Specular X-ray Reflectivity Research Articles

Calcite (1 0 4)–water interface structure, revisited

The structure of the calcite (104)–water interface is reassessed using a new set of high-precision specular X-ray reflectivity measurements. In situ measurements of the specular reflectivity signal to a vertical structural resolution of 0.45Å are used to define the interfacial structure, including vertical displacement patterns of the Ca and CO3 groups as well as the nature of interfacial water. These new data show two organized interfacial water layers, consistent with previous results, and distortion of the interfacial calcite structure to a depth of four to six unit cells, at least two deeper than previously reported. These results are in reasonable agreement with recent computational studies, at least in terms of the locations of the first and second water layers. The difference between the interfacial structure derived from previous X-ray reflectivity results and that presented here emphasizes the need for high-precision measurements to provide a robust understanding of the interfacial structures of reactive minerals in aqueous environments.

Monovalent Ion Adsorption at the Muscovite (001)–Solution Interface: Relationships among Ion Coverage and Speciation, Interfacial Water Structure, and Substrate Relaxation

The interfacial structure between the muscovite (001) surface and aqueous solutions containing monovalent cations (3 × 10(-3) m Li(+), Na(+), H(3)O(+), K(+), Rb(+), or Cs(+), or 3 × 10(-2) m Li(+) or Na(+)) was measured using in situ specular X-ray reflectivity. The element-specific distribution of Rb(+) was also obtained with resonant anomalous X-ray reflectivity. The results demonstrate complex interdependencies among adsorbed cation coverage and speciation, interfacial hydration structure, and muscovite surface relaxation. Electron-density profiles of the solution near the surface varied systematically and distinctly with each adsorbed cation. Observations include a broad profile for H(3)O(+), a more structured profile for Li(+) and Na(+), and increasing electron density near the surface because of the inner-sphere adsorption of K(+), Rb(+), and Cs(+) at 1.91 ± 0.12, 1.97 ± 0.01, and 2.26 ± 0.01 Å, respectively. Estimated inner-sphere coverages increased from ~0.6 to 0.78 ± 0.01 to ~0.9 per unit cell area with decreasing cation hydration strength for K(+), Rb(+), and Cs(+), respectively. Between 7 and 12% of the Rb(+) coverage occurred as an outer-sphere species. Systematic trends in the vertical displacement of the muscovite lattice were observed within ~40 Å of the surface. These include a <0.1 Å shift of the interlayer K(+) toward the interface that decays into the crystal and an expansion of the tetrahedral-octahedral-tetrahedral layers except for the top layer in contact with solution. The distortion of the top tetrahedral sheet depends on the adsorbed cation, ranging from an expansion (by ~0.05 Å vertically) in 3 × 10(-3)m H(3)O(+) to a contraction (by ~0.1 Å) in 3 × 10(-3) m Cs(+). The tetrahedral tilting angle in the top sheet increases by 1 to 4° in 3 × 10(-3) m Li(+) or Na(+), which is similar to that in deionized water where the adsorbed cation coverages are insufficient for full charge compensation.

INVESTIGATION OF SOL-GEL GROWN ZnO THIN FILM: WAVELET ANALYSIS AND SIMULATED ANNEALING OPTIMIZED X-RAY REFLECTIVITY

In this study ZnO thin film was fabricated by sol-gel spin coating method on glass substrate. X-ray reflectivity (XRR) and its optimization by simulated annealing (SA) technique have been used for characterization and extracting physical parameters of the film. The model independent information was needed to establish data analyzing process for XRR before optimization process. This independent information was extracted from wavelet transform of Fresnel reflectivity normalized XRR. This transformation yields thickness of each coated layer. This information was a keynote for constructing optimization process. Specular XRR optimization yielded structural parameters such as thickness, roughness of surface and interface and electron density profile of the film. Acceptable agreement exists between results obtained from wavelet transformation and XRR fitting.

