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The performance of multilayers in optical components, such as those used in neutron scattering instruments, is crucially dependent on the achievable interface width. We have shown how the interface width of Ni/Ti multilayers can be improved using the incorporation of B4C to inhibit the formation of nanocrystals and limit interdiffusion and intermetallic reactions at the interfaces. A modulated ion-assistance scheme was used to prevent intermixing and roughness accumulation throughout the layer stack. In this work we investigate the incorporation of low-neutron-absorbing 11B4C for Ni/Ti neutron multilayers. Combined fitting of neutron reflectivity and X-ray reflectivity measurements shows an elimination of accumulated roughness for the 11B4C containing multilayers with a mean interface width of 4.5 Å, resulting in an increase in reflectivity at the first Bragg peak by a factor of 2.3 and 1.5 for neutron and X-ray measurements, respectively.

We have performed grazing incidence neutron small angle scattering using a fan shaped incident beam focused along one dimension. This allows significantly reduced counting times for measurements of lateral correlations parallel to an interface or in a thin film where limited depth resolution is required. We resolve the structure factor of iron inclusions in aluminium oxide and show that the ordering of silica particles deposited on a silicon substrate depends on their size. We report hexagonal packing for 50 nm but not for 200 nm silica spheres deposited by a modified Langmuir-Schaefer method on a silicon substrate. For the 200 nm particles we extract the particles shape from the form factor. Moreover, we report dense packing of the particles spread on a free water surface. We name this method π-GISANS to highlight that it differs from GISANS as it gives lateral information while averaging the in-depth structure.

Vapor phase infiltration into a self-assembled block copolymer (BCP) to create a hybrid material in one of the constituent blocks can enhance the etch selectivity for pattern transfer. Multiple pulse infiltration into carbohydrate-based high-χ BCP has previously been shown to enable sub-10 nm feature pattern transfer. By optimizing the amount of infiltrated material, the etch selectivity should be further improved. Here, an investigation of semi-static sequential infiltration synthesis of trimethyl aluminum (TMA) and water into maltoheptaose (MH) films, and into hydroxyl-terminated poly(styrene) (PS-OH) films, was performed, by varying the process parameters temperature, precursor pulse duration, and precursor exposure length. It was found that, by decreasing the exposure time from 100 to 20 s, the volumetric percentage on included pure Al2O3 in MH could be increased from 2 to 40 vol% at the expense of a decreased infiltration depth. Furthermore, the degree of infiltration was minimally affected by temperature between 64 and 100 °C. Shorter precursor pulse durations of 10 ms TMA and 5 ms water, as well as longer precursor pulses of 75 ms TMA and 45 ms water, were both shown to promote a higher degree, 40 vol%, of infiltrated alumina in MH. As proof of concept, 12 nm pitch pattern transfer into silicon was demonstrated using the method and can be concluded to be one of few studies showing pattern transfer at such small pitch. These results are expected to be of use for further understanding of the mechanisms involved in sequential infiltration synthesis of TMA/water into MH, and for further optimization of carbohydrate-based etch masks for sub-10 nm pattern transfer. Enabling techniques for high aspect ratio pattern transfer at the single nanometer scale could be of high interest, e.g., in the high-end transistor industry.

Devices with tunable magnetic noncollinearity are important components of superconducting electronics and spintronics, but they typically require epitaxial integration of several complex materials. The spin-polarized neutron reflectometry measurements on La1-xSrxMnO3 homojunction arrays with modulated Sr concentration reported herein have led to the discovery of magnetic fan structures with highly noncollinear alignment of Mn spins and an emergent periodicity twice as large as the array's unit cell. The neutron data show that these magnetic superstructures can be fully long-range ordered, despite the gradual modulation of the doping level created by charge transfer and chemical intermixing. The degree of noncollinearity can be effectively adjusted by low magnetic fields. Notwithstanding their chemical and structural simplicity, oxide homojunctions thus show considerable promise as a platform for tunable complex magnetism and as a powerful design element of spintronic devices.

