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

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.

The long-range alignment of supramolecular structures must be engineered as a first step toward advanced nanopatterning processes aimed at miniaturizing features to dimensions below 5 nm. This study introduces a facile method of directing the orientation of supramolecular columns over wafer-scale areas using faceted surfaces. Supramolecular columns with features on the sub-5 nm scale were highly aligned in a direction orthogonal to that of the facet patterning on unidirectional and nanoscopic faceted surface patterns. This unidirectional alignment of supramolecular columns is also observed by varying the thickness of the supramolecular film or by altering the dimensions of the facet pattern. The ordering behavior of the supramolecular columns can be attributed to the triangular depth profile of the bottom facet pattern. Furthermore, this directed self-assembly principle allows for the continuous alignment of supramolecular structures across ultralarge distances on flexible patterned substrates.

Self-assembly of anisotropic nanomaterials into ordered multidimensional (2D and 3D) arrays facilitate versatile collective properties. Monitoring of this self-assembly processes is essential to control the emerging properties of these nanostructured materials. We report here results of in situ X-ray reflectivity (XRR) and grazing incidence small-angle X-ray scattering (GISAXS) studies carried out at the air–liquid interface to understand the self-assembly process of ZnS nanorods (NRs) in real-time. Our study shows that at high surface pressure, ZnS NRs self-assemble into a bilayer 2D square superlattice, coupled by their organic surface ligands along the out-of-plane direction with NRs lying side by side flat in the in-plane direction at the liquid surface. Upon increasing subphase temperature, we observed a transformation of the 2D superlattice into a 3D multilayer structure of the nanorods. On the basis of the extracted parameters (film thickness, electron density of each layer, and in-plane lattice parameters), we propose a packing model of the hierarchical self-assembly of anisotropic NRs on the water surface.

Polymer–metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics...

Conventional additives like 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) play an essential role in optimization of blend film morphology of polymer solar cells (PSCs). However, they have halogenated elements in their end groups, which are harmful to the environment and humans, limiting large-scale applications. In this work, a novel non-toxic and non-halogen additive, dibenzyl ether (DE), was introduced into PTB7-Th:PC71BM based PSCs, and the role of the DE additive was systemically investigated. The results showed that DE additive can not only adjust phase separation and optimize the morphology of blend film, but also promote the mobility of hole and electron. The grazing-incidence small-angle X-ray scattering (GISAXS) showed that the introduction of DE increased the interface area between PTB7-Th and PC71BM, which can promote exciton dissociation, and achieve better charge transport. Transient photovoltage (TPV) and transient photocurrent (TPC) measurements show that carrier recombination of the additive-containing devices can be effectively inhibited with improved charge transport efficiency of the active layer. Consequently, the devices with DE additive achieve power conversion efficiency (PCE) of 9.53% and a fill factor (FF) of 70.41%. Our non-toxic and non-halogen additive provides a potential solution for the preparation of environmental-friendly PSCs in the future.

Gold/titanium dioxide (Au/TiO2) nanohybrid materials have been widely applied in various fields because of their outstanding optical and photocatalytic performance. By state-of-the-art polymer templating, it is possible to make uniform nanostructured TiO2 layers with potentially large-scale processing methods. We use customized polymer templating to achieve TiO2 nanostructures with different morphologies. Au/TiO2 hybrid thin films are fabricated by sputter deposition. An in-depth understanding of the Au morphology on the TiO2 templates is achieved with in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition. The resulting Au nanostructure is largely influenced by the TiO2 template morphology. Based on the detailed understanding of the Au growth process, characteristic distances can be selected to achieve tailored Au nanostructures at different Au loadings. For selected sputter-deposited Au/TiO2 hybrid thin films, the optical response with a tailored localized surface plasmon resonance is demonstrated.

Understanding the kinetics of the crystallization process for organometal halide perovskite formation is critical in determining the crystalline, nanoscale morphology and therefore the electronic properties of the films produced during thin film formation from solution. In this work, in situ grazing incidence small-angle X-ray scattering (GISAXS) and optical microscopy measurements are used to investigate the processes of nucleation and growth of pristine mixed halide perovskite (MAPbI3-x Cl x ) crystalline films deposited by bar coating at 60 °C, with and without additives in the solution. A small amount of 1,8-diiodooctane (DIO) and hydriodic acid (HI) added to MAPbI3-x Cl x is shown to increase the numbers of nucleation centers promoting heterogeneous nucleation and accelerate and modify the size of nuclei during nucleation and growth. A generalized formation mechanism is derived from the overlapping parameters obtained from real-time GISAXS and optical microscopy, which revealed that during nucleation, perovskite precursors cluster before becoming the nuclei that function as elemental units for subsequent formation of perovskite crystals. Additive-free MAPbI3-x Cl x follows reaction-controlled growth, in contrast with when DIO and HI are present, and it is highly possible that the growth then follows a hindered diffusion-controlled mechanism. These results provide important details of the crystallization mechanisms occurring and will help to develop greater control over perovskite films produced.

The thermal stability of Cu/W nano-multilayers deposited on a Si substrate using ion beam deposition was analyzed in situ by GISAXS and transmission EDX—a combination of methods permitting the observation of diffusion processes within buried layers. Further supporting techniques such as XRR, TEM, WAXS, and AFM were employed to develop an extensive microstructural understanding of the multilayer before and during heating. It was found that the pronounced in-plane compressive residual stress and defect population induced by ion beam deposition result in low thermal stability driven by thermally activated self-interstitial and vacancy diffusion, ultimately leading to complete degradation of the layered structure at moderate temperatures. The formation of Cu protrusions was observed, and a model was formulated for stress-assisted Cu diffusion driven by Coble creep along W grain boundaries, along with the interaction with Si substrate, which showed excellent agreement with the observed experimental data. The model provided the explanation for the experimentally observed strong correlation between thin film deposition conditions, microstructural properties, and low thermal stability that can be applied to other multilayer systems.

