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The hydration and thermal response kinetics of the cross-linked thermoresponsive copolymer poly((diethylene glycol monomethyl ether methacrylate)-co-poly(ethylene glycol) methyl ether methacrylate), abbreviated as P(MEO2MA-co-OEGMA300), thin film on a hydrophobic polyacrylonitrile (PAN) substrate coating, which resembles a synthetic fabric, is probed by in situ neutron reflectivity (NR). The PAN and monomer (MEO2MA and OEGMA300) solutions are sequentially spin-coated onto a silicon (Si) substrate. Afterward, plasma treatment is applied to realize the cross-linking of PAN and monomers. The as-prepared cross-linked P(MEO2MA-co-OEGMA300) film on the hydrophobic PAN substrate coating presents a two-layer structure: a substrate-near layer, which is a mixture of PAN and P(MEO2MA-co-OEGMA300), and a main layer, which is composed of pure hydrophilic P(MEO2MA-co-OEGMA300). During hydration in D2O vapor atmosphere, the hydrophobic PAN component prevents the formation of D2O enrichment in the substrate-near layer. However, an additional vapor-near layer is observed on top of the main layer, which is enriched with D2O. The hydration process is constrained by the cross-linking points in the film, inducing the relaxation time to be longer than that in a spin-coated P(MEO2MA-co-OEGMA300) film. Because the as-prepared cross-linked film presents a transition temperature (TT) at 38 °C, the hydrated film switches to the collapsed state when the temperature is increased from 23 to 50 °C. The response to a thermal stimulus is also slower due to the existence of the internal cross-linking points as compared to the spin-coated film. Interestingly, no reswelling is observed at the end of the thermal stimulus, which can be also attributed to the presence of internal cross-linking points.

The swelling and solvation of 100-200 nm thin films of a diblock copolymer consisting of a short poly(methyl methacrylate) (PMMA) block and a long poly(N-isopropylacrylamide) (PNIPAM) block are investigated in mixed water/methanol vapors. The processes are followed in real time using spectral reflectance (SR), time-of-flight neutron reflectometry (ToF-NR), and Fourier transform infrared (FT-IR) spectroscopy, applying two neutron scattering contrast variation sequences. After hydration in pure water vapor, the vapor composition (relative to a flow rate of 1 L/min ≙ 100%) is changed to 70% water (D2O/H2O) and 30% methanol (CH3OH/CD3OH). Upon the mixed vapor stimulus, a two-step response is found, in which an initially enhanced swelling of the films is followed by a contraction. Differences in the solvent exchange kinetics found in ToF-NR experiments coincide with characteristic changes in the FT-IR spectra. While the initially enhanced swelling of the films is driven by the absorption of methanol, the film contraction is related to the release of both solvents, with almost no further change in solvent composition. In analogy to the coil-to-globule transition encountered in the polymer solution, these film response characteristics are attributed to the cononsolvency behavior of PNIPAM in water/methanol mixtures.

Abnormal fast dehydration and rehydration of light- and thermo-dual-responsive copolymer films of poly(oligo(ethylene glycol) methyl ether methacrylate-co-6-(4-phenylazophenoxy)hexyl acrylate), abbreviated as P(OEGMA300-co-PAHA), are triggered by UV radiation. Both rapid kinetic processes are probed by in situ neutron reflectivity (NR). The transition temperatures (TTs) of P(OEGMA300-co-PAHA) are 53.0 (ambient conditions) and 52.5 °C (UV radiation, λ = 365 nm). Thin P(OEGMA300-co-PAHA) films show a random distribution of OEGMA300 and PAHA segments. They swell in a D2O vapor atmosphere at 23 °C (below TT) to a swelling ratio d/das-prep of 1.61 ± 0.01 and exhibit a D2O volume fraction φ(D2O) of 39.3 ± 0.5%. After being exposed to UV radiation for only 60 s, d/das-prep and φ(D2O) significantly decrease to 1.00 ± 0.01 and 13.4 ± 0.5%, respectively. Although the UV-induced trans-cis isomerization of the azobenzene in PAHA induces increased hydrophilicity, the configuration change causes a breaking of the intermolecular hydrogen bonds between OEGMA300 and D2O molecules and unexpected film shrinkage. As compared to thermal stimulus-induced dehydration, the present dehydration rate is 100 times faster. Removal of the UV radiation causes immediate rehydration. After 200 s, d/das-prep and φ(D2O) recover to their hydrated states, which is also 30 times faster than the initial hydration. At 60 °C (above TT), thin P(OEGMA300-co-PAHA) films switch to their collapsed state and are insensitive to UV radiation. Thus, the UV-induced fast dehydration and rehydration depend on the existence of hydrogen bonds.

The impact of thermal history on the kinetic response of thin thermoresponsive diblock copolymer poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate), abbreviated as PMEO2MA-b-POEGMA300, films is investigated by in situ neutron reflectivity. The PMEO2MA and POEGMA300 blocks are both thermoresponsive polymers with a lower critical solution temperature. Their transition temperatures (TTs) are around 25 °C (TT1, PMEO2MA) and 60 °C (TT2, POEGMA300). Thus, by applying different temperature protocols (20 to 60 or 20 to 40 to 60 °C), the PMEO2MA-b-POEGMA300 thin films experience different thermal histories: the first protocol directly switches from a swollen to a collapsed state, whereas the second one switches first from a swollen to a semicollapsed and finally to a collapsed state. Although the applied thermal histories differ, the response and final state of the collapsed films are very close to each other. After the thermal stimulus, both films present a complicated response composed of an initial shrinkage, followed by a rearrangement. Interestingly, a subsequent reswelling of the collapsed film is only observed in the case of having applied a thermal stimulus of 20 to 40 °C. The normalized film thickness and the D2O amount of each layer in the PMEO2MA-b-POEGMA300 films are consistent at the end of the two different thermal stimuli. Hence, it can be concluded that the thermal history does not influence the final state of the PMEO2MA-b-POEGMA300 films upon heating. Based on this property, these thin films are especially suitable for the temperature switches on the nanoscale, which may experience different thermal histories.