Ultra-high vacuum deposition and characterization of silicon nitride thin films

Silicon nitride thin films were deposited on (100) Si wafers in an ultra-high vacuum system using a Si effusion cell and reactive nitrogen from a radio-frequency plasma source. The films were characterized using infrared transmission spectroscopy, infrared reflectance, Rutherford backscattering spectrometry, spectroscopic ellipsometry, specular x-ray reflectivity, wet etching in a buffered-oxide etch solution, and the electrical characterization of metal-insulator-semiconductor capacitors. High-quality, stoichiometric silicon nitride films with a refractive index of 2.05 at 632.8 nm are produced when the deposition temperature is 750 °C. Lower deposition temperatures produce nitrogen-rich silicon nitride films with lower refractive index, lower density, greater tendency toward oxidation in ambient air, faster etching in a buffered oxide etch solution, and greater electrical leakage. A deposition model involving thermal evolution of weakly-bonded excess N is proposed to explain our observations.

Evolution of nanoscale roughness in Cu/SiO2 and Cu/Ta interfaces

Synchrotron x-ray scattering was used to study the evolution of interface roughness with annealing for a series of Cu thin films. The films were encapsulated in SiO2 or Ta/SiO2 and prepared by sputter deposition. Specular x-ray reflectivity was used to determine the root mean square roughness for both the upper and the lower Cu/SiO2 (or Cu/Ta) interfaces. The lateral roughness was studied by diffuse x-ray reflectivity. Annealing the films at 600 °C resulted in a smoothing of only the upper interface for the Cu/SiO2 samples, while the lower Cu/SiO2 interfaces and both interfaces for the Ta encapsulated films did not evolve significantly. This difference in kinetics is consistent with the lower diffusivity expected of Cu in a Cu/Ta interface (compared to a Cu/SiO2 interface) and the mechanical rigidity of the lower Cu/SiO2 interface. As a function of roughness wavelength, the upper Cu/SiO2 interfaces exhibited a roughness decay with annealing that was only 12.5% of that expected for classical capillarity driven smoothening of a free surface.

Decay of interfacial fluid ordering probed by X-ray reflectivity

To what extent is the ordering of fluids at interfaces governed by the bulk structure of the fluid? In order to address this question, we have studied a dense, charge-stabilized colloidal suspension at the fluid–air interface and at two different solid–fluid interfaces using specular X-ray reflectivity. The experimental data are well described by a simple model of a stratified fluid, with the wall–particle potential mainly affecting the position of the first particle layer with respect to the interface. The decay of the fluid's density profile can for all the studied interfaces be described by a characteristic wavelength and a decay length, both of which are independently determined from the bulk phase using small-angle X-ray scattering. This latter finding is consistent with theoretical predictions and recent surface-force experiments.

Resonant soft x-ray scattering from stepped surfaces of SrTiO3

We studied the resonant diffraction signal from stepped surfaces of SrTiO3 at the Ti 2p → 3d (L2,3) resonance in comparison with x-ray absorption (XAS) and specular reflectivity data. The steps on the surface form an artificial superstructure suitable as a model system for resonant soft x-ray diffraction. A small step density on the surface is sufficient to produce a well defined diffraction peak. We determined the optical parameters of the sample across the resonance and found that the differences between the energy dependence of the x-ray absorption signal, the specular reflectivity and the step-related peak reflect the different quantities probed in these signals. When recorded at low incidence or detection angles, XAS and specular reflectivity spectra are strongly distorted by the changes of the angle of total reflection with energy. The resonant diffraction spectrum is less affected and can be used as a spectroscopic probe even in less favorable geometries.

A comparative study of Langmuir surfactant films: Grazing incidence x-ray off-specular scattering vs. x-ray specular reflectivity

Surface monolayers assembled on a liquid sub-phase represent a class of systems that is of great interest for studies of phase transitions in quasi-2D systems, chemical self-assembly, surfactant behavior, and biologically relevant monolayers and membranes. X-ray scattering is ideal for studying structural, dynamic, and mechanical properties of these surface monolayers at nanoscale due to the penetrating ability and short wavelength of x-rays. We show here that grazing incidence x-ray off-specular scattering (GIXOS) provides rapid access to in-plane and out-of-plane nanoscale structure, surface fluctuating modes, and potentially bending stiffness. We show that analysis of GIXOS data is highly sensitive to resolution effects. We further present detailed analysis of GIXOS from phospholipid 1,2-dipalmitoyl-phosphatidyl-choline C40H80NO8P (DPPC) and obtain quantitative, angstrom-resolution details of electron density profile normal to the surface that is comparable to those that are obtained from specular x-ray reflectivity measurements. We compare these GIXOS results to x-ray reflectivity measurements performed on the same samples. While electron density and main structural characteristics (such as monolayer thickness) obtained by GIXOS agree with x-ray reflectivity results, the interfaces of GIXOS-derived density profiles are found to be systematically sharper than those obtained with x-ray reflectivity. The possible reasons for these differences are discussed.