Optimizing and monitoring the growth conditions of Pt films, often used as bottom electrodes in multiferroic material systems, represents a highly relevant issue that is of importance for controlling the crystalline quality and performance of ferroelectric oxides such as, e.g. LuFeO3. We performed a time-resolved monitoring of the growth and morphology of Pt films during pulsed laser deposition (PLD) in dependence on the grown film effective thickness and on the growth temperature Tg using in situ grazing incidence small-angle X-ray scattering (GISAXS). Through real-time analysis and modeling of GISAXS patterns, we could fully characterize the influence of Tg on the morphology and on the growth kinetics of the Pt layers. Consequently, critical and characteristic effective thicknesses for the transitions nucleation phase (I)/coalescence phase (II) and coalescence phase (II)/coarsening phase (III) could be determined. In combination with complementary microscopic imaging and chemical mapping via combined SEM/EDXS, we demonstrate the occurrence of a morphological progression in the Pt PLD-grown Pt films, changing from grains at room temperature to a 3D-island morphology at 300 degrees C, further to a hole-free structure at 500 degrees C, and finally to a channel structure for 700 and 900 degrees C. The film topography, as characterized by atomic force microscopy (AFM), favors the PLD growth of Pt layers at temperatures beyond 700 degrees C where the film is homogeneous, continuous, and hole-free with a flat and smooth surface. The double dependency of the percolation transition on the film effective thickness and on the growth temperature has been established by measuring the electrical conductivity.

Copper (Cu) as an excellent electrical conductor and the amphiphilic diblock copolymer polystyrene-block-poly(ethylene oxide) (PS-b-PEO) as a polymer electrolyte and ionic conductor can be combined with an active material in composite electrodes for polymer lithium-ion batteries (LIBs). As interfaces are a key issue in LIBs, sputter deposition of Cu contacts on PS-b-PEO thin films with high PEO fraction is investigated with in situ grazing-incidence small-angle X-ray scattering (GISAXS) to follow the formation of the Cu layer in real-time. We observe a hierarchical morphology of Cu clusters building larger Cu agglomerates. Two characteristic distances corresponding to the PS-b-PEO microphase separation and the Cu clusters are determined. A selective agglomeration of Cu clusters on the PS domains explains the origin of the persisting hierarchical morphology of the Cu layer even after a complete surface coverage is reached. The spheroidal shape of the Cu clusters growing within the first few nanometers of sputter deposition causes a highly porous Cu-polymer interface. Four growth stages are distinguished corresponding to different kinetics of the cluster growth of Cu on PS-b-PEO thin films: (I) nucleation, (II) diffusion-driven growth, (III) adsorption-driven growth, and (IV) grain growth of Cu clusters. Percolation is reached at an effective Cu layer thickness of 5.75 nm.

This study proposes a plasmonic resonance-tunable nanocomposite thin film, which applies to a color filter, heat mirror, semi-transparent color electrode, and electromagnetic shield, given that the size and structure of nanoclusters can be controlled by a sputtering power density. The structural and functional properties of silver/plasma-polymer-fluorocarbon (Ag/PPFC) nanocomposite thin films, which were sputtered by ternary composite targets, were investigated with various compositions and sputtering power densities. The growth of Ag nanoclusters of the thin film was suppressed as the sputtering power density increased due to the rich functional group of -CFx- fluorine. As a result, a continuous color change from blue to yellow could be expressed on films given the precise control of the surface plasmonic resonance phenomenon. Grazing-incidence small-angle scattering (GISAXS) analysis indicated that the sputtering power density had a significant effect on the size, distribution, and orientation of the Ag nanoclusters in the thin film. For low sputtering power densities, Ag nanoclusters were forming aggregations along the out-of-plane direction, but as the sputtering power density increased, the nanoclusters showed random distribution instead of large aggregates. We also demonstrated applications of Ag/PPFC nanocomposite thin films to a color filter, heat mirror, semi-transparent electrode, and electromagnetic shield. In addition, the fabrication of a large-area film (400 × 700 mm2) showed that the approach applies highly to industries.

PbS quantum dot (QD) solar cells demonstrate great potential in solar energy conversion with a broad and flexible spectral response. Even though long-term storage stabilities of QD solar cells were reported in literature, the operation stability from a more practical aspect, to date, has been not yet investigated. Herein, we observe the structure degradation process of a PbS QD-ink based solar cell during the device operation. Simultaneously to probing the solar cell parameters, the overall structure evolutions of the QDs in both, active layer and hole transport layer of the solar cell are studied with grazing-incidence small- and wide-angle X-ray scattering (GISAXS/GIWAXS). We find a spontaneous decrease of the QD inter-dot distance with an increase in the spatial disorder in the active layer (PbX2–PbS QDs, X = I, and Br) during the operation induced degradation. Consequently, the structure disorder-induced broadening of the energy state distribution is responsible for the decrease in open-circuit voltage Voc leading to the device degradation. These findings elucidate the origin of light-soaking as well as the structure degradation of QD ink-based solar cells and indicate that the stability of the device can be realized by the positional stabilization of the QDs in the QD solid.

