Grazing Incidence Small Angle Neutron Research Articles

Grazing-incidence small-angle neutron scattering at high pressure (HP-GISANS): a soft matter feasibility study on grafted brush films

Grazing-incidence small-angle neutron scattering (GISANS) under pressure (HP-GISANS) at the solid (Si)–liquid (D2O) interface is demonstrated for the pressure-induced lateral morphological characterization of the nanostructure in thin (<100 nm) soft matter films. We demonstrate feasibility by investigating a hydrophobic {poly[(2,2,3,3,4,4,5,5-octafluoro)pentyl methacrylate]} (POFPMA)–hydrophilic {poly[2-(dimethylamino)ethyl methacrylate]} (PDMAEMA) brush mixture of strong incompatibility between the homopolymers, anchored on Si, at T = 45°C for two pressures, P = 1 bar and P = 800 bar. Our GISANS results reveal nanostructural rearrangements with increasing P, underlining P-induced effects in tethered polymer brush layers swollen with bulk solvent.

Strategy to simulate and fit 2D grazing-incidence small-angle X-ray scattering patterns of nanostructured thin films.

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

Three-dimensional structure of hybrid magnetic skyrmions determined by neutron scattering

Magnetic skyrmions are topologically protected chiral spin textures which present opportunities for next-generation magnetic data storage and logic information technologies. The topology of these structures originates in the geometric configuration of the magnetic spins - more generally described as the structure. While the skyrmion structure is most often depicted using a 2D projection of the three-dimensional structure, recent works have emphasized the role of all three dimensions in determining the topology and their response to external stimuli. In this work, grazing-incidence small-angle neutron scattering and polarized neutron reflectometry are used to determine the three-dimensional structure of hybrid skyrmions. The structure of the hybrid skyrmions, which includes a combination of N\'eel-like and Bloch-like components along their length, is expected to significantly contribute to their notable stability, which includes ambient conditions. To interpret the neutron scattering data, micromagnetic simulations of the hybrid skyrmions were performed, and the corresponding diffraction patterns were determined using a Born approximation transformation. The converged magnetic profile reveals the magnetic structure along with the skyrmion depth profile, including the thickness of the Bloch and N\'eel segments and the diameter of the core.

Advanced polarization analysis capability on the very small-angle neutron scattering instrument at the NIST Center for Neutron Research

The Very Small Angle Neutron Scattering (VSANS) diffractometer at the National Institute of Standards and Technology has been commissioned and is in the user program. A large available space of nearly 2 m along the beam in the sample area not only enhances the existing SANS polarization analysis capability, but also makes it possible for implementation of other polarization analysis capabilities which would not be easily available on existing SANS instruments, including grazing-incidence small-angle neutron scattering with polarization analysis and spherical neutron polarimetry. We present two polarized setups, one for high magnetic sample fields and the other for low magnetic sample fields, together with a versatile and flexible operational platform for polarized beam experiments. The design of a magnetostatic cavity device that provides better field homogeneity and thus longer 3He polarization relaxation time is discussed. It consists of an end-compensated magnetic shielded solenoid with non-identical holes to accommodate the divergent scattered beam in a constrained distance. Significant improvement in polarized neutronic performance, 3He polarization relaxation time, and an extended momentum transfer range for polarization analysis are presented. Improved neutron polarizing devices, double V-shaped supermirror polarizer, adiabatic radio-frequency spin flipper, and a 3He spin analyzer have yielded an initial instrumental flipping ratio of 100, allowing for higher sensitivity to detection of weak magnetic features in the sample.

Grazing-incidence small angle neutron scattering achieved in spectrometer SANS-Suanni of transmission geometry

Current work presents the design and applications of the grazing-incidence small-angle neutron scattering (GISANS) based on SANS-Suanni spectrometer at the 20 MW China Mianyang research reactor (CMRR)-based neutron center. A multi-dimensional sample stage with both front and back slits were designed and set up on SANS-Suanni for achieving the geometry. Experimentally, thin films samples with mono-dispersed silica on sapphire substrates were prepared for collecting two-dimensional (2D) GISANS patterns at beam size setting of 4 mm width and 5 mm height. Typical signals such as the specular reflection peak, Yoneda peak, as well as the sample scattering, etc. were obtained. Moreover, integrated 1D GISANS profiles in different directions, namely vertical and horizontal directions of the incident beam (0V, 0H), and horizontal direction of the Yoneda peak (YH) were obtained via rectangular integration. Accordingly, incident angle (αi) as about 0.76° and the contrast of the sample systems as around 4.07 × 1010 cm−2 were determined. Moreover, the overlapping of 0H curves and the SANS profiles indicates that GISANS can cover some of the structural information as SANS provided, along with the capability of measuring the thin film samples.