Vapor phase infiltration into a self-assembled block copolymer (BCP) to create a hybrid material in one of the constituent blocks can enhance the etch selectivity for pattern transfer. Multiple pulse infiltration into carbohydrate-based high

Sequential infiltration synthesis (SIS) into poly(styrene)-block-maltoheptaose (PS-b-MH) block copolymer using vapors of trimethyl aluminum and water was used to prepare nanostructured surface layers. Prior to the infiltration, the PS-b-MH had been self-assembled into 12 nm pattern periodicity. Scanning electron microscopy indicated that horizontal alumina-like cylinders of 4.9 nm diameter were formed after eight infiltration cycles, while vertical cylinders were 1.3 nm larger. Using homopolymer hydroxyl-terminated poly(styrene) (PS-OH) and MH films, specular neutron reflectometry revealed a preferential reaction of precursors in the MH compared to PS-OH. The infiltration depth into the maltoheptaose homopolymer film was found to be 2.0 nm after the first couple of cycles. It reached 2.5 nm after eight infiltration cycles, and the alumina incorporation within this infiltrated layer corresponded to 23 vol % Al2O3. The alumina-like material, resulting from PS-b-MH infiltration, was used as an etch mask to transfer the sub-10 nm pattern into the underlying silicon substrate, to an aspect ratio of approximately 2:1. These results demonstrate the potential of exploiting SIS into carbohydrate-based polymers for nanofabrication and high pattern density applications, such as transistor devices.

Graphite intercalation compounds (GICs) are a group of layered materials that are suitable as monochromators for cold neutrons. KC

Sequential infiltration synthesis (SIS) into poly(styrene)-block-maltoheptaose (PS-b-MH) block copolymer using vapors of trimethyl aluminum and water was used to prepare nanostructured surface layers. Prior to the infiltration, the PS-b-MH had been self-assembled into 12 nm pattern periodicity. Scanning electron microscopy indicated that horizontal alumina-like cylinders of 4.9 nm diameter were formed after eight infiltration cycles, while vertical cylinders were 1.3 nm larger. Using homopolymer hydroxyl-terminated poly(styrene) (PS–OH) and MH films, specular neutron reflectometry revealed a preferential reaction of precursors in the MH compared to PS–OH. The infiltration depth into the maltoheptaose homopolymer film was found to be 2.0 nm after the first couple of cycles. It reached 2.5 nm after eight infiltration cycles, and the alumina incorporation within this infiltrated layer corresponded to 23 vol % Al2O3. The alumina-like material, resulting from PS-b-MH infiltration, was used as an etch mask to transfer the sub-10 nm pattern into the underlying silicon substrate, to an aspect ratio of approximately 2:1. These results demonstrate the potential of exploiting SIS into carbohydrate-based polymers for nanofabrication and high pattern density applications, such as transistor devices.

The strength of the interlayer exchange coupling in [Fe/MgO]$$_N$$ N (001) superlattices with 2 ≤ N ≤ 10 depends on the number of bilayer repeats (N). The exchange coupling is antiferromagnetic for all the investigated thicknesses while being nine times larger in a sample with N = 4 as compared to N = 2. The sequence of the magnetic switching in two of the samples (N = 4, N = 8) is determined using polarized neutron reflectometry. The outermost layers are shown to respond at the lowest fields, consistent with having the weakest interlayer exchange coupling. The results are consistent with the existence of quantum well states defined by the thickness of the Fe and the MgO layers as well as the number of repeats (N) in [Fe/MgO]$$ _{N}$$ N (001)superlattices.

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.

Intercalation of dyes into thin multilayered graphene oxide (GO) films was studied by neutron reflectivity and X-ray diffraction. Methylene blue (MB) penetrates the interlayer space of GO in ethanol solution and remains intercalated after the solvent evaporation, as revealed by the expansion of the interlayer lattice and change in chemical composition. The sorption of MB by thin GO films is found to be significantly stronger compared to the sorption of Crystal violet (CV) and Rose bengal (RB). This effect is attributed to the difference in the geometrical shape of planar MB and essentially nonflat CV and RB molecules. Graphite oxides and restacked GO films are found to exhibit different methylene blue (MB) sorptions. MB sorption by precursor graphite oxide and thin spin-coated films of GO is significantly stronger compared to freestanding micrometer-thick membranes prepared by vacuum filtration. Nevertheless, the sorption capacity of GO membranes is sufficient to remove a significant part of the MB from diluted solutions tested for permeation in several earlier studies. High sorption capacity results in strong modification of the GO structure, which is likely to affect permeation properties of GO membranes. Therefore, MB is not suitable for testing size exclusion effects in the permeation of GO membranes. It is not only hydration or solvation diameter but also the exact geometrical shape of molecules that needs to be taken into account considering size effects for penetration of molecules between GO layers in membrane applications.

