Off-specular Reflectivity Research Articles

Cinematic reflectometry using QIKR, the quite intense kinetics reflectometer.

The Quite Intense Kinetics Reflectometer (QIKR) will be a general-purpose, horizontal-sample-surface neutron reflectometer. Reflectometers measure the proportion of an incident probe beam reflected from a surface as a function of wavevector (momentum) transfer to infer the distribution and composition of matter near an interface. The unique scattering properties of neutrons make this technique especially useful in the study of soft matter, biomaterials, and materials used in energy storage. Exploiting the increased brilliance of the Spallation Neutron Source Second Target Station, QIKR will collect specular and off-specular reflectivity data faster than the best existing such machines. It will often be possible to collect complete specular reflectivity curves using a single instrument setting, enabling "cinematic" operation, wherein the user turns on the instrument and "films" the sample. Samples in time-dependent environments (e.g., temperature, electrochemical, or undergoing chemical alteration) will be observed in real time, in favorable cases with frame rates as fast as 1Hz. Cinematic data acquisition promises to make time-dependent measurements routine, with time resolution specified during post-experiment data analysis. This capability will be deployed to observe such processes as in situ polymer diffusion, battery electrode charge-discharge cycles, hysteresis loops, and membrane protein insertion into lipid layers.

General treatment of off-specular resonant soft x-ray magnetic scattering using the distorted-wave Born approximation: Numerical algorithm and experimental studies with hybrid chiral domain structures

We present a numerical algorithm for the simulation of resonant x-ray magnetic scattering in reflection geometry for an arbitrary three-dimensional magnetization distribution over a multilayer sample utilizing the distorted-wave Born approximation. Our approach takes the medium boundary matrix approach for specular reflection, and the Born approximation typically used for off-specular reflection, combines the two, and adds the contribution from transmission through the sample before and after a reflection event. The algorithm is then tested on experimental data from an ${\mathrm{Al}}_{2}{\mathrm{O}}_{3}$/Co/Pt multilayer sample with hybrid N\'eel/Bloch/N\'eel domain walls at incidence angles at and near multilayer Bragg angles, and photon energies near the Co ${L}_{3}$ absorption edge, achieving high levels of agreement with experimental data. Incorporating the transmission components into the algorithm was found to explain the dichroism observed in scattering from Bloch-type domain walls, and uncovered the likely importance of diffuse scattering in transmission from the polycrystalline grain walls along the optical path of the x rays in the sample---a theme which deserves further investigation.

Chemical Identification in the Specular and Off-Specular Rough-Surface Scattered Terahertz Spectra Using Wavelet Shrinkage.

We present the development and implementation of a novel wavelet shrinkage technique for the retrieval of obscured characteristic resonant signatures in the scattered terahertz (THz) reflectivity of molecular crystals. In this implementation, the wavelet basis functions associated with the absorption features were identified using the second-order total variation of the wavelet coefficients. Additionally, wavelet coefficients at certain scales were modified using the phase function corrections and wavelet hard thresholding. Reconstruction of the original spectra using these modified wavelet coefficients yielded the exact resonant frequencies of the chemicals, which were otherwise unrecognizable in the spectral artifacts of the rough surface scattering. We examined the robustness of this method over controlled levels of rough surface scattering, validated using the Kirchhoff approximation, in spectroscopic targets made from α-lactose monohydrate and 4-aminobenzoic acid (PABA), which have close spectral lines. We successfully retrieved the spectral absorption fingerprints in both specular and off-specular reflection geometries. This technique can be utilized for stand-off material characterization using the THz reflection spectroscopy in uncontrolled environments and potentially can be adopted for other broadband spectroscopic modalities.

Versatile four-axis gonioreflectometer for bidirectional reflectance distribution function measurements on anisotropic material surfaces

The bidirectional reflectance distribution function (BRDF) data are essential for analyzing and modeling the material appearance of anisotropic surfaces. In order to acquire four-dimensional BRDF on the anisotropic material surfaces, a four-axis gonioreflectometer was designed and implemented. The instrument consists of a collimated, broadband light source, a four-axis rotation mechanism, a spectroradiometer, and a control system. The instrument is able to carry out spectral BRDF measurements over most of the incident and reflection hemispheres and the entire visible spectrum. One thousand twenty-four samples are obtained over the spectral range of 380 to 760 nm. The angular resolution of the BRDF measurement is <0.1 deg with good repeatability. A relative calibration method was adopted to obtain the absolute values of BRDFs. Various scanning schemes can be carried out by the instrument to scan the designated angular domains, enabling the instrument to capture material appearance with strong, distinctive anisotropic highlights and translucency. The obtained BRDF data of a textile sample demonstrate the instrument capability of capturing complex light scattering behaviors, including off-specular reflection peaks, off-plane reflection peaks, and backscattering. The designers of novel material appearance and computer graphics community will benefit from this work.