Using Grazing-Incidence Small-Angle Neutron Scattering to Study the Orientation of Block Copolymer Morphologies in Thin Films

We used grazing-incidence small-angle neutron scattering (GISANS) to probe the depth-dependent orientation of self-assembled morphologies of block copolymers. A hydrophobic–hydrophobic block copolymer, poly(solketal methacrylate)-block-polystyrene (PSM-b-PS), was synthesized and spin-coated into films tens of nanometers in thickness where the polymers adopted a disordered state. PSM-b-PS was then hydrolyzed by exposing the polymer thin film to trifluoroacetic acid vapor or embedding a photoacid generator in the film during spin coating, followed by exposure to UV light. The hydrolysis converted the block copolymer into a hydrophilic–hydrophobic block copolymer, poly(glycerol monomethacrylate)-block-polystyrene (PGM-b-PS), significantly increasing the segmental interaction parameter (χ) and causing microphase separation of the copolymers. GISANS was used to study the depth-dependent structure of the films and revealed that the orientation of the microphase-separated structure differed at the polymer–air and polymer–substrate interfaces. In the regions where the lamellae were parallel to the interfaces, the orientation propagated into the film from the interfaces. However, in the areas where the lamellae were perpendicular to the interfaces, the orientation did not persist with increasing distance from the interfaces.

Neutron adiabaticity and its impact on data analysis, illustrated for polarized GISANS

The significance of neutron spin adiabaticity in the data analysis of polarized Grazing Incidence Small Angle Neutron Scattering (GISANS) is discussed, with the aim of minimizing the number of simulation parameters of complex magnetic models within the neutron scattering cross-section. We illustrate how an estimate of the neutron polarization direction and adiabaticity can be obtained by magnetic field and neutron ray-tracing simulations and compare the results with measurements of the magnetic field map for the beamline used in the GISANS experiment. We show how small deviations from the neutron polarization direction with respect to the magnetic field vector at the sample position significantly affect the data analysis, and how this can be considered within the magnetic model of the scattering cross section using the Distorted Wave Born Approximation.

The GISANS instrument at the HBS

This manuscript describes a concept of a grazing incidence small-angle neutron scattering (GISANS) instrument for the high brilliance source (HBS). The HBS being a compact pulsed neutron source using a moderate energy proton accelerator which allows for very compact moderators and shielding, and flexible pulse repetition rates. Similar to many other instrument concepts for this source, the lowest proposed HBS pulse frequency of 24 Hz with a relatively large detector distance is the optimal choice for the instrument described here in terms of obtained intensity and Q-range (i.e. scattering vector range). Such a configuration has the added advantage of good Q-resolution, which is important when scattering depths need to be resolved well. This is especially the case for GISANS when the incident angle is close to the critical angle of total reflection. The performance obtained from detailed ray-tracing computer simulations predict a high performance instrument that will be comparable to reflectometers and small angle neutron scattering (SANS) instruments at high-flux reactor sources such as the Forschungsreaktor Munich (FRM-2) and others.