The linear shrinkage behavior in thermoresponsive diblock copolymer films and its potential application in temperature sensors are investigated. The copolymer is composed of two thermoresponsive blocks with different transition temperatures (TTs): di(ethylene glycol) methyl ether methacrylate (MEO2MA; TT1 = 25 °C) and poly(ethylene glycol) methyl ether methacrylate (OEGMA300; TT2 = 60 °C) with a molar ratio of 1:1. Aqueous solutions of PMEO2MA-b-POEGMA300 show a three-stage transition upon heating as seen with optical transmittance and small-angle X-ray scattering: dissolution (T TT2). Due to the restrictions in the polymer chain arrangement introduced by the solid Si substrate, spin-coated PMEO2MA-b-POEGMA300 films exhibit an entirely different internal structure and transition behavior. Neutron reflectivity shows the absence of an ordered structure normal to the Si substrate in as-prepared PMEO2MA-b-POEGMA300 films. After exposure to D2O vapor for 3 h and then increasing the temperature above its TT1 and TT2, the ordered structure is still not observed. Only a D2O enrichment layer is formed close to the hydrophilic Si substrate. Such PMEO2MA-b-POEGMA300 films show a linear shrinkage between TT1 and TT2 in a D2O vapor atmosphere. This special behavior can be attributed to the synergistic effect between the restrained collapse of the PMEO2MA blocks by the still swollen POEGMA300 blocks and the impedance of chain arrangement by the Si substrate. Based on this unique behavior, spin-coated PMEO2MA-b-POEGMA300 films are further prepared into a temperature sensor by implementing Ag electrodes. Its resistance decreases linearly with temperature between TT1 and TT2.

Order-disorder transitions between glassy phases are common in nature and yet a comprehensive survey on the entailed structural changes is challenging since the constituents are in the micro-scale. Vortex matter in type-II superconductors is a model system where some of these experimental challenges can be tackled. Samples with point disorder present a glassy transition on increasing the density of vortices. A glassy yet quasi-crystalline phase, the Bragg glass, nucleates at low densities. The vortex glass stable at high densities is expected to be disordered, however its detailed structural properties remained experimentally elusive. Here we show that the vortex glass has large crystallites with in-plane positional displacements growing algebraically and short-range orientational order. Furthermore, the vortex glass has a finite and almost constant correlation length along the direction of vortices, in sharp contrast with strong entanglement. These results are important for the understanding of disorder-driven phase transitions in glassy condensed matter. Fil: Aragón Sánchez, Jazmín. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Cortés Maldonado, Raúl. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Cejas Bolecek, Néstor René. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Rumi, Gonzalo Agustín. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Pedrazzini, Pablo. Comisión Nacional de Energía Atómica. Gerencia del Area de Investigación y Aplicaciones No Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Bajas Temperaturas; Argentina Fil: Dolz, Moira Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich". Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto de Física Aplicada "Dr. Jorge Andrés Zgrablich"; Argentina Fil: Nieva, Gladys Leonor. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina Fil: Van Der Beek, Cornelis Jacominus. Université Paris Sud; Francia. Centre National de la Recherche Scientifique; Francia Fil: Konczykowski, Marcin. Ecole Polytechnique. Departement Physique. Laboratoire Des Solides Irradies; Francia Fil: Dewhurst, Charles D.. Institut Laue Langevin; Francia Fil: Cubitt, Robert. Institut Laue Langevin; Francia Fil: Kolton, Alejandro Benedykt. Comisión Nacional de Energía Atómica. Gerencia del Área Investigaciones y Aplicaciones No Nucleares. Gerencia de Física (CAB). Grupo de Teoría de Sólidos; Argentina Fil: Pautrat, Alain. École Nationale Supérieure d’Ingénieurs de Caen. Centre de Recherche; Francia Fil: Fasano, Yanina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche | Comisión Nacional de Energía Atómica. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología. Unidad Ejecutora Instituto de Nanociencia y Nanotecnología - Nodo Bariloche; Argentina

Silicon is a promising anode material for lithium ion batteries due to its ten times higher specific capacity compared to commercially used graphite anodes. However, silicon anodes suffer from strong capacity fading and low Coulombic efficiency during cycling. Here we analyzed crystalline silicon anodes by operando neutron reflectometry in combination with electrochemical impedance spectroscopy. The lithiation/delithiation processes were investigated over four cycles revealing a successive growth of the lithiated zone. Moreover, the loss of Coulombic efficiency could be directly correlated to a layer formation and its dissolution on the silicon surface that suppressed the insertion of lithium ions into the silicon anode. The comparison of the currents obtained by the scattering length density profiles and the potentiostat revealed that after an initial parasitic side reaction had occurred current losses of less than 5% could be achieved. While the lithiation was hindered by side reactions the delithiation process encountered no significant problems. The results obtained by electrochemical impedance spectroscopy suggested that a layer with high charge transfer resistance was formed after each delithiation step. Hence, these operando studies provide valuable insights into the correlation of surface formation processes and the loss in Coulombic efficiency.

