +, and H 3O +) on muscovite surfaces were investigated by molecular dynamics (MD) simulations. The direct comparison of calculated X-ray reflectivity profiles and electron density profiles with experiments revealed the precise structure at the aqueous monovalent electrolyte solutions/muscovite interface. To explain the experimentally observed electron density profiles for the CsCl solution–muscovite interface, the co-adsorption of Cs + and Cl − ion pairs would be necessary. Two types of inner-sphere complexes and one type of outer-sphere complex were observed for hydrated Li + ions near the muscovite surface. For Na +, K +, Cs +, and H 3O + ions, the inner-sphere complexes were stable on the muscovite surface. The density oscillation of water molecules was observed to approximately 1.5 nm from the muscovite surface. The number of peaks and the locations for the density of water oxygen atoms were almost similar among the water molecules coordinated to Li +, Na +, K +, and H 3O + ions adsorbed on the muscovite surfaces. The water molecules around Cs + ions that were adsorbed to muscovite surfaces seemed to avoid coordinating with Cs + ions on the surface, and the density of water oxygen near the muscovite surface decreased relative to that in a bulk state. There was no significant difference in self-diffusion, viscosity, retention time, and reorientation time of water molecules among different cations adsorbed to muscovite surfaces. These translational and rotational motions of water molecules located at less than 1 nm from the muscovite surfaces were slower than those in a bulk state. A significant difference was observed for the exchange times of water molecules around monovalent cations. The exchange time of water molecules was long around Li + ions and decreased with an increase in the ionic radius.

Shaped silicon wafers obtained by hot plastic deformation: performance evaluation for future astronomical x-ray telescopes

In order to develop lightweight and high angular resolution x-ray mirrors, we have investigated hot plastic deformation of 4 in. silicon (111) wafers. A sample wafer was deformed using hemispherical dies with a curvature radius of 1000 mm. The measured radius of the deformed wafer was 1030 mm, suggesting that further conditioning is indispensable for better shaping. For the first time to our knowledge, x-ray reflection on a deformed wafer was detected at Al K(alpha) 1.49 keV. An estimated surface roughness of <1 nm from the x-ray reflection profile was comparable to that of a bare silicon wafer without deformation. Hence, no significant degradation of the microroughness was seen.