Deciphering perovskite decomposition in a humid atmosphere with TOF-GISANS

Doping or alloying of the cations on the A-site and halides on the X site of ABX3 perovskites has been demonstrated as a successful technique for improving moisture stability of perovskite films for optoelectronic applications. Despite structural and electrical stability improvements, these films still undergo moisture induced degradation to Lead Iodide and other photo-inactive phases, reducing device lifetime and performance. Understanding of their moisture induced degradation has been limited by the contrast mechanisms and sensitivity of optical and x-ray scattering techniques. Time-of-Flight Grazing Incidence Small Angle Neutron Scattering (TOF-GISANS) presents itself as a powerful alternative capable of identifying low atomic weight phases and offering depth resolution. Herein we use TOF-GISANS to begin to uncover moisture induced degradation pathways in various mixed perovskite systems fabricated under ambient conditions and exposed to 90% rH in the dark for up to 12 h, showing poor stoichiometric homogeneity through the bulk of the film and facile formation of deuterated by-products at ambient temperatures. We find evidence indicative of formation of PbI2, and PbBr2 from peaks apparent in scattering from the surface of MAPbI3, FA0.83MA0.17Pb(I0.83Br0.17)3, and FA0.83Cs0.17Pb(I0.83Br0.17)3 thin films, with degradation less pronounced in the latter films containing Cs. Deuterated by-products form readily, resulting in decreasing average particle size as perovskite crystals swell and fragment from the grain periphery inwards. Cs0.05(FA0.83MA0.17)0.95Pb(I0.84Br0.16)3 shows impressive phase resilience compared to the other mixtures, with minimal segregation to other phases observed in vertical cuts through the 2D scattering image, though still exhibits deleterious morphological degradation. TOF-GISANS is demonstrated as a powerful tool for characterisation of these materials, with significant potential for future investigations into phase changes in thin films.

Distributions of Deuterated Polystyrene Chains in Perforated Layers of Blend Films of a Symmetric Polystyrene-block-poly(methyl methacrylate)

We have examined the spatial distributions of polymer chains in blend films of weakly segregated polystyrene-block-poly(methyl methacrylate) [P(S-b-MMA)] and deuterated polystyrene (dPS). By fine-tuning the composition (ϕPS+dPS = 63.8 vol %) of the total PS/dPS component and annealing temperature (230 and 270 °C), P(S-b-MMA)/dPS blend films mainly form perforated layers with a parallel orientation (hereafter PLs//). The distributions of dPS in PLs// were probed by grazing-incidence small-angle neutron scattering (GISANS) and time-of-flight neutron reflectivity (ToF-NR). GISANS and ToF-NR results offer evidence that dPS chains preferentially locate at the free surface and within the PS layers for blend films that were annealed at 230 °C. Upon annealing at 270 °C, dPS chains distribute within PS layers and perforated PMMA layers. Nevertheless, dPS chains still retain a surface preference for thin films. In contrast, such surface segregation of dPS chains is prohibited for thick films when annealed at 270 °C.

Resonant enhancement of grazing incidence neutron scattering for the characterization of thin films

We use signal enhancement in a quantum resonator for the characterization of a thin layer of vanadium hydride using neutron reflectometry and demonstrate that pressure-concentration isotherms and expansion coefficients can be extracted from the measurement of totally externally reflected neutrons only. Moreover, a consistent data analysis of the attenuation cross section allows us to detect and quantify off-specular and small angle scattering. As our experiments are effective direct beam measurements, combined with resonant signal enhancement, counting times become considerably reduced. This allows us to overcome the challenges resulting from the comparatively low brilliance of neutron beams for grazing incidence scattering experiments. Further, we discuss the potential of resonant enhancement to increase any scattering, which is of particular interest for grazing incidence small angle neutron scattering and spectroscopy.

Influence of NaCl on the Structure and Dynamics of Phospholipid Layers

We present a structural and dynamical analysis of the influence of NaCl on multilayer stacks of phospholipids on a solid surface. To this end, multilayer stacks of phospholipids (L-α-phosphatidylcholine, abbreviated as SoyPC) are investigated with neutron reflectometry, grazing-incidence small-angle neutron scattering (GISANS) and grazing-incidence neutron-spin echo spectroscopy (GINSES). We show both that the NaCl influence on the structure is predominantly on water-head group interface and also, that the change in dynamics is restricted to an associated change in the inter-plane viscosity. Using this knowledge, it is possible to model the dynamical behavior of a phospholipid membrane in response to a salt concentration of the solvent using only a single parameter, namely the in-plane viscosity. The excellent agreement with our previously published model also strongly supports the existence of a thermally excited surface mode in phospholipid membranes for close-to-physiological conditions.