Nanomaterials 11(1), 251 (2021). doi:10.3390/nano11010251, Magnetic Weyl semimetals are newly discovered quantum materials with the potential for use in spintronic applications. Of particular interest is the cubic Heusler compound Co$_{2}$MnGa due to its inherent magnetic and topological properties. This work presents the structural, magnetic and electronic properties of magnetron co-sputtered Co$_{2}$MnGa thin films, with thicknesses ranging from 10 to 80 nm. Polarized neutron reflectometry confirmed a uniform magnetization through the films. Hard x-ray photoelectron spectroscopy revealed a high degree of spin polarization and localized (itinerant) character of the Mn d (Co d) valence electrons and accompanying magnetic moments. Further, broadband and field orientation-dependent ferromagnetic resonance measurements indicated a relation between the thickness-dependent structural and magnetic properties. The increase of the tensile strain-induced tetragonal distortion in the thinner films was reflected in an increase of the cubic anisotropy term and a decrease of the perpendicular uniaxial term. The lattice distortion led to a reduction of the Gilbert damping parameter and the thickness-dependent film quality affected the inhomogeneous linewidth broadening. These experimental findings will enrich the understanding of the electronic and magnetic properties of magnetic Weyl semimetal thin films, Published by MDPI, Basel

This study presents how sequential infiltration synthesis of trimethyl aluminium and water into a carbohydrate-based block copolymer was used to enable pattern transfer of 6 nm half-pitch horizontal cylinders into silicon. Specular neutron reflectometry measurements of poly(styrene)-block-maltoheptaose self-assembled into horizontal cylinders indicate an increasing content of alumina after each sequential infiltration cycle, comparing 0, 1, 2, and 4 cycles, with alumina content reaching 2.4 vol% after four infiltrations cycles. Dry etching processes in inductively coupled plasma reactive ion etching for sub-10 nm patterns were developed, using a two-step technique: O2-plasma for polymer removal and a reactive ion etching of Si using a mixture of SF6 and C4F8 gases. Etch selectivity of more than 2:1 of silicon over alumina-like etch mask material was achieved. To evaluate the etching process, the etched Si structures were measured and characterized by scanning electron microscopy. These results are expected to be of use for nanofabrication and applications in the sub-10 nm regime.

Neutron reflectivity (NR) measurements have been employed to study the interfacial structuring and composition of electroresponsive boundary layers formed by an ionic liquid (IL) lubricant at an electrified gold interface when dispersed in a polar solvent. The results reveal that both the composition and extent of the IL boundary layers intricately depend on the bulk IL concentration and the applied surface potential. At the lowest concentration (5% w/w), a preferential adsorption of the IL cation at the gold electrode is observed, which hinders the ability to electro-induce changes in the boundary layers. In contrast, at higher IL bulk concentrations (10 and 20% w/w), the NR results reveal a significantly larger concentration of the IL ions at the gold interface that exhibit significantly greater electroresponsivity, with clear changes in the layer composition and layer thickness observed for different potentials. In complementary atomic force microscopy (AFM) measurements on an electrified gold surface, such IL boundary layers are demonstrated to provide excellent friction reduction and electroactive friction (known as tribotronics). In agreement with the NR results obtained, clear concentration effects are also observed. Together such results provide valuable molecular insight into the electroactive structuring of ILs in solvent mixtures, as well as provide mechanistic understanding of their tribotronic behaviours.

Permeation of multilayered graphene oxide (GO) membranes by polar solvents is known to correlate with their swelling properties and amount of sorbed solvent. However, quantitative estimation of sorption using standard (e.g., gravimetric) methods is technically challenging for few nanometers thick GO membranes/films exposed to solvent vapors. Neutron reflectivity (NR) was used here to evaluate the amount of solvents intercalated into the film which consists of only ∼31.5 layers of GO. Analysis of NR data recorded from the GO film exposed to vapors of polar solvents provides information about change of film thickness due to swelling, amount of intercalated solvent, and selectivity in sorption of solvents from binary mixtures. A quantitative study of GO film sorption was performed for D2O, d-methanol, ethanol, dimethyl sulfoxide (DMSO), acetonitrile, dimethylformamide (DMF), and acetone. Using isotopic contrast, we estimated selectivity in sorption of ethanol/d-methanol mixtures by the GO film. Estimation of sorption selectivity was also performed for D2O/DMF, D2O/DMSO, and D2O/acetonitrile binary mixtures. Sorption of polar solvents was compared for the thin GO film, micrometer thick free standing GO membranes, and graphite oxide powders.

