Effect of Thermal Stimulus on Kinetic Rehydration of Thermoresponsive Poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate) Thin Films Probed by In Situ Neutron Reflectivity.

The kinetic rehydration of thin di-block copolymer poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate) (PO2-b-PO300) films containing two thermoresponsive components is probed by in situ neutron reflectivity (NR) with different thermal stimuli in the D2O vapor atmosphere. The transition temperatures (TTs) of PO2 and PO300 blocks are 25 and 60 °C, respectively. After the one-step stimulus (rapid decrease in temperature from 60 to 20 °C), the film directly switches from a collapsed to a fully swollen state. The rehydration process is divided into four steps: (a) D2O condensation, (b) D2O absorption, (c) D2O evaporation, and (d) film reswelling. However, the film presents a different rehydration behavior when the thermal stimulus is separated into two smaller steps (first decrease from 60 to 40 °C and then to 20 °C). The film first switches from a collapsed to a semiswollen state caused by the rehydrated PO300 blocks after the first step of thermal stimulus (60 to 40 °C) and then to a swollen state induced by the rehydrated PO2 blocks after the second step (40 to 20 °C). Thus, the kinetic responses are distinct from that after the one-step thermal stimulus. Both the time and extent of condensation as well as evaporation processes are significantly reduced in these two smaller steps. However, the final states of the rehydrated PO2-b-PO300 films are basically identical irrespective of the applied thermal stimulus. Thus, the final state of thermoresponsive di-block copolymer films is not affected by the external thermal stimuli, which is beneficial for the design and preparation of sensors or switches based on thermoresponsive polymer films.

A Self-Ordered Nanostructured Transparent Electrode of High Structural Quality and Corresponding Functional Performance.

The preparation of a highly ordered nanostructured transparent electrode based on a combination of nanosphere lithography and anodization is presented. The size of perfectly ordered pore domains is improved by an order of magnitude with respect to the state of the art. The concomitantly reduced density of defect pores increases the fraction of pores that are in good electrical contact with the underlying transparent conductive substrate. This improvement in structural quality translates directly and linearly into an improved performance of energy conversion devices built from such electrodes in a linear manner.

Hydration and Thermal Response Kinetics of a Cross-Linked Thermoresponsive Copolymer Film on a Hydrophobic PAN Substrate Coating Probed by In Situ Neutron Reflectivity.

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.

Impact of Thermal History on the Kinetic Response of Thermoresponsive Poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol)methyl ether methacrylate) Thin Films Investigated by In Situ Neutron Reflectivity.

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.

Hydration and Dehydration Kinetics: Comparison between Poly( N-isopropyl methacrylamide) and Poly(methoxy diethylene glycol acrylate) Films.

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 °C and PMDEGA 41 °C). After hydration in unsaturated D2O vapor at 23 °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.

Effect of chain architecture on the swelling and thermal response of star-shaped thermo-responsive (poly(methoxy diethylene glycol acrylate)-block-polystyrene)3 block copolymer films.

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 °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 °C, 45 °C and 50 °C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.

Lithium-Salt-Containing High-Molecular-Weight Polystyrene-block-Polyethylene Oxide Block Copolymer Films.

Ionic conductivity in relation to the morphology of lithium-doped high-molecular-weight polystyrene-block-polyethylene oxide (PS-b-PEO) diblock copolymer films was investigated as solid-state membranes for lithium-ion batteries. The tendency of the polyethylene (PEO) block to crystallize was highly suppressed by increasing both the salt-doping level and the temperature. The PEO crystallites completely vanished at a salt-doping ratio of Li/EO>0.08, at which the PEO segments were hindered from entering the crystalline unit of the PEO chain. A kinetically trapped lamella morphology of PS-b-PEO was observed, due to PEO crystallization. The increase in the lamella spacing with increasing salt concentration was attributed to the conformation of the PEO chain rather than the volume contribution of the salt or the previously reported increase in the effective interaction parameter. Upon loading the salt, the PEO chains changed from a compact/highly folded conformation to an amorphous/expanded-like conformation. The ionic conductivity was enhanced by amorphization of PEO and thereby the mobility of the PEO blocks increased upon increasing the salt-doping level.

Cobalt nanoparticles growth on a block copolymer thin film: a time-resolved GISAXS study.