BRDF of human skin in the visible spectrum

PurposeSignificant research has been carried out in terms of development of new bidirectional reflectance distribution function (BRDF) instruments; however, there is still little research available regarding spectral BRDF measurements of human skin. This study aims to investigate the variation in human skin reflectance using a new fibre optic-based spectral-BRDF measurement device.Design/methodology/approachDesign of this system mainly involves use of multiple fibre optics to illuminate and detect light reflected from a sample, whereas a hemispherical dome was 3D printed to mount the fibres at various slant/tilt angles. To investigate the spectral differences in BRDF of human skin, 3 narrowband filters in the visible spectrum were used, whereas measurements were taken from the back of the hand for Caucasian and Asian skin types.FindingsThe experiments demonstrate that the BRDF of human skin varies with wavelengths in the visible spectrum and it is also different for Caucasian and Asian skin types. Both skin types exhibit off-specular reflection with increase in angle of incidence and show less variation with respect to viewing angles when the angle of incidence is normal to the surface.Research implicationsA database of spectral BRDF measurements of human skin will help not only in creating realistic skin renderings but also in development of novel skin reflectance models for biomedical and machine vision applications. The measurements would also provide means to validate the predictions from existing light transport/spectral simulation models for human skin and will ultimately help in the accurate diagnosis and simulation of various skin disorders.Originality/valueThe proposed system provides fast scatter measurements by utilising multiple fibres to detect light simultaneously at different angles while also allowing easy switching between incident light directions. Due to its flexible design and contact-based measurements, the device is independent of errors due to sample movements and does not require any image registration. Also, measurements taken from the device show that the BRDF of skin varies significantly in the visible spectrum and it is different for Caucasian and Asian skin types.

Numerical reproduction and explanation of road surface mirages under grazing-angle scattering.

The mirror-like reflection image of the road surface under grazing-angle scattering can be easily observed in daily life. It was suggested that road surface mirages may occur due to a light-enhancing effect of the rough surface under grazing-angle scattering. The main purpose of this work is to explain the light-enhancing mechanism of rough surfaces under grazing-angle scattering. The off-specular reflection from a random rough magnesium oxide ceramic surface is analyzed by using the geometric optics approximation method. Then, the geometric optics approximation method is employed to develop a theoretical model to predict the observation effect of the grazing-angle scattering phenomenon of the road surface. The rough surface is assumed to consist of small-scale rough surface facets. The road surface mirage is reproduced from a large number of small-scale rough surface facets within the eye's resolution limit at grazing scattering angles, as the average bidirectional reflectance distribution function value at the bright location is about twice that of the surface in front of the mirage. It is suggested that the light-enhancing effect of the rough surface under grazing-angle scattering is not proper to be termed as "off-specular reflection," since it has nothing to do with the "specular" direction with respect to the incident direction.

The Search for Nanobubbles by Using Specular and Off-Specular Neutron Reflectometry.

We apply specular and off-specular neutron reflection at the hydrophobic silicon/water interface to check for evidence of nanoscopic air bubbles whose presence is claimed after an ad hoc procedure of solvent exchange. Nanobubbles and/or a depletion layer at the hydrophobic/water interface have long been discussed and generated a plethora of controversial scientific results. By combining neutron reflectometry (NR), off-specular reflectometry (OSS), and grazing incidence small angle neutron scattering (GISANS), we studied the interface between hydrophobized silicon and heavy water before and after saturation with nitrogen gas. Our specular reflectometry results can be interpreted by assuming a submolecular sized depletion layer and the off-specular measurements show no change with nitrogen super saturated water. This picture is consistent with the assumption that, following the solvent exchange, no additional nanobubbles are introduced at significant concentrations (if present at all). Furthermore, we discuss the results in terms of the maximum surface coverage of nanobubbles that could be present on the hydrophobic surface compatibly with the sensitivity limit of these techniques.

Light depolarization in off-specular reflection on submicro rough metal surfaces with imperfectly random roughness.