Hafnium aluminates films with 50 mol% of Hf were deposited onto Si(100) using atomic layer deposition. The films were annealed by RTP at 1000 o C for 60 s in pure N 2 or N 2 +5%O 2 and by LASER at 1200 o C for 1ms in pure N 2 . Then, they were characterized by X-ray spectroscopies, ellipsometry, Rutherford backscattering and scanning electron microscopy. For thin films annealed by RTP in N 2 , phase separation takes place, promoting the formation of HfO2 and Al2.4 O3.6 crystalline phases. In contrast, the films annealed by LASER remain predominantly amor phous with crystalline facets of Al 2.4 O 3.6 . Also, non-homogeneous distribution of the chemical elements within the dielectrics gave rise to the formation of several regions which can be viewed as sub-layers, each of them with arbitrary electron density and thickness. As a result, Kratky curves pointed out to the coexistence of different features described by different gyration radius yielding GISAXS scattering profiles with polydispersive character istics. Finally, the samples annealed by RTP were interpreted as agglomerates of spheroids with different sizes (1.1-2.2 nm) and with different crystalline phases whereas the samples annealed by LASER were interpreted as larger spheroids of crystalline Al 2.4 O 3.6 (1.7-2.7nm) embedded in a matrix predominantly amorphous.

Spray deposition is a scalable and cost-effective technique for the fabrication of magnetic hybrid films containing diblock copolymers (DBCs) and magnetic nanoparticles. However, it is challenging to obtain spray-deposited anisotropic magnetic hybrid films without using external magnetic fields. In the present work, spray deposition is applied to prepare perpendicular anisotropic magnetic hybrid films by controlling the orientation of strontium hexaferrite nanoplatelets inside ultra-high-molecular-weight DBC polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films. During spray deposition, the evolution of DBC morphology and the orientation of magnetic nanoplatelets are monitored with in situ grazing-incidence small-angle X-ray scattering (GISAXS). For reference, a pure DBC film without nanoplatelets is deposited with the same conditions. Solvent-controlled magnetic properties of the hybrid film are proven with solvent vapor annealing (SVA) applied to the final deposited magnetic films. Obvious changes in the DBC morphology and nanoplatelet localization are observed during SVA. The superconducting quantum interference device data show that ferromagnetic hybrid polymer films with high coercivity can be achieved via spray deposition. The hybrid films show a perpendicular magnetic anisotropy before SVA, which is strongly weakened after SVA. The spray-deposited hybrid films appear highly promising for potential applications in magnetic data storage and sensors.

Slot-die printing, a large-scale deposition technique, is applied to fabricate mesoporous titania films. Printing is interesting, for example, for scaling up solar cells where titania films with an interconnected mesoporous network and a large surface-to-volume ratio are desired as photoanodes. A fundamental understanding of the structure evolution during printing is of high significance in tailoring these films. In this work, we provide important insights into the self-assembly of the slot-die-printed titania/polystyrene-block-poly(ethylene oxide) (PS-b-PEO) micelles into ordered hybrid structures in real time via in situ grazing-incidence small-angle X-ray scattering (GISAXS). GISAXS allows for tracking both vertical and lateral structure development of the film formation process. In the hybrid film, a face-centered cubic (FCC) structure is preferentially formed at the interfaces with air and with the substrate, while a defect-rich mixed FCC and body-centered cubic (BCC) structure forms in the bulk. After calcination, the surface and inner morphologies of the obtained nanostructured titania films are compared with the spin-coated analogues. In the printed films, the initially formed nanoscale structure of the hybrid film is preserved, and the resulting mesoporous titania film shows a superior order as compared with the spin-coated thin films which can be beneficial for future applications.

Poorly crystalline iron­(III) (hydr)­oxide nanoparticles are ubiquitous in environmental systems and play a crucial role in controlling the fate and transport of contaminants. Yet, the thermodynamic and kinetic parameters, e.g., the effective interfacial (α′) and apparent activation (Ea) energies, of iron­(III) (hydr)­oxide nucleation on earth-abundant mineral surfaces have not been determined, which hinders an accurate prediction of iron­(III) (hydr)­oxide formation and its interactions with other toxic or reactive ions. Here, for the first time, we report experimentally obtained α′ and Ea for iron­(III) (hydr)­oxide nucleation on quartz mineral surfaces by employing a flow-through, time-resolved grazing incidence small-angle X-ray scattering (GISAXS). GISAXS enabled the in situ detection of iron­(III) (hydr)­oxide nucleation rates under different supersaturations (σ, achieved by varying pH 3.3–3.6) and temperatures (12–35 °C). By quantitative analyses based on classical nucleation theory, α′ was obtained to be 34.6 mJ/m2 and Ea was quantified as 32.8 kJ/mol. The fundamental thermodynamic and kinetic parameters obtained here will advance our fundamental understanding of the surface chemistry and nucleation behavior of iron­(III) (hydr)­oxides in subsurface and water treatment systems as well as their effects on the fate and transport of pollutants in natural and engineered water systems. The in situ flow-through GISAXS method can also be adapted to quantify thermodynamic and kinetic parameters at interfaces for many important solid–liquid environmental systems.

Tunable electrostatic interactions in thin films from (C-co-D)-b-B-b-A-b-B-b-(C-co-D)-type pentablock quaterpolymers featuring hydrophobic end blocks as well as pH-responsive and hydrophilic midblo...