In situ observation of x-ray irradiation effect by using a multiwave x-ray diffraction phenomenon

In situ observation of the complex scattering amplitude of x-ray specular reflection (amplitude reflectivity) was performed by using a method with a multiwave x-ray diffraction phenomenon. The method can be applied to the noncrystalline layers on a single crystal and allows us to determine its amplitude reflectivity with only a 0.01 degree of crystal rotation, that is, the area irradiated by the incident x rays is almost unchanged during the measurement. We used this method to observe an irradiation effect induced by monochromatic synchrotron x-rays that occurred on a Si(001) single crystal covered with a native oxide layer. The obtained time evolution of the amplitude reflectivities exhibited counterclockwise behavior in the complex plane, indicating that the thickness of the noncrystalline layer on the crystalline substrate was increased by the irradiation.

On the theory of X-ray coherent reflection from a rough surface

A solution of the problem of X-ray specular reflection from a statistically rough surface is presented. It is based on using the Green function formalism. The Kirchhoff formula is used to describe the transmission of the wave field through a rough interface. Generally, microscopically exact expressions for the coefficients of transmission through a rough surface and reflection from it are obtained by taking multiple scattering effects into account. Averaging of the obtained expressions over possible realizations of random roughness of the interface between media allows to obtain rigorous expressions for specular reflection and transmission coefficients. The behavior of exact solutions in the limiting case of infinite correlation lengths is studied. It is shown that, in this case, the obtained solution corresponds to the Debye-Waller normalization. Expressions for the reflection and transmission coefficients making it possible to carry out numerical calculations are obtained in the Bourret approximation of multiple-scattering theory.

Profile structures of the voltage-sensor domain and the voltage-gated K+-channel vectorially oriented in a single phospholipid bilayer membrane at the solid-vapor and solid-liquid interfaces determined by x-ray interferometry

One subunit of the prokaryotic voltage-gated potassium ion channel from Aeropyrum pernix (KvAP) is comprised of six transmembrane α helices, of which S1-S4 form the voltage-sensor domain (VSD) and S5 and S6 contribute to the pore domain (PD) of the functional homotetramer. However, the mechanism of electromechanical coupling interconverting the closed-to-open (i.e., nonconducting-to-K(+)-conducting) states remains undetermined. Here, we have vectorially oriented the detergent (OG)-solubilized VSD in single monolayers by two independent approaches, namely "directed-assembly" and "self-assembly," to achieve a high in-plane density. Both utilize Ni coordination chemistry to tether the protein to an alkylated inorganic surface via its C-terminal His_{6} tag. Subsequently, the detergent is replaced by phospholipid (POPC) via exchange, intended to reconstitute a phospholipid bilayer environment for the protein. X-ray interferometry, in which interference with a multilayer reference structure is used to both enhance and phase the specular x-ray reflectivity from the tethered single membrane, was used to determine directly the electron density profile structures of the VSD protein solvated by detergent versus phospholipid, and with either a moist He (moderate hydration) or bulk aqueous buffer (high hydration) environment to preserve a native structure conformation. Difference electron density profiles, with respect to the multilayer substrate itself, for the VSD-OG monolayer and VSD-POPC membranes at both the solid-vapor and solid-liquid interfaces, reveal the profile structures of the VSD protein dominating these profiles and further indicate a successful reconstitution of a lipid bilayer environment. The self-assembly approach was similarly extended to the intact full-length KvAP channel for comparison. The spatial extent and asymmetry in the profile structures of both proteins confirm their unidirectional vectorial orientation within the reconstituted membrane and indicate retention of the protein's folded three-dimensional tertiary structure upon completion of membrane bilayer reconstitution. Moreover, the resulting high in-plane density of vectorially oriented protein within a fully hydrated single phospholipid bilayer membrane at the solid-liquid interface will enable investigation of their conformational states as a function of the transmembrane electric potential.