Flexible Sample Environment for the Investigation of Soft Matter at the European Spallation Source: Part II—The GISANS Setup

The FlexiProb project is a joint effort of three soft matter groups at the Universities of Bielefeld, Darmstadt, and Munich with scientific support from the European Spallation Source (ESS), the small-K advanced diffractometer (SKADI) beamline development group of the Jülich Centre for Neutron Science (JCNS), and the Heinz Maier-Leibnitz Zentrum (MLZ). Within this framework, a flexible and quickly interchangeable sample carrier system for small-angle neutron scattering (SANS) at the ESS was developed. In the present contribution, the development of a sample environment for the investigation of soft matter thin films with grazing-incidence small-angle neutron scattering (GISANS) is introduced. Therefore, components were assembled on an optical breadboard for the measurement of thin film samples under controlled ambient conditions, with adjustable temperature and humidity, as well as the optional in situ recording of the film thickness via spectral reflectance. Samples were placed in a 3D-printed spherical humidity metal chamber, which enabled the accurate control of experimental conditions via water-heated channels within its walls. A separately heated gas flow stream supplied an adjustable flow of dry or saturated solvent vapor. First test experiments proved the concept of the setup and respective component functionality.

Flexible Sample Environment for the Investigation of Soft Matter at the European Spallation Source: Part II—The GISANS Setup

The FlexiProb project is a joint effort of three soft matter groups at the Universities of Bielefeld, Darmstadt, and Munich with scientific support from the European Spallation Source (ESS), the small-K advanced diffractometer (SKADI) beamline development group of the Julich Centre for Neutron Science (JCNS), and the Heinz Maier-Leibnitz Zentrum (MLZ).Within this framework, a flexible and quickly interchangeable sample carrier system for small-angle neutron scattering (SANS) at the ESS was developed. In the present contribution, the development of a sample environment for the investigation of soft matter thin films with grazing-incidence small-angle neutron scattering (GISANS) is introduced. Therefore, components were assembled on an optical breadboard for the measurement of thin film samples under controlled ambient conditions, with adjustable temperature and humidity, as well as the optional in situ recording of the film thickness via spectral reflectance. Samples were placed in a 3D-printed spherical humidity metal chamber, which enabled the accurate control of experimental conditions via water-heated channels within its walls. A separately heated gas flow stream supplied an adjustable flow of dry or saturated solvent vapor. First test experiments proved the concept of the setup and respective component functionality.

Grazing Incidence Small-Angle Neutron Scattering: Background Determination and Optimization for Soft Matter Samples

Grazing incidence small-angle neutron scattering (GISANS) provides access to interfacial properties, e.g., in soft matter on polymers adsorbed at a solid substrate. Simulations in the frame of the distorted wave Born approximation using the BornAgain software allow to understand and quantify the scattering pattern above and below the sample horizon, in reflection and transmission, respectively. The small-angle scattering from the interfacial layer, visible around the transmitted beam, which might contribute also on the side of the reflected beam, can be understood in this way and be included into the analysis. Background reduction by optimized sample cell design is supported by simulations, paving the way for an optimized GISANS cell.

Direct observation of spin correlations in an artificial triangular lattice Ising spin system with grazing-incidence small-angle neutron scattering.

The triangular lattice with Ising magnetic moments is an archetypical example of geometric frustration. In the case of dipolar-coupled out-of-plane moments, the geometric frustration results in a disordered classical spin-liquid state at higher temperatures while the system is predicted to transition to an anti-ferromagnetic stripe ground state at low temperatures. In this work we fabricate artificial triangular Ising spin systems without and with uniaxial in-plane compression to tune the nature and temperature of the correlations. We probe the energy scale and nature of magnetic correlations by grazing-incidence small-angle neutron scattering. In particular, we apply a newly-developed empirical structure-factor model to describe the measured short-range correlated spin-liquid state, and find good agreement with theoretical predictions. We demonstrate that grazing-incidence neutron scattering on our high-quality samples, in conjunction with detailed modeling of the scattering using the Distorted Wave Born Approximation, can be used to experimentally quantify the spin-liquid-like correlations in highly-frustrated artificial spin systems.