Grazing-incidence small-angle X-ray scattering (GISAXS) patterns have multiple superimposed contributions from the shape of the nanoscale structure, the coupling between the particles, the partial pair correlation, and the layer geometry. Therefore, it is not easy to identify the model manually from the huge amounts of combinations. The convolutional neural network (CNN), which is one of the artificial neural networks, can find regularities to classify patterns from large amounts of combinations. CNN was applied to classify GISAXS patterns, focusing on the shape of the nanoparticles. The network found regularities from the GISAXS patterns and showed a success rate of about 90% for the classification. This method can efficiently classify a large amount of experimental GISAXS patterns according to a set of model shapes and their combinations.

Electrodeposition is a powerful tool for the bottom-up fabrication of novel electronic devices. This necessitates a complete understanding of the deposition process beyond the classical description using current transients. Recent calculations predict deviations within the spatial arrangement of electrodeposited particles, away from random nucleation. The spatial arrangement of Au particles generated through aqueous electrodeposition on a nontemplated substrate is investigated by grazing incidence small-angle X-ray scattering (GISAXS). We show that GISAXS is able to reveal spatial correlations within deposited particles that are not easily detectable by microscopy.

Grazing-incidence small-angle X-ray scattering coupled with computed tomography (CT) has enabled the visualization of the spatial distribution of nanostructures in thin films. In this study, to optimize the CT image quality, total variation regularization is introduced to minimize sinogram image noise and artifacts., Grazing-incidence small-angle X-ray scattering (GISAXS) coupled with computed tomography (CT) has enabled the visualization of the spatial distribution of nanostructures in thin films. 2D GISAXS images are obtained by scanning along the direction perpendicular to the X-ray beam at each rotation angle. Because the intensities at the q positions contain nanostructural information, the reconstructed CT images individually represent the spatial distributions of this information (e.g. size, shape, surface, characteristic length). These images are reconstructed from the intensities acquired at angular intervals over 180°, but the total measurement time is prolonged. This increase in the radiation dosage can cause damage to the sample. One way to reduce the overall measurement time is to perform a scanning GISAXS measurement along the direction perpendicular to the X-ray beam with a limited interval angle. Using filtered back-projection (FBP), CT images are reconstructed from sinograms with limited interval angles from 3 to 48° (FBP-CT images). However, these images are blurred and have a low image quality. In this study, to optimize the CT image quality, total variation (TV) regularization is introduced to minimize sinogram image noise and artifacts. It is proposed that the TV method can be applied to downsampling of sinograms in order to improve the CT images in comparison with the FBP-CT images.

We present results of a systematic study of the morphology of etched ion tracks in amorphous SiO2 using a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy. We focus on the analysis of SAXS data obtained in grazing incidence (GISAXS) configuration from conical etched channels with a base radius of less than 50 nm. Swift heavy ion irradiation of 2 μm thick thermally grown SiO2 layers with 185 MeV Au ions was conducted at the ANU Heavy Ion Accelerator Facility in Canberra, Australia. Low irradiation fluences of 109 ions per cm2 were chosen to minimize overlap of the etched structures. Irradiated samples were etched in aqueous hydrofluoric acid (HF) with concentrations of 5%, for etching times between 30 and 90 s. In grazing incidence configuration, we obtain good data quality from the very small cones, since the X-ray beam interacts with a greater proportion of the sample at the very low incidence angle compared with normal transmission mode.

The development of diblock copolymer (DBC) nanocomposite films containing magnetic nanoparticles (NPs) with diameters (D) over 20 nm is a challenging task. To host large iron oxide NPs (Fe3O4, D = 27 ± 0.6 nm), an ultrahigh molecular weight (UHMW) linear DBC polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is used as a template in the present work. Due to hydrogen bonding between the carboxylic acid ligands of the NPs and the ester groups in PMMA, the NPs show an affinity to the PMMA block. The localization of the NPs inside the DBC is investigated as a function of the NP concentration. At low NP concentrations, NPs are located preferentially at the interface between PS and PMMA domains to minimize the interfacial tension caused by the strong segregation strength of the UHMW DBC. At high NP concentrations (≥10 wt %), chain-like NP aggregates (a head-to-tail orientation) are observed in the PMMA domains, resulting in a change of the morphology from sphere to ellipsoid for part of the PMMA domains. Magnetic properties of the hybrid films are probed via superconducting quantum interference device magnetometry. All hybrid films show ferrimagnetism and are promising for potential applications in magnetic data storage.

Mesoporous thin film architectures are an important class of materials that exhibit unique properties, which include high surface area, versatile surface functionalization, and bicontinuous percolation paths through a broad library of pore arrangements on the 10 nm length scale. Although porosimetry of bulk materials via sorption techniques is common practice, the characterization of thin mesoporous films with small sample volumes remains a challenge. A range of techniques are geared toward providing information over pore morphology, pore size distribution, surface area and overall porosity, but none of them offers a holistic evaluation and results are at times inconsistent. In this work, we present a tutorial overview for the reliable structural characterization of mesoporous films. Three model samples with variable pore size and porosity prepared by block copolymer (BCP) coassembly serve for a rational comparison. Various techniques are assessed side-by-side, including scanning electron microscopy (SEM), atomic force microscopy (AFM), grazing incidence small-angle X-ray scattering (GISAXS), and ellipsometric porosimetry (EP). We critically discuss advantages and limitations of each technique and provide guidelines for reliable implementation.