The interactions between perfluoroalkyl substances (PFASs) and a phospholipid bilayer (1,2-dimyristoyl-sn-glycero-3-phosphocholine) were investigated at the molecular level using neutron reflectometry. Representative PFASs with different chain length and functional groups were selected in this study including: perfluorobutane sulfonate (PFBS), perfluorohexanoate (PFHxA), perfluorohexane sulfonate (PFHxS), perfluorononanoate (PFNA), perfluorooctane sulfonate (PFOS), and perfluorooctane sulfonamide (FOSA). All PFASs were found to interact with the bilayer by incorporation, indicating PFAS ability to accumulate once ingested or taken up by organisms. The interactions were observed to increase with chain length and vary with the functional group as SO

In present study we exploited Langmuir technique to produce self-assembled arrays composed of monodisperse iron oxide nanoparticles 10 nm and 20 nm in diameter and of their binary mixture. A combination of in-situ X-ray reflectometry and Grazing-incident small-Angle X-ray scattering was used to obtain in-plane and out-of-plane structure of the arrays directly on the water surface. Surface pressure isotherms and X-ray reflectometry analysis showed that monodisperse 10 nm nanoparticles form a highly ordered monolayer, while 20 nm particles pack in three-dimensional clusters with a short-range (nearest-neighbor) correlations between the particles. In a binary mixture of 10 nm and 20 nm nanoparticles composed in proportion 3:1 the self-assembly process results in a structure where the monolayer of 10 nm particles is perturbed by the larger particles. Non-trivial mixing causes an enlargement of interparticle distance but keeps the symmetry of two-dimensional lattice of smaller nanoparticles. Estimation of the acting interactions and micromagnetic simulation suggest the optimal formation for monodisperse and binary ensembles.

We report on the polarized neutron reflectometry investigation of monolayer of magnetic iron oxide nanoparticles assembled by the Langmuir-Schaefer method. After deposition onto a solid substrate the polarized neutron reflectometry measurements in the external magnetic field were carried out. Thickness, density, roughness and in-depth resolved magnetization profile of the resulted layer were obtained from accurate fitting routine.

Physical review applied 12(2), 024047 (2019). doi:10.1103/PhysRevApplied.12.024047, Chiral magnetism that manifests in the existence of skyrmions or chiral domain walls offers an alternative way for creating anisotropies in magnetic materials that might have large potential for application in future spintronic devices. Here we show experimental evidence for an alternative type of in-plane exchange-bias effect present at room temperature that is created from a chiral 90∘ domain wall at the interface of a ferrimagnetic-ferromagnetic $\mathrm{Dy-Co/Ni-Fe}$ bilayer system. The chiral interfacial domain wall forms due to the exchange coupling of $\mathrm{Ni-Fe}$ and $\mathrm{Dy-Co}$ at the interface and the presence of Dzyaloshinskii-Moriya interaction in the $\mathrm{Dy-Co}$ layer. As a consequence of the preferred chirality of the interfacial domain wall, the sign of the exchange-bias effect can be reversed by changing the perpendicular orientation of the $\mathrm{Dy-Co}$ magnetization. The chirality-created tunable exchange bias in $\mathrm{Dy-Co/Ni-Fe}$ is very robust against high in-plane magnetic fields $\mathrm{(μ0H≤6T)}$ and does not show any aging effects. Therefore, it overcomes the limitations of conventional exchange-bias systems., Published by American Physical Society, College Park, Md. [u.a.]