Characterization of Zinc Oxide Thin Film Using Atomic Force Microscopy and Optimized X-Ray Reflectivity by Genetic Algorithm

For the nanostructured thin films, the study of surface physical parameters is often of crucial importance. For example, the transport properties of ZnO thin film are strongly affected by the geometry of this film. In this study sol—gel ZnO thin film was spin coated on glass substrate. The inverse problem of thin film characterization is formulated as a parameter identification problem in which a set of parameters corresponding to the thin film property can be found by minimizing fitness functions formulated using theoretical and experimental X-ray reflectivity. Atomic force microscopy (AFM) measurements used as an independent procedure for extracting structural parameters of the film and accurate interpretation of X-ray reflectivity data. After applying Fractal calculations on the AFM measured data the Genetic algorithm (GA) method was applied for extracting other important structural parameters. Optimization of specular X-ray reflectivity by GA method gives information along the depth such as thickness, roughness, and electron density profile of layers in the film.

ZnO thin film characterization by X-ray reflectivity optimization using genetic algorithm and Fourier transformation

Zinc oxide (ZnO) thin film was fabricated by sol–gel spin coating method on glass substrate. X-ray reflectivity (XRR) and its optimization have been used for characterization and extracting physical parameters of the film. Genetic algorithm (GA) has been applied for this optimization process. The model independent information was needed to establish data analyzing process for X-ray reflectivity before optimization process. Independent information was exploited from Fourier transform of Fresnel reflectivity normalized X-ray reflectivity. This Fourier transformation (Auto Correlation Function) yields thickness of each coated layer on substrate. This information is a keynote for constructing optimization process. Specular X-ray reflectivity optimization yields structural parameters such as thickness, roughness of surface and interface and electron density profile of the film. Acceptable agreement exists between results obtained from Fourier transformation and X-ray reflectivity fitting.

X-ray radiation damage of organic semiconductor thin films during grazing incidence diffraction experiments

Since modern synchrotrons with highly intense X-ray beams are in use to investigate organic materials, the stability of soft matter materials during beam exposure is a crucial issue. Grazing incidence X-ray diffraction and specular X-ray reflectivity measurements were performed on thin films of organic semiconducting materials, like poly(3-hexylthiophene) (P3HT), sexithiophene and pentacene. These films were irradiated with an average flux density between 1015 and 1016photons/(smm2) and evidenced a different stability in synchrotron X-ray radiation. The semi-crystalline P3HT showed a clear intensity decrease of the 100 Bragg peak and 020 Bragg peak compared to the rather stable diffraction features of the molecular crystals sexithiophene and pentacene. The difference in synchrotron X-ray radiation stability is explained by the interaction of the X-ray beam with the individual chemical components in the molecules as well as by the different crystallinities of the materials. Furthermore, the semi-crystalline P3HT film exhibited an increase of film thickness after irradiation and the surface roughness slightly decreased. To summarize, this study shows a strong influence of synchrotron X-ray radiation to specific organic thin films like e.g. P3HT, while others like pentacene and sexithiophene are observed as quite stable.

&lt;i&gt;In Situ&lt;/i&gt; X-Ray Reflectivity Study of Imprint in Ferroelectric Thin Films

The structural origin of imprint in Pb(Zr,Ti)O3 (PZT) ferroelectric thin films derived by chemical solution deposition with Pt top and bottom electrodes was studied by in-situ high-resolution X-ray specular reflectivity of synchrotron radiation. Global structural parameters of density, thickness, and surface or interface roughness of each component layer in the thin film sample were obtained. No generation of interfacial layers with a different electron density from PZT and no interface roughening were observed at the interfaces of PZT and Pt during imprint. Thus, the results suggest that the imprint effect is more likely a bulk or electronic defects-related phenomenon.

Correlation of interface roughness for ion beam sputter deposited W/Si multilayers

W/Si multilayers having 5, 7, 9, 13, 17, and 25 layers have been deposited on c-Si substrates by Ion Beam Sputtering technique and have been characterized by specular and diffused grazing incidence X-ray reflectivity measurements. Information regarding the density, thickness and interface widths of individual layers of the multilayer stacks have been obtained from the theoretical fitting of the specular reflectivity spectra while fitting of the diffused X-ray reflectivity have yielded information regarding roughness and diffusivity at the individual interfaces along with the in-plane correlation lengths of roughness of the individual layers and the vertical correlation length of the whole multilayer structure. Investigations have been carried out on the different behavior of W-on-Si and Si-on-W interfaces and on the variation of the above parameters with the increase in number of layers in the multilayer structures.