Depolarization at a rough surface relates to its roughness and irregularity (e.g., sags and crests) besides the material property. However, there is still lack of general theory to clearly describe the relationship between depolarization ratios and surface conditions, and one important reason is that the mechanism of depolarization relates to geometric parameters such as microcosmic height/particle distributions of sub-micro to nm levels. To study the mechanism in more detail, a compact laser instrument is developed, and depolarization information of a linearly polarized incident light is used for analyzing the roughness, during which a He-Ne laser source (λ = 632.8 nm) is used. Three nickel specimens with RMS roughness (Rq) less than λ/4 are fabricated and tested. Six different areas in each specimen are characterized in detail using an AFM. Rq are in the range of 34.1-155.0 nm, and the heights are non-Gaussian distribution in the first specimen and near-Gaussian distribution in the others. Off-specular inspection is carried out exactly on these 18 characterized areas, and results show that the cross-polarization ratios match quite well with Rq values of the first sample that has Rq ≤ λ/10 (or Rt ≤ λ), while they match well with maximum height, Rt, values of the other two that have Rt > λ (the maximum derivation is 11%). In addition, since this instrument is simple, portable, stable, and low-cost, it has great potential for practical online roughness testing after a linear calibration.

Dewetting Process of Deuterated Polystyrene and Poly(vinyl methyl ether) Blend Thin Films via Phase Separation

We studied the structure development in the dewetting process of deuterated polystyrene (dPS) and poly(vinyl methyl ether) (PVME) thin films, which were prepared by a spin-coating method on a quartz substrate, after the temperature jump into the two-phase region, using time-resolved specular and off-specular neutron reflectivity (NR), specular X-ray reflectivity (XR), light scattering (LS), and optical microscope (OM) measurements. The OM and specular XR measurements showed that there clearly existed an incubation period before dewetting. In the incubation period, composition fluctuations between dPS and PVME were developed due to phase separation. The specular NR results revealed that composition fluctuations began to occur just after the temperature jump along the depth direction over the film, giving rise to the composition gradient heterogeneously over the film. Composition fluctuations were also observed in the in-plane direction by the off-specular NR and LS measurements: the off-specular NR measure...

Temperature-driven surface morphology evolution of poly(3-hydroxybutyrate) single layer and poly(3-hydroxybutyrate)/poly(vinyl phenol) bilayer on Si wafers

The specular and off-specular X-ray reflectivities were efficiently employed to study the evolution of surface morphology as a function of temperature in a single layer of poly(3-hydroxybutyrate) (PHB) and a bilayer of PHB/poly(vinyl phenol) (PVPh) on Si substrates. The results indicate that the changes of thickness and surface roughness caused by pre-melting of PHB crystals are not obvious for the single layer, whereas the surface roughness of the PHB layer and the intensity of the off-specular X-ray reflectivity for the bilayer exhibit a remarkable non-monotonic change in the temperature range of 100–150°C; the roughness parameter evaluated by the specular X-ray reflectivity reaches its maximum at 120°C. The interaction at the interface between PVPh and PHB certainly contributes to the non-monotonic changes. Such interaction also affects the crystallization and melting behavior of PHB thin film greatly. The crystallization of PHB thin film is inhibited even on the glassy surface of PVPh sublayer. In the melting process, the PHB crystals on PVPh sublayer feature a three-section melting curve separated by a plateau region of 120–140°C.

Using off-specular ellipsometry spectra of dielectric grating-coupled plasmon mode for biosensing

We performed spectroscopic ellipsometry measurements of the specular and off-specular reflections of a one-dimensional polymethyl methacrylate grating on a Au-coated glass substrate and analyzed the data with efficient theoretical modeling. Very good agreement is obtained between calculation and experiment for both specular and off-specular reflections. It is found that the resonance peak of the off-specular reflection is much sharper than specular reflection at a wavelength that matches the condition for exciting the interface (surface plasmon) mode. When different media are used as the ambient, we found that the off-specular reflection near the surface-plasmon resonance can give significant enhancement in detection sensitivity compared with the corresponding specular reflection. This study may open a new way for biosensing. To analyze the data, we also developed a method to compute quasi-photonic band structures for periodic structures with frequency-dependent complex dielectric constants.

BioRef: A versatile time-of-flight reflectometer for soft matter applications at Helmholtz–Zentrum Berlin

BioRef is a versatile novel time-of-flight reflectometer featuring a sample environment for in situ infrared spectroscopy at the reactor neutron source BER II of the Helmholtz Zentrum Berlin für Materialien und Energie (HZB). After two years of design and construction phase the instrument has recently undergone commissioning and is now available for specular and off-specular neutron reflectivity measurements. BioRef is especially dedicated to the investigation of soft matter systems and studies at the solid-liquid interface. Due to flexible resolution modes and variable addressable wavelength bands that allow for focusing onto a selected scattering vector range, BioRef enables a broad range of surface and interface investigations and even kinetic studies with subsecond time resolution. The instrumental settings can be tailored to the specific requirements of a wide range of applications. The performance is demonstrated by several reference measurements, and the unique option of in situ on-board infrared spectroscopy is illustrated by the example of a phase transition study in a lipid multilayer film.