Swelling of Hummers graphene oxide (HGO) membranes in a set of progressively longer liquid alcohols (methanol to 1-nonanol) was studied using synchrotron radiation XRD after air ageing over prolonged periods of time. Both precursor graphite oxides and freshly prepared HGO membranes were found to swell in the whole set of nine liquid alcohols with an increase of interlayer spacing from approximate to 7 angstrom (solvent free) up to approximate to 26 angstrom (in 1-nonanol). A pronounced effect of ageing on swelling in alcohols was found for HGO membranes stored in air. The HGO membranes aged for 0.5-1.5 years show progressively slower swelling kinetics, a non-monotonic decrease of saturated swelling in some alcohols and complete disappearance of swelling for alcohol molecules larger than hexanol. Moreover, the HGO membranes stored under ambient conditions for 5 years showed a nearly complete absence of swelling in all alcohols but preserved swelling in water. In contrast, precursor graphite oxide powder showed unmodified swelling in alcohols even after 4 years of ageing. Since the swelling defines the size of permeation channels, the ageing effect is one of the important parameters which could explain the strong variation in reported filtration/separation properties of GO membranes. The time and conditions of air storage require standardization for better reproducibility of results related to performance of GO membranes in various applications. The ageing of GO membranes can be considered not only as a hindrance/degradation for certain applications, but also as a method to tune the swelling properties of HGO membranes for better selectivity in sorption of solvents and for achieving better selective permeability.

Thickness and substrate dependence of film growth, morphology, unit-cell structure, and electronic structures was thoroughly investigated for picene, the zigzag connected 5-ring molecule, by employing complementary techniques of in situ real-time X-ray reflectivity/diffraction, in situ electron spectroscopies, and atomic force microscopy. A different kind of thickness dependent structural transition was observed on SiO2 and graphite, resulting in a distinct electronic structure. On SiO2 picene films with 3D crystalline domains are formed with nearly upright molecular orientation from the initial growth stage. With increasing the film thickness the in-plane dimensions of the unit cell in the initially grown domains become smaller (in other words, more compressed), and, at the same time, crystalline domains with a more relaxed structure are nucleating on top of the compressed domains. In spite of such structural changes, the electronic structure, namely energy position of the highest occupied molecular orbi...

The H5 program with the complete rebuild of the guide system and the upgrade or renovation of all instruments leads to a tremendous increase of the instrument performances. The improvement was obtained both in terms of more useful flux and upgrade of the different instruments (e.g. higher field density for IN15). In addition, the industrial application instrument D50 offers an addition to the ILL instrument suite (see p. 27 in this issue). With the commissioning of the new spin echo spectrometer WASP in 2016, the H5 program will be completed and a considerable improvement for the ILL instrument park will be finalized.

Metal rare-earth magnetic/nonmagnetic Ho/Y superlattice structures possess a coherent spin helix propagating through many superlattice layer repetitions. An external magnetic field applied in the film plane induces a nonzero average chirality of the helices. It is shown that the direction of the applied in-plane field can modify the value and sign of the chirality parameter $\ensuremath{\gamma}$. The dependence of $\ensuremath{\gamma}$ on the relative angle of applied field during the field-cooling procedure has an oscillatory character and can be described by simple sinusoidal function with \ensuremath{\pi} periodicity. The experimental finding is discussed from the point of view of an interbalance between Zeeman energy, magnetocrystalline anisotropy, and induced uniaxial anisotropy.

The morphology and the magnetic and conducting properties of an amorphous multilayer nanosystem [(Co45Fe45Zr10)35(Al2O3)65/a-Si:H]36 consisting of (Co45Fe45Zr10)35(Al2O3)65 magnetic layers and semiconducting hydrogenated amorphous silicon (a-Si:H) layers of various thicknesses have been studied. Using a combination of methods (including polarized neutron reflectometry and grazing incidence small-angle X-ray scattering), it is shown that the magnetic and electrical properties of these multilayer structures are determined by their morphology. It is established that the magnetization and electric resistance of a sample is a nonmonotonic function of the a-Si:H layer thickness. Both characteristics are at a minimum for a structure with a semiconductor layer thickness of 0.4 nm. Samples with silicon layer thicknesses below 0.4 nm represent a three-dimensional structure of Co45Fe45Zr10 grains weakly ordered in space, while in samples with silicon layer thicknesses above 0.4 nm, these grains are packed in layers alternating in the vertical direction. The average lateral distance between nanoparticles in the layer plane has been determined, from which the dimensions of metal grains in each sample have been estimated.