The crystallization behavior of the low band gap polymer poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'''-di(2-octyldodecyl)2,2';5',2'';5'',2'''-quaterthiophen-5,5'''-diyl)] (PffBT4T-2OD) induced in printed mesoporous titania films with different pore sizes is studied to optimize the crystal orientation for an application in hybrid solar cells. The correlation between the crystal structure of PffBT4T-2OD and the titania pore size is investigated with a combination of grazing incidence wide-angle X-ray scattering (GIWAXS) and grazing incidence small-angle X-ray scattering (GISAXS). For comparison, poly(3-hexylthiophene) (P3HT) is also backfilled into the same four types of printed titania mesoporous scaffolds. Both, lattice constants and crystal sizes of edge-on oriented P3HT crystals decrease with increasing the titania pore size. Similarly and irrespective of the crystal orientation, a denser stacking of PffBT4T-2OD chains is found for larger pore sizes of the titania matrix. For an edge-on orientation, also bigger PffBT4T-2OD crystals are favorably formed in smaller pores, whereas for a face-on orientation, PffBT4T-2OD crystals increase with increasing size of the titania pores. Thus, the best ratio of face-on to edge-on crystals for PffBT4T-2OD is obtained through infiltration into large titania pores.

The highly ordered perpendicularly aligned cylindrical and lamellar microdomains within block copolymer (BCP) films have important applications in diverse fields. However, the fast normal orientation of self-assembled nanostructures on arbitrary substrates without tedious pre- and postprocessing has been a challenging issue in manufacturing miniaturized devices. Here, we outline the potential for extending the hierarchical self-assembly within azobenzene-containing PS-b-PMA(Az) films to inherently assist in the formation of normally aligned domains using a rapid thermal annealing process (140 °C for 5 min). Liquid crystalline (LC) mesogens in PS-b-PMA(Az) films self-assemble to form a parallelly aligned sematic phase after thermal annealing, as confirmed by grazing-incidence small-angle X-ray scattering (GISAXS), wide-angle X-ray diffraction (WAXD) and ultraviolet-visible (UV-vis) spectra. This sub-phase contributes to broadening of the PS-cylinder-phase window (0.083 ≤ fPS < 0.49) and ∼12 nm PS cylinder structures. Perpendicular cylinders or lamellae are observed on various substrates, such as silicon wafers, flexible polyethylene terephthalate (PET) sheets and conductive aluminum foils. Additionally, the good reactive ion etching (RIE) rate difference between the two blocks makes these BCPs more attractive for advancing the field of BCP lithographic applications for fabricating flexible microelectronic devices.

Colloidal PbS quantum dots (QDs) are attractive for solution-processed thin-film optoelectronic applications. In particular, directly achieving QD thin-films by printing is a very promising method for low-cost and large-scale fabrication. The kinetics of QD particles during the deposition process play an important role in the QD film quality and their respective optoelectronic performance. In this work, the particle self-organization behavior of small-sized QDs with an average diameter of 2.88 ± 0.36 nm is investigated for the first time in situ during printing by grazing-incidence small-angle X-ray scattering (GISAXS). The time-dependent changes in peak intensities suggest that the structure formation and phase transition of QD films happen within 30 seconds. The stacking of QDs is initialized by a templating effect, and a face-centered cubic (FCC) film forms in which a superlattice distortion is also found. A body-centered cubic nested FCC stacking is the final QD assembly layout. The small size of the inorganic QDs and the ligand collapse during the solvent evaporation can well explain this stacking behavior. These results provide important fundamental understanding of structure formation of small-sized QD based films prepared via large-scale deposition with printing with a slot die coater.

Bulk heterojunction (BHJ) organic solar cells have gained increasing attention in the past few years. In this work, active layers of a wide-bandgap polymer donor with benzodithiophene units PBDB-T-2F and a non-fullerene small molecule acceptor IT-M are assembled into photovoltaic devices with different amounts of solvent additive 1,8-diiodooctane (DIO). The influence of DIO on the nanoscale film morphology and crystalline structure as well as the charge carrier dynamics of the active layers are investigated by combining grazing-incidence small-angle X-ray scattering (GISAXS), grazing-incidence wide-angle X-ray scattering (GIWAXS), X-ray reflectivity (XRR), UV-visible (UV-vis) absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), time-resolved photoluminescence (TRPL) and space charge limited current measurements, which are correlated with the corresponding performance of the solar cells. At 0.5 vol% DIO addition, the wide-bandgap non-fullerene organic solar cells show the best performance due to high open-circuit voltage and short-circuit current resulting from an improved charge carrier management due to the optimal inner nanoscale morphology of the active layers in terms of surface enrichment, crystallinity and crystalline orientation.

Nanometer thin films of Nafion ionomer interfaced with platinum form the functional electrodes in many electrochemical devices including fuel cells and electrolyzers. To impart facile proton conduction in a Nafion ionomer, sufficient hydration of the Nafion ionomer is necessary to create a percolating network of water-filled nanometer-sized hydrophilic domains that manifest as macroscopic swelling. This hydration behavior of the ionomer thin films is poorly understood especially for films confined on electrochemically relevant Pt substrates. In this work, we present the evolution of hydration-dependent microscopic hydrophilic domains and macroscopic expansion of a 55 nm thin Nafion film on a Pt substrate. The cross-correlation among the film macro-expansion from ellipsometry, the micro-expansion from GISAXS, and the water distribution from neutron reflectometry (NR) explains the observed non-affine behavior of the film which can be attributed to the randomly and spatially non-uniform distribution of water domains. A correlation between the macroscopic factor (ε/τ) for protonic conductivity, and the domain size and swelling is presented for the first time. In addition, interfacial water between Pt and the ionomer interface is estimated at 75% and 84% RH, and an increase in domain size with RH is discussed to explain the increased activity and oxygen diffusivity with RH.