Advanced Small-Angle Scattering Instrument Available in the Tokyo Area. Time-Of-Flight, Small-Angle Neutron Scattering Developed on the iMATERIA Diffractometer at the High Intensity Pulsed Neutron Source J-PARC

A method of time-of-flight, small-angle neutron scattering (TOF-SANS) has been developed based on the iMATERIA powder diffractometer at BL20, of the Materials and Life Sciences Facility (MLF) at the high-intensity proton accelerator (J-PARC). A large-area detector for SANS, which is composed of triple-layered 3He tube detectors, has a hole at its center in order to release a direct beam behind and to detect ultra-small-angle scattering. As a result, the pulsed-neutron TOF method enables us to perform multiscale observations covering 0.003 < q (Å−1) < 40 (qmax/qmix = 1.3 × 104) and to determine the static structure factor S(q) and/or form factor P(q) under real-time and in-situ conditions. Our challenge, using unique sample accessories of a super-conducting magnet and polarized neutron, is dynamic nuclear polarization (DNP) for contrast variation, especially for industrial use. To reinforce conventional SANS measurements with powder materials, grazing-incidence small-angle neutron scattering (GISANS) or reflectivity is also available on the iMATERIA instrument.

3D printed spherical environmental chamber for neutron reflectometry and grazing-incidence small-angle neutron scattering experiments.

In neutron scattering on soft matter, an important concern is the control and stability of environmental conditions surrounding the sample. Complex sample environment setups are often expensive to fabricate or simply not achievable by conventional workshop manufacturing. We make use of state-of-the-art 3D metal-printing technology to realize a sample environment for large sample sizes, optimized for investigations on thin film samples with neutron reflectometry (NR) and grazing-incidence small-angle neutron scattering (GISANS). With the flexibility and freedom of design given by 3D metal-printing, a spherical chamber with fluidic channels inside its walls is printed from an AlSi10Mg powder via selective laser melting (SLM). The thin channels ensure a homogeneous heating of the sample environment from all directions and allow for quick temperature switches in well-equilibrated atmospheres. In order to optimize the channel layout, flow simulations were carried out and verified in temperature switching tests. The spherical, edgeless design aids the prevention of condensation inside the chamber in case of high humidity conditions. The large volume of the sample chamber allows for high flexibility in sample size and geometry. While a small-angle neutron scattering (SANS) measurement through the chamber walls reveals a strong isotropic scattering signal resulting from the evenly orientated granular structure introduced by SLM, a second SANS measurement through the windows shows no additional background originating from the chamber. Exemplary GISANS and NR measurements in time-of-flight mode are shown to prove that the chamber provides a stable, background free sample environment for the investigation of thin films.

Organic solar cells probed with advanced neutron scattering techniques

Neutron scattering techniques provide unique insights into the active layer morphology of organic solar cells. The nanoscale morphology, the thin film vertical composition, and the intermixing on a molecular level, which all strongly have an impact on the performance of organic solar cells, can be probed with neutrons. In addition to the static structure, also fast dynamics occurring in the active material is accessible with neutrons. This perspective letter highlights the power of grazing incidence small angle neutron scattering and quasi-elastic neutron scattering experiments after shortly introducing into the working principle of organic solar cells.

Surface distortion of Fe dot-decorated TiO2 nanotubular templates using time-of-flight grazing incidence small angle scattering

Physical properties of nanoclusters, nanostructures and self-assembled nanodots, which in turn are concomitantly dependent upon the morphological properties, can be modulated for functional purposes. Here, in this article, magnetic nanodots of Fe on semiconductor TiO2 nanotubes (TNTs) are investigated with time-of-flight grazing incidence small-angle neutron scattering (TOF-GISANS) as a function of wavelength, chosen from a set of three TNT templates with different correlation lengths. The results are found corroborating with the localized scanning electron microscopy (SEM) images. As we probe the inside and the near-surface region of the Fe-dotted TNTs with respect to their homogeneity, surface distortion and long-range order using TOF-GISANS, gradual aberrations at the top of the near-surface region are identified. Magnetization measurements as a function of temperature and field do not show a typical ferromagnetic behavior but rather a supermagnetic one that is expected from a nonhomogeneous distribution of Fe–dots in the intertubular crevasses.