The swelling of thin diblock copolymer (DBC) films is investigated in situ at 22 °C in pure water vapor as well as in mixed water / methanol vapor. The DBC consists of a zwitterionic poly(sulfobetaine) block, poly[3-((2-(methacryloyloxy)ethyl)-dimethylammonio) propane-1-sulfonate] (PSPE), and a nonionic poly(N-sopropylmethacrylamide) (PNIPMAM) block. The swelling in water vapor (either H2O or D2O) and the thin-film response to methanol vapor exchange (i.e., a part of the H2O vapor is exchanged by CD3OH vapor and a part of the D2O vapor is exchanged by CH3OH vapor) are followed with simultaneous time-offlight neutron reflectometry (ToF-NR) and spectral reflectance (SR) measurements. In situ Fourier transform infrared (FTIR)spectroscopy complements these data. Exposure to H2O vapor leads to a slightly higher degree of swelling and amount of absorbed H2O compared to D2O. Upon methanol exchange, the PSPE-b-PNIPMAM thin film undergoes two contractions, which are assigned to the specific responses of the individual polymer blocks of the DBC. Due to its isotope sensitivity, FTIR confirms these two separate contraction processes of the blocks on a molecular level and reveals the role of each polymer block during swelling in water vapor and upon the methanol exchange. Thus, four distinct film regimes with different thicknesses dependencies on the vapor composition can be established, thereby enabling a quarternary nanoswitch.

Magnetic skyrmions are nanosized topological spin textures stabilized by a delicate balance of magnetic energy terms. The chemical substitution of the underlying crystal structure of skyrmion-hosting materials offers a route to manipulate these energy contributions but also introduces additional effects such as disorder and pinning. While the effects of doping and disorder have been well studied in B20 metallic materials such as ${\mathrm{Fe}}_{1\ensuremath{-}x}{\mathrm{Co}}_{x}\mathrm{Si}$ and ${\mathrm{Mn}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x}\mathrm{Si}$, the consequences of chemical substitution in the magnetoelectric insulator ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$ have not been fully explored. In this work we utilize a combination of AC magnetometry and small-angle neutron scattering to investigate the magnetic phase transition dynamics in pristine and Zn-substituted ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$. The results demonstrate that the first-order helical-conical phase transition exhibits two thermally separated behavioral regimes: at high temperatures, the helical and conical domains transform by large-scale, continuous rotations, while at low temperatures, the two phases coexist. Remarkably, the effects of pinning in the substituted sample are less prevalent at low temperatures compared to high temperatures, despite the reduction of available thermal activation energy. We attribute this behavior to the large, temperature-dependent, cubic anisotropy unique to ${\mathrm{Cu}}_{2}\mathrm{O}\mathrm{Se}{\mathrm{O}}_{3}$, which becomes strong enough to overcome the pinning energy at low temperatures. Consideration and further exploration of these effects will be crucial when engineering skyrmion materials towards future applications.

Neutron reflectivity is a powerful technique for characterizing interfaces in many areas of science. The traditional method of time of flight for measuring the wavelength of neutrons in a white beam is extremely wasteful, as the vast majority of neutrons must be absorbed in the choppers in order to produce a pulsed beam. A prism operates continuously, with a transmission up to two orders of magnitude higher than choppers. The wavelength-dependent deflection of the beam by the prism, coupled with a high spatial resolution detector, results in excellent wavelength resolution. The theory of how the resolution is considerably enhanced by curving the surface of the prism is described in detail for a real experimental arrangement. It is demonstrated how this can be used for faster neutron reflectometry, including the merging of different angles and subtraction of background. The technique shows considerable promise for neutron reflectivity, opening up new areas of science particularly in the realms of kinetics and small samples.

To enable a renewable energy future, electro- chemical energy storage remains as one of the main challenges of today’s society. Lithium-ion batteries have been shown to be of great potential in that respect, but they still suffer from safety instabilities arising from the use of flammable liquid electrolytes. Solid electrolytes are an interesting alternative that provide the required safety properties. We introduce a highly stable solid single-ion diblock copolymer electrolyte poly(deuterated styrene)- block-poly(poly(ethylene glycol) methyl ether styrene-co-lithium styrene sulfonyl(trifluoromethane sulfonyl)imide), denoted PS(d)-b-P(SPEG-co-STFSILi). Lithium metal batteries based on PS(d)-b-P(SPEG-co-STFSILi) are probed in operando with small-angle neutron scattering in order to investigate their suitability as safe batteries using lithium metal anodes. We compare cell operation when cycling at 0.5 C at 80 °C to 0.7 C at 90 °C, which represent severe working conditions for the battery. More than 200 cycles are performed, showing the inflation of the ionic pathways through cycling at 0.7 C, whereas at 0.5 C and 80 °C, battery performance and morphology remain unchanged.