Road surface mirage: A bunch of hot air?

The inferior mirage from road surfaces is a common phenomenon, which can be easily seen in everyday life. It has been recognized in the literature as a light refraction phenomenon due to the refractive index gradient caused by the temperature gradient in the air strata above the road surfaces. However, it was also suggested that the mirage is just a phenomenon of specular reflection at grazing incidence. Because of the lack of reasonable and quantitative evidence, the generally accepted light refraction theory has not yet been refuted. Here we show some mirror-like reflection images captured from a road surface stretch in Yujiashan North Road, Wuhan, China, when there was no obvious temperature gradient on or above the road, measured on a winter day in December 2009. This provided direct evidence to doubt the temperature induced light refraction mechanism of the inferior mirage. Furthermore, the critical grazing angle of about 0.2° to the road plane where the mirror-like reflection appears could not make the rough surface scatter incident light as a smooth surface according to the Rayleigh criterion. Therefore the phenomenon is a mirrorlike observation effect of scattering from the surface, which cannot be entirely explained by light refraction via air strata. The results demonstrate that the image-formation mechanism and the observer-based-analysis method shown here potentially offer a means of understanding a wide range of scattering phenomena from rough surfaces at grazing angle; for example, the superior mirages of unusual brightness occasionally observed over frozen lakes and the off-specular reflection phenomenon.

Advanced Neutron Reflectometer for Investigation on Dynamic/Static Structures of Soft-Interfaces in J-PARC

A novel neutron reflectometer with horizontal geometry will be established at BL16 in Materials and Life Science Experimental Facility (MLF) of Japan Proton Accelerator Research Complex (J-PARC) as a successor of a reflectometer ARISA-II. ARISA-II corresponding to a single neutron beam downward at 2.22 deg has achieved off-specular and time-resolved reflectivity measurements. The novel reflectometer is designed so as to receive two tilted neutron beams (2.22 & 5.71 deg), which gives us an opportunity in investigation on a free liquid surface. The reflectometer can provide a micro-sized beam by slit collimation and obtain a fair reflectivity with small sample area. Also, T0 chopper and neutron focusing mirror are newly introduced. The T0 chopper can suppress the background due to fast neutrons. The focusing mirror produces further reduction of measurement time not only for specular reflection by focusing neutrons on a sample, but also grazing incidence small-angle neutron scattering (GISANS) measurements by focusing on a detector.

Simultaneous measurement of X-ray specular reflection and off-specular diffuse scattering from liquid surfaces using a two-dimensional pixel array detector: the liquid-interface reflectometer of BL37XU at SPring-8

An X-ray reflectometer for simultaneous measurement of specular and off-specular reflection of liquid surfaces is described. The reflectometer, equipped with a two-dimensional single X-ray photon-counting pixel array detector obtained the full range of X-ray specular and off-specular reflections in an extremely short time (1 s). Both the specular and off-specular reflection of water exhibited good agreement with the predicted capillary-wave theory within the appropriate instrumental resolution. The approach is also demonstrated on an aqueous solution of 1-dodecyl-3-methylimidazolium chloride. The monolayer in which the dodecyl chain faces upwards and the Cl(-) anion locates next to the imidazolium ring formed on the water surface was found to be laterally homogeneous. The use of a pixel array detector will be particularly powerful for in situ measurements to investigate both out-of-plane and in-plane structures simultaneously, not only for liquid surfaces but also for other thin films.

Supported bilayers: Combined specular and diffuse X-ray scattering

A method is proposed for the analysis of specular and off-specular reflectivity from supported lipid bilayers. Both thermal fluctuations and the "static" roughness induced by the substrate are carefully taken into account. Examples from supported bilayers and more complex systems comprising a bilayer adsorbed or grafted on the substrate and another "floating" bilayer are given. The combined analysis of specular and off-specular reflectivity allows the precise determination of the structure of adsorbed and floating bilayers, their tension, bending rigidity and interaction potentials. We show that this new method gives a unique opportunity to investigate phenomena like protrusion modes of adsorbed bilayers and opens the way to the investigation of more complex systems including different kinds of lipids, cholesterol or peptides.