Metal top electrodes such as gold are widely used in organic solar cells. The active layer can be optimized by modifications of the polymer band gap via side-chain engineering, and low band gap polymers based on benzodithiophene units such as PTB7 and PTB7-Th are successfully used. The growth of gold contacts on PTB7 and PTB7-Th films is investigated with in situ grazing incidence small-angle X-ray scattering (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS) during the sputter deposition of gold. From GIWAXS, the crystal structure of the gold film is determined. Independent of the type of side chain, gold crystals form in the very early stages and improve in quality during the sputter deposition until the late stages. From GISAXS, the nanoscale structure is determined. Differences in terms of gold cluster size and growth phase limits for the two polymers are caused by the side-chain modification and result in a different surface coverage in the early phases. The changes in the diffusion and coalescence behavior of the forming gold nanoparticles cause differences in the morphology of the gold contact in the fully percolated regime, which is attributed to the different amount of thiophene rings of the side chains acting as nucleation sites.

Grazing incidence small- and wide-angle scattering (GISAXS, GIWAXS) are widely applied for the study of organic thin films, be it for the characterization of nanostructured morphologies in block copolymers, nanocomposites, or nanoparticle assemblies, or the packing and orientation of small aromatic molecules and conjugated polymers. Organic thin films typically are uniaxial powders, with specific crystallographic planes oriented parallel to the substrate surface. The associated fiber texture scattering patterns are complicated by refraction corrections and multiple scattering. We present an interactive graphics tool to index such patterns.

Increasing miniaturization and complexity of nanostructures require innovative metrology solutions with high throughput that can assess complex 3D structures in a non-destructive manner. EUV scatterometry is investigated for the characterization of nanostructured surfaces. The reconstruction is based on a rigorous simulation using a Maxwell solver based on finite-elements and is statistically validated with a Markov-Chain Monte Carlo sampling method. Here it is shown that this method is suitable for the dimensional characterization of the nanostructures and the investigation of oxide or contamination layers. In comparison to grazing-incidence small-angle X-rayscattering (GISAXS) EUV allows to probe smaller areas. The influence of the divergence on the diffracted intensities in EUV is much lower than in GISAXS, which also reduces the computational effort of the reconstruction.

Applied Sciences 11(19), 8970 (2021). doi:10.3390/app11198970, Here, we report on adding an important dimension to the fundamental understanding of the evolution of the thin film micro structure evolution. Thin films have gained broad attention in their applications for electro-optical devices, solar-cell technology, as well storage devices. Deep insights into fundamental functionalities can be realized via studying crystallization microstructure and formation processes of polycrystalline or epitaxial thin films. Besides the fundamental aspects, it is industrially important to minimize cost which intrinsically requires lower energy consumption at increasing performance which requires new approaches to thin film growth in general. Here, we present a state of the art sputtering technique that allows for time-resolved in situ studies of such thin film growth with a special focus on the crystallization via small angle scattering and X-ray diffraction. Focusing on the crystallization of the example material of BaTiO$_3$, we demonstrate how a prototypical thin film forms and how detailed all phases of the structural evolution can be identified. The technique is shaped to enable a versatile approach for understanding and ultimately controlling a broad variety of growth processes, and more over it demonstrate how to in situ investigate the influence of single high temperature sputtering parameters on the film quality. It is shown that the whole evolution from nucleation, diffusion adsorption and grain growth to the crystallization can be observed during all stages of thin film growth as well as quantitatively as qualitatively. This can be used to optimize thin-film quality, efficiency and performance., Published by MDPI, Basel

The internal structures of thin films, having nanoholes and densely branched morphologies and prepared from a long chain polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, were characterized. Using grazing-incidence small- and wide-angle X-ray scattering (GISAXS & GIWAXS), the thickness of the lamellar mesophase repeat unit and the orientation of the PEO crystalline chain stems within the thin film were determined. The dimensions of the internal structures and their orientations were linked to the surface morphologies measured by atomic force microscopy. For the nanoholes morphology, the film thicknesses were found to deviate from an integer multiple of the diblock copolymer lamellar units (~ 70 nm) promoting the hole textures. Dewetted architectures were obtained by annealing freshly prepared films under toluene/water vapour environment at an elevated temperature. After that, some PEO chains were able to crystallize within the dewetted large holes resulting in a densely branched morphology (DBM). The crystalline chain stems of the crystalline lamellar, within the dewetted large holes, were found to be roughly perpendicular to the film substrate with thicknesses of about 10 nm. This is in agreement with the diffusion-limited aggregated model.

Layer-by-layer polyelectrolyte self-assembly, a common method for preparing high-quality ultra-thin films, was employed to direct the self-assembly behavior of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer for the first time. Differing from the previous neutral polymer brushes anchored to silicon substrates via chemical modification, polyelectrolyte multilayers (PEMs) were anchored by electrostatic interaction and provided a stable, smooth, and neutral interface. In the present study, PS-b-PMMA was deposited on poly(acrylamide hydrochloride)/poly(acrylic acid) (PAH/PAA) PEMs prepared by layer-by-layer self-assembly to successfully yield vertical nanodomains after thermal annealing. Seven layered PEMs revealed an excellent, smooth surface, with a low roughness of 0.6 nm. The periodic structure with interlamellar spacing of 47 nm was determined by grazing-incidence small-angle X-ray scattering (GISAXS). The morphology of the PS-b-PMMA nanodomains depended on the polyanion-to-polycation concentration ratio, which is related to the interaction between the block copolymer and the substrate. Our results demonstrate that layer-by-layer self-assembly is a helpful method for the phase separation of block polymers and the fabrication of vertical, ordered nanodomains.