The isothermal vacuum-induced dehydration of thin films made of poly(methoxy diethylene glycol acrylate) (PMDEGA), which were swollen under ambient conditions, is studied. The dehydration behavior of the homopolymer film as well as of a nanostructured film of the amphiphilic triblock copolymer polystyrene- block -poly(methoxy diethylene glycol acrylate)- block -polystyrene, abbreviated as PS- b -PMDEGA- b -PS, are probed, and compared to the thermally induced dehydration behavior of such thin thermo-responsive films when they pass through their LCST-type coil-to globule collapse transition. The dehydration kinetics is followed by in-situ neutron reflectivity measurements. Contrast results from the use of deuterated water. Water content and film thickness are significantly reduced during the process, which can be explained by Schott second order kinetics theory for both films. The water content of the dehydrated equilibrium state from this model is very close to the residual water content obtained from the final static measurements, indicating that residual water still remains in the film even after prolonged exposure to the vacuum. In the PS- b -PMDEGA- b -PS film that shows micro-phase separation, the hydrophobic PS domains modify the dehydration process by hindering the water removal, and thus retarding dehydration by about 30%. Whereas residual water remains tightly bound in the PMDEGA domains, water is completely removed from the PS domains of the block copolymer film.

Previous observations of metastable magnetic skyrmions have shown that close to the equilibrium pocket the metastable state has a short lifetime, and therefore, rapid cooling is required to generate a significant skyrmion population at low temperatures. Here, we report that the lifetime of metastable skyrmions in crystals of Cu2OSeO3 is extended by a factor of 50 with the introduction of only 2.5% zinc doping, allowing over 50% of the population to survive when field cooling at a rate of just 1 K/min. Our systematic study suggests that the lifetime enhancement is due to the increase in the pinning site density, rather than an alteration to the energy barrier of the decay process. We expect that doping can be exploited to control the lifetime of the metastable SkL state in other chiral magnets, offering a method of engineering skyrmion materials towards application in future devices.

Thermoresponsive films of poly(N-isopropyl methacrylamide) (PNIPMAM) and poly(methoxy diethylene glycol acrylate) (PMDEGA) are compared with respect to their hydration and dehydration kinetics using in situ neutron reflectivity. Both as-prepared films present a homogeneous single-layer structure and have similar transition temperatures of the lower critical solution temperature type (TT, PNIPMAM 38 degrees C and PMDEGA 41 degrees C). After hydration in unsaturated D2O vapor at 23 degrees C, a D2O enrichment layer is observed in PNIPMAM films adjacent to the Si substrate. In contrast, two enrichment layers are present in PMDEGA films (close to the vapor interface and the Si substrate). PNIPMAM films exhibit a higher hydration capability, ascribed to having both donor (N-H) and acceptor (C=O) units for hydrogen bonds. "While the swelling of the PMDEGA films is mainly caused by the increase of the enrichment layers, the thickness of the entire PNIPMAM films increases with time. The observed longer relaxation time for swelling of PNIPMAM films is attributed to the much higher glass transition temperature of PNIPMAM. When dehydrating both films by increasing the temperature above the TT, they react with a complex response consisting of three stages (shrinkage, rearrangement, and reswelling). PNIPMAM films respond faster than PMDEGA films. After dehydration, both films still contain a large amount of D2O, and no completely dry film state is reached for a temperature above their TTs.

We report small angle neutron scattering (SANS) measurements of the skyrmion lattice in (Cu$_{0.976}$Zn$_{0.024}$)$_2$OSeO$_3$ under the application of an electric field. These measurements show an expansion of the skyrmion lattice stability region with electric field similar to that seen in pristine Cu$_2$OSeO$_3$. Furthermore, using time-resolved SANS, we observe the slow formation of skyrmions after an electric or magnetic field is applied, which has not been observed in pristine Cu$_2$OSeO$_3$ crystals. The measured formation times are dramatically longer than the corresponding skyrmion destruction times after the external field is removed, and increase exponentially from 100~s at 52.5~K to 10,000~s at 51.5~K. This thermally activated behaviour indicates an energy barrier for skyrmion formation of 1.57(2)~eV, the size of which demonstrates the huge cost for creating these complex chiral objects., 8 pages, 8 figures

A biskyrmion consists of two bound, topologically stable, skyrmion spin textures. These coffee-bean-shaped objects are observed in real space in thin plates using Lorentz transmission electron microscopy (LTEM). From LTEM imaging alone, it is not clear whether biskyrmions are surface-confined objects, or, analogous to skyrmions in noncentrosymmetric helimagnets, 3D tube-like structures in a bulk sample. Here, the biskyrmion form factor is investigated in single- and polycrystalline-MnNiGa samples using small-angle neutron scattering. It is found that biskyrmions are not long-range ordered, not even in single crystals. Surprisingly all of the disordered biskyrmions have their in-plane symmetry axis aligned along certain directions, governed by the magnetocrystalline anisotropy. This anisotropic nature of biskyrmions may be further exploited to encode information.

Graphite intercalation compounds (GICs) are a group of layered materials that are suitable as monochromators for cold neutrons. KC24 is a particularly interesting compound in this regard as it features a large c-axis lattice spacing of 8.74 A, high reflectivity, and the possibility to produce large crystals with mosaicity that matches the beam divergence of cold neutron guides. GICs can be synthesized with different levels of intercalation, known as the stage of the compounds. Each stage displays a specific d-spacing. Impure GIC-monochromators containing multiple stages produce mixing of neutron wavelengths, which complicates data analysis on neutron reflectometers. We discuss the implications of GIC crystal purity and stage contamination for neutron reflectometry and show how GIC crystals can be characterized by time-of-flight neutron diffraction providing an efficient and quantifiable measure of the reflected wavelength spectrum. This allows taking into account multiple wavelength contaminations and ascertains the robustness of reflectometry measurements.