Highly oriented hybrid thin films composed of rod-shaped CdSe nanocrystals and poly(3-hexylthiophene) are prepared by mechanical rubbing. The orientation distribution of both CdSe nanorods and crystalline P3HT domains is determined by a combination of transmission electron microscopy (electron diffraction, low dose high-resolution TEM, and tomography), grazing incidence X-ray diffraction measurements, and UV-vis spectroscopy. After rubbing, P3HT crystalline domains show a preferential face-on orientation ((010) contact plane) and the chains align parallel to the rubbing direction. CdSe nanorods also align parallel to the rubbing direction, but the level of alignment is a function of their concentration in the polymer matrix: the lower their concentration, the higher the level of in-plane orientation of both the nanorods and the polymer chains. GIXD and electron diffraction suggest that CdSe nanorods adopt a preferential contact plane on the substrate after rubbing. The high in-plane alignment of the nanorods is mainly due to the orientation of the surrounding P3HT matrix. In particular, low dose HR-TEM shows that the local orientation of individual NRs matches the orientation of the surrounding pi-stacked P3HT chains. For a high NR concentration, bundling of NRs into larger aggregates prevents their efficient alignment by rubbing.

The development of third-generation synchrotron sources has inspired qualitative and quantitative breakthroughs in structural studies of monomolecular organic layers. To study such systems formed at the gas–liquid interface, grazing-incidence diffraction (GID) has proved to be the most powerful technique. Until quite recently, in most cases, GID was performedviaa scanning approach with use of a collimating system in front of the detector to eliminate the effect of parallax and to achieve the required angular resolution. Owing to the long counting time required, this kind of measurement often introduces significant radiation damage to a sample and considerably restricts time-resolved studies, preventing the pursuit of emerging scientific areas such as the investigation of fast kinetic structural changes in two-dimensional systems. This problem can apparently become a real obstacle for the application of the scanning GID technique at fourth-generation synchrotron sources because of the extremely high X-ray fluxes involved. This article discusses the possibility of significantly reducing the measuring time and avoiding the beam parallax problem by using a high-brilliance submillimetre beam and a large-area two-dimensional detector (e.g.PILATUS) in a single-shot GID measurement on large-area sample surfaces. Both theoretical considerations of the problem and experimental GID results from monomolecular layers of behenic acid at the gas–water interface are presented, with a detailed description of the experimental conditions. The possibility of a diffraction imaging study of the texture of Langmuir monomolecular layers is demonstrated.

The control on the charge transport properties of ternary organic photovoltaic P3HT:PCBM:QBT devices is enabled by modulating the distribution of P3HT polymorphs in the device photoactive layers. Negligible amounts of QBT induce striking modifications in the P3HT lamellar stacking direction, forming both densely packed and non-densely packed P3HT chains. The former reduce the charge carrier recombination rate, enabling an increased fill factor and short-circuit device photocurrent.

The drying process of the bulk heterojunction (BHJ) layer has a strong impact on the solar cell performance for the well-investigated material system P3HT:PC61BM. For higher performing low-bandgap polymers and C71 fullerene derivatives, no comprehensive studies of the BHJ structure evolution during film drying are available. In this work we investigate the structure formation of the low-bandgap polymer poly{[4,40-bis(2-ethylhexyl)dithieno(3,2-b;20,30-d)silole]-2,6-diyl-alt-(2,1,3-benzothidiazole)-4,7-diyl} (PSBTBT) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) in the transition from wet to solid by in-situ grazing incidence X-ray diffraction (GIXD) and laser reflectometry simultaneously. The nucleation and crystallization of PSBTBT differs from the interface-induced crystallization of P3HT and occurs partially in the solution. It is shown that PSBTBT:PC71BM blend nanomorphology and optoelectronic device properties are rather insensitive to the drying process in the investigated temperature range...