Nanoporous layers are widely spread in nature and among artificial devices. However, complex characterization of extensively nanoporous thin films showing porosity-dependent softening lacks consistency and reliability when using different analytical techniques. We introduce herein, a facile and precise method of such complex characterization by multi-harmonic QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring) measurements performed both in the air and liquids (Au-Zn alloy was used as a typical example). The porosity values determined by QCM-D in air and different liquids are entirely consistent with that obtained from parallel RBS (Rutherford Backscattering Spectroscopy) and GISAXS (Grazing-Incidence Small-Angle Scattering) characterizations. This ensures precise quantification of the nanolayer porosity simultaneously with tracking their viscoelastic properties in liquids, significantly increasing sensitivity of the viscoelastic detection (viscoelastic contrast principle). Our approach is in high demand for quantifying potential-induced changes in nanoporous layers of complex architectures fabricated for various electrocatalytic energy storage and analytical devices., Thin porous layers are largely used, but a reliable method to quantify their porosity is missing. Here the authors demonstrate a method, based on quartz crystal microbalance measurements with dissipation monitoring, for accurate assessment of porosity and mechanical properties in thin porous films.

Recently, lead sulfide (PbS) quantum dots (QDs) have demonstrated great potential in becoming one of the most promising next-generation photoelectrical materials for photodetectors. PbS QDs provide...

The soft-templating method is important in the preparation of ordered mesoporous carbon materials. In the process, careful removal of the block template is a critical step in obtaining a highly ordered mesostructure before carbonization. In this study, the dynamic structure evolution of template removal by means of calcination using both high (3 °C/min) and low (1 °C/min) heating rates was monitored using an in situ GISAXS technique. The real-time d-spacing and order degree parameters including the mesochannel dislocation and grain size of the ordered structure were determined as a function of calcination time. The results showed that the entire structure evolution process could be divided into three stages according to variable rates of d-spacing: glass transition stage, molten phase transition stage, and pyrolysis stage. In the first stage, thermal expansion transition into template shrinkage was observed as the polymer chain transitioned from a rigid to a softer state. Shrinkage of the template occurred, while a highly ordered mesostructured remained. In the second stage, the template became flexible after the molten phase transition, and the rate of structure change gradually increased, accompanied by mesochannel dislocation. Fast pyrolysis occurred in the last stage, the ordered structure was destroyed, and internal stress was released. This phenomenon was also clearly observed when the heating rate was 3 °C/min. The final ratio of dislocation comparing the state before and after template removal was 9.13, which is significantly higher than the value of 5.84 observed with a heating rate of 1 °C/min. The results indicated that the ordered mesostructure after template removal was determined by not only the critical temperature but also the heating profile during the entire process of structure evolution. A hypothetical mechanism is proposed to explain the structure evolution of template removal for ordered mesoporous films prepared by a soft-templating method. A reasonable design for a heating profile for template removal based on this in situ GISAXS study can be an effective method for improving the quality of mesoporous films.

Thin hybrid films with dense magnetic structures for sensor applications are printed using diblock copolymer (DBC) templating magnetic nanoparticles (MNPs). To achieve a high-density magnetic structure, the printing ink is prepared by mixing polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) with a large PS volume fraction and PS selective MNPs. Solvent vapor annealing is applied to generate a parallel cylindrical film morphology (with respect to the substrate), in which the MNP-residing PS domains are well separated by the PMMA matrix, and thus, the formation of large MNP agglomerates is avoided. Moreover, the morphologies of the printed thin films are determined as a function of the MNP concentration with real and reciprocal space characterization techniques. The PS domains are found to be saturated with MNPs at 1 wt %, at which the structural order of the hybrid films reaches a maximum within the studied range of MNP concentration. As a beneficial aspect, the MNP loading improves the morphological order of the thin DBC films. The dense magnetic structure endows the thin films with a faster superparamagnetic responsive behavior, as compared to thick films where identical MNPs are used, but dispersed inside the minority domains of the DBC.

Sr-bearing marine barite [(Ba x , Sr 1− x )SO 4 ] cycling has been widely used to reconstruct geochemical evolutions of paleoenvironments. However, an understanding of barite precipitation in the ocean, which is globally undersaturated with respect to barite, is missing. Moreover, the reason for the occurrence of higher Sr content in marine barites than expected for classical crystal growth processes remains unknown. Field data analyses suggested that organic molecules may regulate the formation and composition of marine barites; however, the specific organic–mineral interactions are unclear. Using in situ grazing incidence small-angle X-ray scattering (GISAXS), size and total volume evolutions of barite precipitates on organic films were characterized. The results show that barite forms on organic films from undersaturated solutions. Moreover, from a single supersaturated solution with respect to barite, Sr-rich barite nanoparticles formed on organics, while micrometer-size Sr-poor barites formed in bulk solutions. Ion adsorption experiments showed that organic films can enrich cation concentrations in the adjacent solution, thus increasing the local supersaturation and promoting barite nucleation on organic films, even when the bulk solution was undersaturated. The Sr enrichment in barites formed on organic films was found to be controlled by solid-solution nucleation rates; instead, the Sr-poor barite formation in bulk solution was found to be controlled by solid-solution growth rates. This study provides a mechanistic explanation for Sr-rich marine barite formation and offers insights for understanding and controlling the compositions of solid solutions by separately tuning their nucleation and growth rates via the unique chemistry of solution–organic interfaces.