Effect of surface modification on protein retention and cell proliferation under strain

When culturing cells on flexible surfaces, it is important to consider extracellular matrix treatments that will remain on the surface under mechanical strain. Here we investigate differences in laminin deposited on oxidized polydimethylsiloxane (PDMS) with plasma treatment (plasma-only) vs. plasma and aminopropyltrimethoxysilane treatment (silane-linked). We use specular X-ray reflectivity (SXR), transmission electron microscopy (TEM), and immunofluorescence to probe the quantity and uniformity of laminin. The surface coverage of laminin is approximately 45% for the plasma-only and 50% for the silane-linked treatment as determined by SXR. TEM and immunofluorescence reveal additional islands of laminin aggregates on the plasma-only PDMS compared with the relatively smooth and uniform silane-linked laminin surface. We also examine laminin retention under strain and vascular smooth muscle cell viability and proliferation under static and strain conditions. Equibiaxial stretching of the PDMS surfaces shows greatly improved retention of the silane-linked laminin over plasma-only. There are significantly more cells on the silane-linked surface after 4 days of equibiaxial strain.

Protein Salting Out Observed at an Air−Water Interface

A protein salting-out process is directly observed at an air−water interface. By using time-resolved X-ray specular reflectivity and off-specular diffuse scattering, we identified several key stages in the adsorption of hen egg white lysozyme in a concentrated NaCl solution, (1) adsorption-induced unfolding, (2) monolayer formation with unfolded proteins, (3) protein refolding, and (4) island formation with the refolded proteins. Stages 3 and 4 are not observed either at the isoelectric point or in the salt-free solution, suggesting that they are induced by screening of the positive charges in the lysozyme by chloride ions. It is considered that the hydrated salt ions act to minimize the water-accessible surface area of the protein, not only enhancing protein dehydration (stages 1 and 2) but also assisting in protein refolding and association (stages 3 and 4). These results provide insight into the early stages of protein crystal nucleation.

Determining Coherence length of X-ray Beam Utilizing Line Grating Structures

Specular x-ray reflectivity has been used successfully to measure the cross section of periodic nanopatterns on flat substrates and in most of the cases the effective medium approximation is found to be adequate for the data analysis. To examine the validity of EMA the coherence length of the X-ray reflectometer was measured quantitatively by extending the scheme used by Salditt et al. A series of linear grating structures with periodicities ranging from 300 nm to 16 µm was studies at various azimuthal angles between the incident X-ray and the lines. A clear break down of EMA was noticed at certain X-ray incident angle depending on the azimuthal angle, this provides a useful pathway for determining the coherent length of the X-ray reflectometer more precisely.

Thickness, Surface Morphology, and Optical Properties of Porphyrin Multilayer Thin Films Assembled on Si(100) Using Copper(I)-Catalyzed Azide−Alkyne Cycloaddition

We report the structure, optical properties and surface morphology of Si(100) supported molecular multilayers resulting from a layer-by-layer (LbL) fabrication method utilizing copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), also known as "click" chemistry. Molecular based multilayer films comprised of 5,10,15,20-tetra(4-ethynylphenyl)porphyrinzinc(II) (1) and either 1,3,5-tris(azidomethyl)benzene (2) or 4,4'-diazido-2,2'-stilbenedisulfonic acid disodium salt (3) as a linker layer, displayed linear growth properties up to 19 bilayers. With a high degree of linearity, specular X-ray reflectivity (XRR) measurements yield an average thickness of 1.87 nm/bilayer for multilayers of 1 and 2 and 2.41 nm/bilayer for multilayers of 1 and 3. Surface roughnesses as determined by XRR data fitting were found to increase with the number of layers and generally were around 12% of the film thickness. Tapping mode AFM measurements confirm the continuous nature of the thin films with roughness values slightly larger than those determined from XRR. Spectroscopic ellipsometry measurements utilizing a Cauchy model mirror the XRR data for multilayer growth but with a slightly higher thickness per bilayer. Modeling of the ellipsometric data over the full visible region using an oscillator model produces an absorption profile closely resembling that of a multilayer grown on silica glass. Comparing intramolecular distances from DFT modeling with experimental film thicknesses, the average molecular growth angles were estimated between 40° and 70° with respect to the substrate surface depending on the bonding configuration.