Polymeric substrates are of importance in plastic electronics. However, polymeric surfaces can exhibit different morphologies depending on whether they are amorphous or semi-crystalline. This work focuses on the impact of the surface structure of bisphenol A polycarbonate substrates on the nucleation and growth of a p-type semi-conductor, namely zinc phthalocyanine (ZnPc). ZnPc films were deposited under high vacuum at different substrate temperatures on oriented semi-crystalline as well as amorphous substrates of PC. The oriented substrates of PC were prepared by a method combining mechanical rubbing and solvent induced crystallization: the substrates show a periodic and regular alternation of oriented crystalline lamellae. Grazing incidence X-ray diffraction shows that the crystalline lamellae of PC have a preferential ( a , c ) contact plane. Moreover, the substrates show a bilayer structure made of a 60 nm-thick semi-crystalline overlayer atop an amorphous underlayer. UV–vis spectroscopy shows that the polymorphism of the ZnPc films is not modified by the surface structure of the PC substrate (amorphous versus semi-crystalline). However, the statistical analysis of domain size and density versus substrate temperature T s evidences different apparent activation energies of the growth mechanism. High Resolution Transmission Electron Microscopy suggests that twinning along a (2 −1 0) plane accounts for the bifurcations of the in-plane b -axis direction of the ZnPc nanocrystals. On oriented substrates of PC, such bifurcations are partly suppressed by the nanocorrugation of the surface, resulting in larger apparent domain sizes and unidirectional in-plane orientation.

Mixed films of perfluorinated pentacene and diindenoperylene are studied for their structural and optical properties on SiO2 and glass substrates. Grazing incidence X-ray diffraction shows that the compounds mix on the molecular level. Two structures are identified. Their out-of-plane lattice spacing is determined by X-ray reflectivity, and their growth morphology is characterized using atomic force microscopy. It is found that one structure consists of molecules in a standing-up and the other in a lying-down orientation. The uniaxial dielectric function of mixed films is determined with spectroscopic ellipsometry, and the in-plane optical extinction coefficient is measured by real-time differential reflectance spectroscopy during growth. The question of intermolecular coupling between perfluorinated pentacene and diindenoperylene is discussed.

The efficiency of organic bulk heterojunction solar cells strongly depends on the multiscale morphology of the interpenetrating polymer-fullerene network. Understanding the molecular assembly and the identification of influencing parameters is essential for a systematic optimization of such devices. Here, we investigate the molecular ordering during the drying of doctor-bladed polymer-fullerene blends on PEDOT:PSS-coated substrates simultaneously using in situ grazing incidence X-ray diffraction (GIXD) and laser reflectometry. In the process of blend crystallization, we observe the nucleation of well-aligned P3HT crystallites in edge-on orientation at the interface at the instant when P3HT solubility is crossed. A comparison of the real-time GIXD study at ternary blends with the binary phase diagrams of the drying blend film gives evidence of strong polymer-fullerene interactions that impede the crystal growth of PCBM, resulting in the aggregation of PCBM in the final drying stage. A systematic dependence of the film roughness on the drying time after crossing P3HT solubility has been shown. The highest efficiencies have been observed for slow drying at low temperatures which showed the strongest P3HT interchain π-π-ordering along the substrate surface. By adding the "unfriendly" solvent cyclohexanone to a chlorobenzene solution of P3HT:PCBM, the solubility can be crossed prior to the drying process. Such solutions exhibit randomly orientated crystalline structures in the freshly cast film which results in a large crystalline orientation distribution in the dry film that has been shown to be beneficial for solar cell performance.

We report an in situ X-ray investigation of the composition dependence on the structural evolution during drying of doctor-bladed blends of poly-(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). This study enables an observation of the microstructure evolution in real time during blend crystallization. P3HT:PCBM blends with ratios of 1:0.5, 1:0.8, and 1:2 exhibit differing structural evolution during the course of solvent evaporation resulting in a different microstructure of the blends upon solidification. Large excess of PCBM over the eutectic composition impedes the π−π packing of P3HT chains and leads to a not yet observed diffraction feature with an associated spacing of 12.6 A, which might originate from a disordered phase of intimate mixed P3HT and PCBM molecules. This work provides a microscopic understanding of the composition dependence of the film formation from solution. The structural results are discussed in relation to the composition dependence of photovoltai...

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a ...

Additional information about the magnetization distribution in magnetic films is obtained with a 3D-polarimetry set-up. A pilot experiment was performed with the neutron polarization aligned perpendicular to the surface of a Fe-film in a magnetic field parallel to its surface. The Larmor-precession in the magnetic field between two current sheets was used to adjust the neutron polarization perpendicular to the sample surface. This new polarization-magnetization configuration was probed with a Fe-film in specular and off-specular scattering. The off-specular scattering is created by the magnetic domain structure of the Fe-film in remanence. The results of specular and off-specular scattering are reproduced by calculations for the configuration of the incoming neutron polarization parallel to the sample surface and the magnetic field and for the configuration of the incoming neutron polarization perpendicular to the sample surface and the magnetic field.