An inhomogeneity of material in W/Si multilayer structures was studied with grazing-incidence small-angle X-ray scattering. The experimental study revealed lateral density fluctuations in the Si spacer layers., A structural characterization of W/Si multilayers using X-ray reflectivity (XRR), scanning transmission electron microscopy (STEM) and grazing-incidence small-angle X-ray scattering (GISAXS) is presented. STEM images revealed lateral, periodic density fluctuations in the Si layers, which were further analysed using GISAXS. Characteristic parameters of the fluctuations such as average distance between neighbouring fluctuations, average size and lateral distribution of their position were obtained by fitting numerical simulations to the measured scattering images, and these parameters are in good agreement with the STEM observations. For the numerical simulations the density fluctuations were approximated as a set of spheroids distributed inside the Si layers as a 3D para­crystal (a lattice of spheroids with short-range ordering but lacking any long-range order). From GISAXS, the density of the material inside the density fluctuations is calculated to be 2.07 g cm−3 which is 89% of the bulk value of the deposited layer (2.33 g cm−3).

To increase the moisture stability of hybrid perovskite photovoltaics, a combination of three-dimensional (3D) and a thin layer of two-dimensional (2D) perovskite incorporating long-chained organic cations is often employed as photoabsorber. However, the detailed interaction between water and 3D/2D perovskite heterojunctions has not been elucidated yet. Using in situ neutron and X-ray scattering techniques, we reveal surprisingly strong water uptake into 3D/2D perovskite films despite the presence of hydrophobic bulky cations. Our results show rapid disproportionation of the initial 2D phase (number of layers, m = 5) in methylammonium lead iodide (MAPI)/2D films into lower m phases under humidity. Nevertheless, the 2D perovskite inhibits the irreversible PbI2 formation, which suggests that the suppression of I– and MA+ ion migration and consequently of MAI escape is related to the improved moisture stability of MAPI/2D perovskite films. In comparison, quadruple-cation perovskites including Rb+ exhibit poo...

Observations of the initial lithiation of NiO electrodes demonstrate how to seed conversion reactions using interfaces in a thin film Ni/NiO bilayer architecture. Operando X-ray reflectivity (XRR) reveals that structural changes in a NiO film begin at potentials near the theoretical reduction potential (1.8-2.0 V) with detectable lithiation of both the buried Ni/NiO interface and the outer NiO surface that occur prior to the reaction of the NiO film. This initial conversion reaction is most pronounced in ultrathin NiO films (∼20 Å) with only small changes to the NiO film surface for thicker films (∼67 Å). The limited reactivity of thicker NiO films probed using operando grazing incidence small-angle X-ray scattering (GISAXS) shows the growth of nanoparticles at the electrode/electrolyte interface during initial lithium ion insertion, with a 16-20 Å average radius. Ex situ X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning transmission electron microscopy/electron energy loss spectroscopy (STEM/EELS) confirm our conclusions about the morphological changes accompanying initial stage of lithiation in these conversion reaction electrodes. The present study reveals the interconnected challenges of solid-solid transitions, overpotentials, interfacial nucleation and kinetics, and transition metal dissolution in conversion-type electrodes that are critical for their use as electrodes in lithium-ion batteries.

A nitrogen-free and slot-die coating fabrication of perovskite solar cells combined with NIR annealing. We develop a fabrication approach of planar inverted structured perovskite solar cell (PSC) in ambient condition with a PCE of 12.4% as compared to that (13.3%) of PSC fabricated in glove box filled with nitrogen. In addition, we demonstrate an alternative post-annealed method by near-infrared (NIR) radiation to traditional heating method by oven. The annealed time by NIR can be shortened from 1500 s to 30 s and the device performance over 10% can be achieved. The present work investigates the NIR effect for different layers in the two-step processing on the cell performance. The grazing-incidence wide-angle and small-angle X-ray scattering (GIWAXS and GISAXS) techniques for the perovskite layers are performed to reveal the crystalline and nano-morphological structures of perovskite layers correlated to thermal and NIR annealing effects. Based on this approach under ambient air, we scale up to the large-area fabrication using the slot-die coating. The performance of slot-die coated PSC can achieve to 12.3%. The critical step is the control of PbI2 layer thickness. We also applied the NIR radiation to the slot-die coated PSC and the PCE of 11.4% can be achieved. Our study paves a facile way to rapid manufacture and mass production of perovskite solar cells.

Soft polymer colloidal water suspensions are extremely important formulations for industrial applications such as water-based environmental-friendly coatings, paints, and adhesives. Homogeneity of the final coating at the micrometer and nanoscale is a crucial factor for optimal coating performance, such as barrier properties against solvent permeation. Here, we investigated the remnant nanostructure in slot-die-coated micrometer-sized thick clear coating films (clearcoats) of three different waterborne polymer colloids (pure soft, pure hard, and soft/hard multiphase), commonly utilized as primers in paint formulations [Mader et al. Prog. Org. Coat. 2011, 71, 123-135], using variable-angle grazing incidence small-angle X-ray scattering (GISAXS) complemented with cross-sectional atomic force microscopy (cs-AFM). After complete macroscopic drying, the coating films exhibit the presence of residual nanostructure with characteristic distance (d*) smaller than the original particle size and even smaller (<< d*) heterogeneity dimensions. These nanostructural heterogeneities (i) develop due to partial particle coalescence, (ii) are preferentially located close to the air-film interface and (iii) demonstrate the tendency to align perpendicular to the air-film interface, implying vertical gradient in hydroplasticization effects having occurred earlier during film formation. The extent and size of the nanostructural heterogeneities, driven by the slot-die coating application, strongly depend on the polymer chemistry (glass transition temperature, T-g) and the colloidal architecture. Last, solvent exposure has a significant impact on the nanostructure, causing the removal of these heterogeneities and leading to a more strongly coalesced film.