We present an operando neutron reflectometry study on the electrochemical incorporation of lithium into crystalline silicon for battery applications. Neutron reflectivity is measured from the ⟨100⟩ surface of a silicon single crystal which is used as a negative electrode in an electrochemical cell. The strong scattering contrast between Si and Li due to the negative scattering length of Li leads to a precise depth profile of Li within the Si anode as a function of time. The operando cell can be used to study the uptake and the release of Li over several cycles. Lithiation starts with the formation of a lithium enrichment zone during the first charge step. The uptake of Li can be divided into a highly lithiated zone at the surface (skin region) (x ∼ 2.5 in LixSi) and a much less lithiated zone deep into the crystal (growth region) (x ∼ 0.1 in LixSi). The total depth of penetration was less than 100 nm in all experiments. The thickness of the highly lithiated zone is the same for the first and second cycle, whereas the thickness of the less lithiated zone is larger for the second lithiation. A surface layer of lithium (x ∼ 1.1) remains in the silicon electrode after delithiation. Moreover, a solid electrolyte interface is formed and dissolved during the entire cycling. The operando analysis presented here demonstrates that neutron reflectivity allows the tracking of the kinetics of lithiation and delithiation of silicon with high spatial and temporal resolution.

The skyrmion lattice state (SkL), a crystal built of mesoscopic spin vortices, gains its stability via thermal fluctuations in all bulk skyrmion host materials known to date. Therefore, its existence is limited to a narrow temperature region below the paramagnetic state. This stability range can drastically increase in systems with restricted geometries, such as thin films, interfaces and nanowires. Thermal quenching can also promote the SkL as a metastable state over extended temperature ranges. Here, we demonstrate more generally that a proper choice of material parameters alone guarantees the thermodynamic stability of the SkL over the full temperature range below the paramagnetic state down to zero kelvin. We found that GaV4Se8, a polar magnet with easy-plane anisotropy, hosts a robust Néel-type SkL even in its ground state. Our supporting theory confirms that polar magnets with weak uniaxial anisotropy are ideal candidates to realize SkLs with wide stability ranges.

The rehydration of thermoresponsive polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene (PS-b-PMDEGA-b-PS) films forming a lamellar microphase-separated structure is investigated by in situ neutron reflectivity in a D2O vapor atmosphere. The rehydration of collapsed PS-b-PMDEGA-b-PS films is realized by a temperature change from 45 to 23 °C and comprises (1) condensation and absorption of D2O, (2) evaporation of D2O, and (3) reswelling of the film due to internal rearrangement. The hydrophobic PS layers hinder the absorption of condensed D2O, and a redistribution of embedded D2O between the hydrophobic PS layers and the hydrophilic PMDEGA layers is observed. In contrast, the rehydration of semiswollen PS-b-PMDEGA-b-PS films (temperature change from 35 to 23 °C) shows two prominent differences: A thicker D2O layer condenses on the surface, causing a more enhanced evaporation of D2O. The rehydrated films differ in film thickness and volume fraction of D2O, which is due to the differ...

The rehydration of thermoresponsive poly(monomethoxydiethylene glycol acrylate) (PMDEGA) films exhibiting a lower critical solution temperature (LCST) type demixing phase transition in aqueous environments, induced by a decrease in temperature, is investigated in situ with real-time neutron reflectivity. Two different starting conditions (collapsed versus partially swollen chain conformation) are compared. In one experiment, the temperature is reduced from above the demixing temperature to well below the demixing temperature. In a second experiment, the starting temperature is below the demixing temperature, but within the transition regime, and reduced to the same final temperature. In both cases, the observed rehydration process can be divided into three stages: first condensation of water from the surrounding atmosphere, then absorption of water by the PMDEGA film and evaporation of excess water, and finally, rearrangement of the PMDEGA chains. The final rehydrated film is thicker and contains more abs...

The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)(3)) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)(3) films show a transition temperature (TT) at 33 degrees C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)(3) films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)(3). However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)(3) films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)(3) films depends on the final temperature. It decreases from (9.7 +/- 0.3)% to (7.0 +/- 0.3)% or (6.0 +/- 0.3)% when the final temperatures are set to 35 degrees C, 45 degrees C and 50 degrees C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.

Thin thermoresponsive films of the triblock copolymer polystyrene-block-poly(methoxydiethylene glycol acrylate)-block-polystyrene (P(S-b-MDEGA-b-S)) are investigated on silicon substrates. By spin coating, homogeneous and smooth films are prepared for a range of film thicknesses from 6 to 82 nm. Films are stable with respect to dewetting as investigated with optical microscopy and atomic force microscopy. P(S-b-MDEGA-b-S) films with a thickness of 39 nm exhibit a phase transition of the lower critical solution temperature (LCST) type at 36.5 degrees C. The swelling and the thermoresponsive behavior of the films with respect to a sudden thermal stimulus are probed with in-situ neutron reflectivity. In undersaturated water vapor swelling proceeds without thickness increase. The thermoresponse proceeds in three steps: First, the film rejects water as the temperature is above LCST. Next, it stays constant for 600 s, before the collapsed film takes up water again. With ATR-FTIR measurements, changes of bound water in the film caused by different thermal stimuli are studied. Hydrogen bonds only form between C=O and water in the swollen film. Above the LCST most hydrogen bonds with water are broken, but some amount of bound water remains inside the film in agreement with the neutron reflectivity data. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that the inner lateral structure is not significantly influenced by the different thermal stimuli.