MNM-1A-2 鏡面・非鏡面X線反射率測定によるタンパク吸着膜構造の統計学的評価(セッション 1A マイクロ・ナノスケールバイオ計測と医用応用)

The purpose of this study is to investigate conformations of antibodies immobilized on three kinds of solid surfaces modified with APTES, AEAPTES or GA and their antigen-binding affinities. In the recent developments in biosensors, although the geometric structure of antibodies determines their sensitivity, few studies have focused on their conformations and its effect on their antigen-binding capacity due to a lack of applicable analysis techniques. In this work, specular and off-specular X-ray reflectivity measurement were employed, which enables us to analyze vertical and lateral multilayer structure. The results showed that the antigen-binding affinity on GA was highest among antibodies immobilized on three modified surfaces, although their conformations were almost the same as 'flat-on' analyzed by specular X-ray reflectivity. In contrast, lateral layer structure analysis by off-specular reflection revealed that protein layer on GA before antigen-binding had a relatively-long lateral correlation length and a low fractal dimension which would cause the reduction of steric hindrance for antigens' access to binding sites of antibodies.

Time-resolved specular and off-specular neutron reflectivity measurements on deuterated polystyrene and poly(vinyl methyl ether) blend thin films during dewetting process

We performed time-resolved specular and off-specular neutron reflectivity measurements on blend thin films 42 and 98 nm thick of deuterated polystyrene and poly(vinyl methyl ether) during dewetting process induced by the phase separation in two phase region using a time-of-flight neutron reflectometer. In the specular measurements we found that the phase separation directed to the depth direction occurred near the air interface as well as near the Si substrate during the incubation period before dewetting. In addition we also found that the phase separation occurred asymmetrically at the two interfaces and inhomogeneously in the film plane, showing that the dewetting was induced by the composition fluctuation mechanism. Off-specular reflectivity was analyzed, for the first time, to evaluate kinetics of structure formation in the film plane during the dewetting process. We found in the analysis that the droplets formation in micrometer scale occurred in the late stage of dewetting.

Hydrated cholesterol: Phospholipid domains probed by synchrotron radiation

X-ray scattering experiments on mixed films of cholesterol and phospholipids at air-water and Si solid-water interfaces were undertaken to glean information on pathological crystallization of cholesterol bilayers. Grazing-incidence X-ray diffraction patterns at the air-water interface of various cholesterol:dipalmitoyl-phosphatidylcholine (Ch:DPPC) monolayer mixtures compressed beyond monolayer collapse yielded the established 10 x 7.5 Ų Ch bilayer motif, for Ch:DPPC molar ratios higher than 2.5:1. Attempts to obtain a diffraction signal from various Ch:phospholipid film mixtures at the Si solid-water interface, indicative of the presence of the Ch bilayer motif, were unsuccessful. Only after removal of sufficient water from the cell was a weak diffraction signal obtained suggestive of a cholesterol film two bilayers thick. Off-specular X-ray reflectivity measurements made on a 1.75:1 mixture of Ch and bovine cardiac phosphatidylcholine (BCPC) deposited as a bilayer on a Si wafer and placed in a cell filled with water yielded positive results. The derived electron density profile showed the presence of a bilayer mixture consistent with a phase separation of cholesterol and BCPC, and possible formation of a crystalline cholesterol bilayer within the hydrated mixed bilayer, but not a proof thereof.

Kinetics of alloy formation at the interfaces in a Ni-Ti multilayer: X-ray and neutron reflectometry study

Vacuum-deposited Ni/Ti multilayers on annealing at different temperatures exhibit formation of ordered alloy layers at interfaces. We have studied in detail the formation of alloy at interfaces of a Ni/Ti multilayer on annealing at $300\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$ and $400\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$ using powder x-ray diffraction, x-ray reflectometry, polarized neutron reflectometry, and off-specular x-ray reflectometry techniques. Correlation among structural, magnetic, and morphological properties in as-deposited Ni/Ti multilayer as well as in a sample annealed at $300\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$ and $400\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$ has been studied. X-ray diffraction technique was used to obtain crystal structure of the sample. Specular x-ray reflectometry and neutron reflectometry were used to determine the growth of alloy layers from density profile, as a function of depth in the sample. From off-specular x-ray reflectivity we found that the in-plane correlation lengths at the interfaces grew with annealing. This is associated with alloy crystallite growth obtained from x-ray reflectometry. Detailed magnetic-moment density profile of as-deposited as well as annealed multilayer sample has been determined by polarized neutron reflectometry measurements, which was used to determine the magnetic nature of the alloy layers. The results show formation of nonmagnetic alloy layers at the interfaces on annealing. From the Bragg-peak intensities of x-ray reflectivity and polarized neutron reflectivity measurements, we have estimated the diffusion lengths after annealing at $300\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$ and $400\text{ }\ifmmode^\circ\else\textdegree\fi{}\text{C}$.