By a combined AFM/X-ray study, we unveil a reconstruction at the organic interface accompanying the Stranski−Kranstanov growth of di-indenoperylene (DIP) deposited on fluorinated cobalt-phthalocyan...

The combination of magnetic and nonmagnetic interactions between the colloidal particles in ferrofluids results in various local inter-particle correlations that, in turn, change the macroscopic properties of the whole system. Therefore, characterization of the particle ensemble is a crucial point, allowing optimization of a ferrofluid for a particular application. Here it is shown how the crystal structure of the particles can be easily obtained in a fast synchrotron light diffraction experiment without any special treatment of the ferrofluid sample. Moreover, from the same diffraction patterns, such important parameters as particle mean size and dispersion are retrieved; these are compared with the corresponding parameters obtained from electron microscopy data. A particular problem of magnetite–maghemite transformation in nanoparticles stabilized by the surfactant shell is pointed out.

Neutron reflectometry was used to study the assembly of magnetite nanoparticles in a water-based ferrofluid close to a silicon surface. Under three conditions, static, under shear and with a magnetic field, the depth profile is extracted. The particles have an average diameter of 11 nm and a volume density of 5% in a D2O–H2O mixture. They are surrounded by a 4 nm thick bilayer of carboxylic acid for steric repulsion. The reflectivity data were fitted to a model using a least square routine based on the Parratt formalism. From the scattering length density depth profiles the following behavior is concluded: the fits indicate that excess carboxylic acid covers the silicon surface and almost eliminates the water in the densely packed wetting layer that forms close to the silicon surface. Under constant shear the wetting layer persists but a depletion layer forms between the wetting layer and the moving ferrofluid. Once the flow is stopped, the wetting layer becomes more pronounced with dense packing and is accompanied by a looser packed second layer. In the case of an applied magnetic field the prolate particles experience a torque and align with their long axes along the silicon surface which leads to a higher particle density.

Surface excitations with energy e and momentum q parallel to the surface can in principle be detected by neutron scattering. The issue is if spin-echo methods, widely used to detect low energy excitations in bulk, can also be used for detecting surface excitations. This issue comes at a time when spin-echo methods are proposed to resolve one of the components of neutron momentum transfer in near surface scattering (SERGIS). The conclusion is that no surface excitation can be measured with momentum perpendicular to the plane of specular reflection, i.e. when q x = 0. If q x ≠ 0, the observation of surface excitations is better carried out in an experiment in which spin-echo is used to resolve energy exchange for the measurement of the momentum transfer.

Magnetic domain walls in thin films can be well analyzed using polarized neutron reflectometry. Well defined streaks in the off-specular spin-flip scattering maps are explained by neutron refraction at perpendicular N\'{e}el walls. The position of the streaks depends only on the magnetic induction within the domains, whereas the intensity of the off-specular magnetic scattering depends on the spin-flip probability at the domain walls and on the average size of the magnetic domains. This effect is fundamentally different and has to be clearly distinguished from diffuse scattering originating from the size distribution of magnetic domains. Polarized neutron reflectivity experiments were carried out using a $^3$He gas spin-filter with a analyzing power as high as 96% and a neutron transmission of approx 35%. Furthermore, the off-specular magnetic scattering was enhanced by using neutron resonance and neutron standing wave techniques., Comment: 5 pages

Bragg diffraction at grazing incidence of neutrons from a magnetic film decomposed into a set of ferromagnetic domains is considered within the frame of the distorted wave Born approximation. It is shown that the diffracted intensity measured as a function of angles of incidence and exit in the direction normal to the surface can provide information on the lateral distribution of domain magnetization. Theoretical results are illustrated by measurements of a mono-crystalline film of iron.

In magnetic colloids of sufficiently high particle concentration, frustration of dipolar interactions could arise as found in spin-glass systems. To understand this situation, a ferrofluid consisting of magnetite particles was frozen in either a horizontal or a vertical field and then 3D neutron-polarisation analysis was performed around the hysteresis loop in both field configurations. The same was done in the fluid state. A comparison of the data leads to the conclusion that frustration plays a key role in the self-organisation of nanoparticles in a frozen magnetic colloid.