The phase separation and molecular intermixing in poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) bulk heterojunction thin films are investigated as a function of the overall PCBM content. The structural length scales, phase sizes, and molecular miscibility ratio in bulk heterojunction films are probed with grazing incidence small-angle neutron scattering (GISANS). The PCBM content is varied between 9 and 67 wt %. For the symmetric P3HT/PCBM ratio, which is typically highly efficient in photovoltaic devices, a structure size of 20 nm, the largest PCBM phases, and 18 vol % dispersed PCBM in the amorphous P3HT phase are found. The molecularly dispersed PCBM content is found to increase with the overall PCBM content. Absorption measurements complement the GISANS investigation.

Alkoxysilane having various functional headgroups (amino and mercapto) and morphologies was deposited by supercritical CO(2) onto a porous dielectric material to replace the metallic barrier used in semiconductor devices. These organic layers were successfully coated with Cu. The morphologies of the stacks were investigated by X-ray and neutron reflectometry and atomic force microscopy. Whereas PVD Cu deposition is not adapted to silanized dielectric material with mercapto and aminopropyltrimethoxysilane but acceptable with aminoethylaminopropyltrimethoxysilane, the MOCVD process is more interesting. XRR and NR data clearly indicate that silane layers remain intact after copper deposition and, depending on the Cu immobilization capability of the chemical function of the silane and its orientation into the layer, the Cu film morphologies are different. Dense, thin films having small Cu grains were obtained with an aminoethylaminopropyltrimethoxysilane layer, and thick films having a low density and large Cu grains were obtained with an aminopropyltrimethoxysilane layer. Nucleation and growth mechanisms are discussed.

Thin thermoresponsive hydrogel films of poly(N-isopropylacrylamide) end-capped with n-butyltrithiocarbonate(nbc- PNIPAM) oil si I icon supports with a gold layer on top, causing an asymmetric confinement, are investigated. For two different gold layer thicknesses (nominally 0.4 and 5 rim), the swelling and switching kinetics are probed with in situ neutron reflectivity. With a temperature jump from 23 to 40 degrees C the film is switched from a swollen into a collapsed state. For the thin gold layer this switching is faster as compared to the thick gold layer. The switching is a two-step process of water release and a subsequent structural relaxation. fit swelling and deswelling cycles, aging of the films is probed. After five cycles, the film exhibits enhanced water storage capacity. Grazing-incidence small-angle X-ray scattering (GISAXS) shows that these gold coated nbc-PNIPAM films do not age with respect to the inner structure but slightly roughen at the gold surface. As revealed by atomic force microscopy, the morphology of the gold layer is changed by the water uptake and release.

We investigate a new type of thin film material which allows for water storage without an increase in film thickness, whereas typically water storage in polymers and polymer films is accompanied with a strong swelling of the film, i.e., a strong increase in the film thickness. So these films will avoid problems related to strains which are caused by swelling. The basic key for the preparation of such thin films is the installation of a glassy network by the use of an asymmetric diblock copolymer polystyrene-block-poly(N-isopropylacrylamide) [P(S-b-NIPAM)] with a long PS and short PNIPAM block in combination with a solvent which is more equal in interaction with both the blocks as compared to water. With in situ neutron reflectivity the water storage and removal are probed. The total film thickness increases only by 2.5% by allowing for a total water storage of 17.4%. Thus the material can be used for coatings to reduce humidity in nano-applications, which might suffer from changes in the water content of the surrounding environment.

Specular neutron reflectivity and nuclear reaction analysis (NRA) are used to measure the interfacial width between poly(9,9-dioctylfluorene) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) in a 500 nm bilayer. Annealing at temperatures up to 280 °C allows us to vary this width over a large range, from ∼1 nm to greater than 30 nm. Approximate calculations using the predictions of self-consistent field theory (SCFT) for both Gaussian and semiflexible chains suggest that in the liquid−liquid regime the Gaussian results of SCFT are valid for this system. We also demonstrate the ability to control the interfacial width in 100 nm bilayers, on both silicon and indium tin oxide (ITO). The procedure of “preannealing” the F8 and F8BT layers, before bringing them together to make a bilayer, allows us to independently control the interfacial width and the properties of the bulk of these 100 nm films.

The relative importance of long- and short-ranged forces on the thermal fluctuations at polymer interfaces was investigated with neutron reflection. Polyolefin blends were synthesised to create polymer pairs with a tuned interaction parameter, allowing the exploration of situations from near criticality to strongly immiscible cases in thin-film systems. We have observed for the polymer interfacial width, a transition from a region where long-ranged forces dominate, at higher degree of incompatibility, to a region approaching criticality where short-ranged truncation forces are more relevant.

Multishell particles were prepared by γ-radiation-induced polymerization of methyl methacrylate (MMA) in polystyrene-block-poly(methacrylic acid) (PS-b-PMA) aqueous micellar solution and their structure was studied by small-angle neutron scattering (SANS). Before polymerization, almost all MMA molecules are distributed in aqueous phase and only 1% of MMA is accumulated inside the micelles. The newly formed polymer (PMMA) is deposited on the surface of PS cores of the original micelles. The effect of the MMA concentration, micelle concentration, absorbed radiation dose, and absorbed dose rate on the characteristics of the resulting particles was examined. The thickness of the PMMA shell (20-218 A for the presented series of samples) can be easily controlled by variation of monomer and/or micelle concentration. Universal plots of the core volume (PS+PMMA) and SANS curve were presented. These plots facilitate choosing proper monomer and micelle concentrations and detecting possible irregularities in the parameters of the resulting particles.

The lateral structure of the adsorbed layer of a nonionic surfactant at a hydrophilic silicon substrate against water was studied over a wide range of surface concentrations of the surfactant by grazing-incidence small-angle neutron scattering (GISANS). For the chosen surfactant, tetraoxyethylene-mono-n-octyl-ether (C8E4), these changes in surface concentration were brought about by varying the temperature at a constant bulk concentration somewhat below the CMC of the surfactant. The GISANS measurements indicate the existence of transient surfactant aggregates without a preferred lateral structure at half coverage of the surface, and a correlation length of similar magnitude as the diameter of the surfactant micelles. This study shows that the picture of distinct surface aggregates of a characteristic size and separation that emerges from AFM studies of saturated surfactant layers on such substrates cannot be generalized to the situation below complete surface coverage.

We discuss some recent findings relating to the structure of interfaces in semiconducting polymer devices. The structure of three different types of interface is characterized via neutron reflectivity and scanning force microscopy. In the first example we find that enrichment of dopant occurs at the surface of a doped polymeric conductor, and that this enriched layer penetrates several nanometres into the material. Secondly, we find that the interface between a semiconducting polymer and an insulating polymer is not molecularly sharp, but is rather broad with a width typically of the order of 1 nm. Finally we present some initial neutron reflectivity measurements on the interface between two different semiconducting polymers (one of which is deuterated). Again we find that this interface is diffuse, with a typical width of the order of a few nanometres.

We report a detailed neutron diffraction study of both pinned and moving magnetic Flux Line Lattice (FLL) in NbTa and PbIn samples. In NbTa, the FLL presents a hexagonal lattice even in the absence of current, meanwhile PbIn presents a strongly dislocated phase. In PbIn, dislocations are eliminated by the application of transport current in agreement with theoretical predictions. On the other hand, the absence of curvature of the flux lines for subcritical currents confirm the presence of surface pinning of the FLL.

μSR and small-angle neutron scattering (SANS) have been used to probe the vortex arrangement in single crystals of the high-Tc superconductor Bi2.15Sr1.85CaCu2O8+δ which have been irradiated with heavy ions to produce columnar defects. The influence of these pinning sites on the spatial arrangement of the vortices is discussed, and the results are compared with numerical simulations.

The morphology of dewetted thin polymer-blend films of deuterated polystyrene (dPS) and polyparamethylstyrene (PpMS) on top of silicon surfaces is investigated. The film thickness of the originally homogeneous films is varied between 19 and 104 A. Compared to the radius of gyration of the unperturbed molecule, R g =106 A , the as-prepared films are confined in the direction perpendicular to the sample surface. The dewetting results from the storage of the samples under toluene vapor atmosphere. Atomic force microscopy (AFM) and grazing incidence small-angle scattering (GISAS) are used. From the differences in the GISAS data measured with X-rays compared to data measured with neutrons a random distribution of the molecules inside the individual droplets is determined. Thus from dewetting under toluene atmosphere no periodicity in the internal structure exists. The, within all methods derived, most prominent in-plane length corresponds to the mean droplet distance. Its function of film thickness is explainable by the spinodal dewetting model.

The adsorption of concentrated solutions of di-2-ethylhexylsodium sulfosuccinate (Aerosol-OT or AOT) at hydrophilic solid/aqueous and air/aqueous solution interfaces was followed by neutron specular reflection. Reflectivity profiles were recorded of protonated AOT in D2O at concentrations of 2 and 5 wt % and over a range of temperatures. Sharp diffraction peaks characteristic of a lamellar phase were observed, and the repeat spacing of the peaks was very sensitive to temperature. The bulk phase diagram in this concentration range over the temperature range 0-65°C was also studied using neutron small angle scattering. For the bulk solution containing 5 wt % AOT, the lamellar phase at 5°C had a repeat distance of 370 ± 30 Å, which dropped to about half that value at 35°C, and to only 115 Å at 65°C. The lamellar spacing decreased as the AOT concentration was lowered; for example, from 325 Å at 5 wt % to 225 Å at 1 wt %, at 15°C. Over some of the concentration and temperature range narrow diffraction peaks were observed for the lamellar phase adsorbed at both interfaces, indicating long-range order in the direction normal to the surface. The repeat spacing in the adsorbed lamellar phase was generally 10-20% smaller than in the bulk solution. Although addition of small amounts of electrolyte (0.1 and 1 mM NaBr) had only a small effect on the small angle scattering from the bulk lamellar phase, it caused the disappearance of the adsorbed lamellar phase. These observations are consistent with an overall attraction of the lamellar phase to the surface in the absence of added electrolyte.

Small Angle Neutron Scattering has been used to observe diffraction from the flux line lattice in the fully isotropic (K, Ba)BiO3high Tcsuperconductor. We show that the flux lines are ordered into a hexagonal lattice at low field (H < He∼ 0.6T ≪ Hg (0) where Hgis the second order vortex glass transition field). The diffracted intensity continuously drops to zero as the field is increased towards He. Those observations are in good agreement with recent theoritical works which suggested that the formation of dislocations becomes favorable above Heleading to a glassy structure. The field Helies close to the onset of the second peak in magnetization measurements indicating that this peak is related to the change in the vortex structure.

The interface between ultrathin deuterated poly(methyl methacrylate) films on polystyrene substrates is subject to a dispersive force driven instability consisting of thermally excited capillary waves. We have studied this example of liquid/liquid spinodal dewetting, using specular and off-specular neutron reflection measurements to characterize the length scale and growth rate of the instability of the buried, polymer interfaces.

In situ the swelling of thin polystyrene (PSd) films by toluene is investigated with specular and off-specular neutron reflectivity. Due to the very high time resolution of 30 s, the initial stages of swelling as well as the fast swelling are detected. Followed by a slow swelling and final stages, in total four different regimes are identified until equilibrium with respect to a homogenously swollen PSd film is reached. Film instabilities are avoided in the absence of any motor movements in the time-of-flight mode of the neutron reflectometer D17.

The switching kinetics of thin thermo-responsive hydrogel films of poly(monomethoxy-diethyleneglycol-acrylate) (PMDEGA) are investigated. Homogeneous and smooth PMDEGA films with a thickness of 35.9 nm are prepared on silicon substrates by spin coating. As probed with white light interferometry, PMDEGA films with a thickness of 35.9 nm exhibit a phase transition temperature of the lower critical solution temperature (LCST) type of 40 degrees C. In situ neutron reflectivity is performed to investigate the thermo-responsive behavior of these PMDEGA hydrogel films in response to a sudden thermal stimulus in deuterated water vapor atmosphere. The collapse transition proceeds in a complex way which can be seen as three steps. The first step is the shrinkage of the initially swollen film by a release of water. In the second step the thickness remains constant with water molecules embedded in the film. In the third step, perhaps due to a conformational rearrangement of the collapsed PMDEGA chains, water is reabsorbed from the vapor atmosphere, thereby giving rise to a relaxation process. Both the shrinkage and relaxation processes can be described by a simple model of hydrogel deswelling.

Neutron reflectivity was used to study the interface between the semiconducting polymer poly(9,9-dioctylfluorene) (PFO) and the insulating polymer poly(methyl methacrylate) (PMMA). The PFO/PMMA interfacial width was measured in the nematic and crystalline phases of the PFO, both with the PMMA on top of the PFO and vice versa. These interfaces are broad compared to atomic length scales, with measured interfacial widths in the range from 10 to 20 A. We found that the interfacial width was independent of both the chosen geometry and the thermal processing history. The equilibrium interfacial width only depended on temperature, with the width in the nematic phase of the PFO being broader than in the crystalline regime.

The lateral structures of dried adsorbed binary mixtures of star polymers were investigated. Blends of protonated and deuterated polybutadiene stars were prepared from cyclohexane solutions and adsorbed onto silicon substrates. The number of arms and the molecular weight of the arms was varied. With grazing incidence small angle scattering techniques (GISAS) and scanning force microscopy (SFM), different dominant in-plane length scales were determined. The morphology of these structures is dominated by blob-like structures created from single stars or agglomerates of star polymers.

Phase separation of the weakly incompatible blend system polystyrene and polyparamethylstyrene confined in isolated droplets is investigated. The droplet geometry imposes a two-dimensional spatial restriction. With specular, diffuse and grazing incidence small-angle neutron scattering the surface topography as well as the chemical morphology inside the droplets is determined. Due to the differences in surface tension, a core–shell-like structure characterized by one most prominent length scale inside the droplets is installed.

A small-angle neutron study of vortex lattices in YBa 2 Cu 3 O 7 showed a diffraction pattern with square symmetry when the applied field was along the c axis with the four main spots aligned with the crystallographic {110} directions. With the field 30 o from the c axis, a hexagonal lattice exists. At intermediate angles, a fraction of the flux lines follow the c axis and the two lattices coexist. The temperature dependence of the intensity deviates markedly from conventional predictions

The interfacial width of polyolefins blends has been probed as a function of distance away from the critical point by using neutron reflectivity. For strongly immiscible polymer pairs, the width of the interface increases slowly when the degree of immiscibility is decreased and the interfacial width varies with the interaction parameter $\ensuremath{\chi}$ of the polymers. Closer to the critical point the dependence on the degree of miscibility becomes stronger and the way in which the interfacial width diverges, as criticality is approached, is related to both the chain length and $\ensuremath{\chi}$. The self-consistent field theory numerical calculations, with the additional contribution due to capillary waves, provides a good description of the width of the interface between two polymer bulk phases in particular at intermediate values of the degree of immiscibility.

Small-angle neutron diffraction measurements from the flux lattice in a single crystal of the cubic Laves' phase superconductor, CeRu2, are reported. The mixed state is described in terms of aligned rigid bundles of vortices. The bundle diameters decrease above 1 2 H c 2 (consistent with collective weak pinning theory) and become comparable with the penetration length at a field at which a ‘peak effect’ is seen in magnetisation measurements. A clear memory of field histories that pass through the ‘peak effect’ region is also found; however, some of the induced disorder can be removed by subsequently cycling the field.

We report that the flux-line lattice in the cubic superconductor Pr(Os4Sb12 is strongly distorted from an ideal hexagonal lattice at very low temperatures in a small applied field. We attribute this to the presence of gap nodes in the superconducting state on at least some Fermi-surface sheets.