Cobalt sputter deposition on a nanostructured polystyrene-block-poly(ethylene oxide), P(S-b-EO), template is followed in real time with grazing incidence small-angle X-ray scattering (GISAXS). The polymer template consists of highly oriented parallel crystalline poly(ethylene oxide) (PEO) domains that are sandwiched between two polystyrene (PS) domains. In-situ GISAXS shows that cobalt atoms selectively decorate the PS domains of the microphase-separated polymer film and then aggregate to form surface metal nanopatterns. The polymer template is acting as a directing agent where cobalt metal nanowires are formed. At high metal load, the characteristic selectivity of the template is lost, and a uniform metal layer forms on the polymer surface. During the early stage of cobalt metal deposition, a highly asymmetric nanoparticles agglomeration is dominating structure formation. The cobalt nanoparticles mobility in combination with the high tendency of the nanoparticles to coalescence and to form immobile large-sized particles at the PS domains are discussed as mechanisms of structure formation.

Kinetics of collapse transition and cluster formation in a thermoresponsive micellar solution of P(S-b-NIPAM-b-S) induced by a temperature jump.

Structural changes at the intra- as well as intermicellar level were induced by the LCST-type collapse transition of poly(N-isopropyl acrylamide) in ABA triblock copolymer micelles in water. The distinct process kinetics was followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while a micellar solution of a triblock copolymer, consisting of two short deuterated polystyrene endblocks and a long thermoresponsive poly(N-isopropyl acrylamide) middle block, was heated rapidly above its cloud point. A very fast collapse together with a multistep aggregation behavior is observed. The findings of the transition occurring at several size and time levels may have implications for the design and application of such thermoresponsive self-assembled systems.

Time-resolved ultrathin cobalt film growth on a colloidal polymer template.

Cobalt (Co) sputter deposition onto a colloidal polymer template is investigated using grazing incidence small-angle X-ray scattering (GISAXS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). SEM and AFM data picture the sample topography, GISAXS the surface and near-surface film structure. A two-phase model is proposed to describe the time evolution of the Co growth. The presence of the colloidal template results in the correlated deposition of an ultrathin Co film on the sample surface and thus in the creation of Co capped polystyrene (PS) colloids. Well below the percolation threshold, the radial growth is restricted and only height growth is observed.

A novel experimental approach for nanostructure analysis: simultaneous small-angle X-ray and neutron scattering.

Exploiting small-angle X-ray and neutron scattering (SAXS/SANS) on the same sample volume at the same time provides complementary nanoscale structural information in two different contrast situations. Unlike an independent experimental approach, the truly combined SAXS/SANS experimental approach ensures the exactness of the probed samples, particularly for in situ studies. Here, an advanced portable SAXS system that is dimensionally suitable for installation in the D22 zone of ILL is introduced. The SAXS apparatus is based on a Rigaku switchable copper/molybdenum microfocus rotating-anode X-ray generator and a DECTRIS detector with a changeable sample-to-detector distance of up to 1.6 m in a vacuum chamber. A case study is presented to demonstrate the uniqueness of the newly established method. Temporal structural rearrangements of both the organic stabilizing agent and organically capped gold colloidal particles during gold nanoparticle growth are simultaneously probed, enabling the immediate acquisition of correlated structural information. The new nano-analytical method will open the way for real-time investigations of a wide range of innovative nanomaterials and will enable comprehensive in situ studies on biological systems. The potential development of a fully automated SAXS/SANS system with a common control environment and additional sample environments, permitting a continual and efficient operation of the system by ILL users, is also introduced.

Thin films of photoactive polymer blends.

The morphology inside photoactive blended films of two conjugated homopolymers poly [(1-methoxy)-4-(2-ethylhexyloxy)-p-phenylene-vinylene] (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT) is investigated. For both homopolymers a linear dependence of the installed film thickness from the concentration of the polymer solution used in spin coating is probed. This dependence allows preparation of an efficient series of blended films with constant thickness and different blending ratios. Information about the lateral structure inside the films is gained from grazing incidence small angle X-ray scattering. At the calculated critical blending ratio the smallest lateral separation between adjacent domains is found representing the highest surface contact between both homopolymers in the films. The presence of wetting layers at both interfaces as detected with X-ray reflectivity and atomic force microscopy is promising for photovoltaic applications. UV/Vis spectroscopy complements the structural investigation.

Preservation of the morphology of a self-encapsulated thin titania film in a functional multilayer stack: an X-ray scattering study.

Tailoring of the titania morphology is achieved by the combination of a triblock copolymer, acting as structure-directing agent, and a sol-gel chemistry enabling the incorporation of the provided inorganic material (titania) into the selected phase of the triblock copolymer. Spin-coating of the solution on FTO-coated glass, followed by plasma etching and calcination of the thin film results in the formation of self-encapsulated crystalline titania nanostructures. The fabricated nanostructures are coated stepwise with dye, conductive polymers and gold forming a functional multilayer stack. An advanced small-angle scattering technique probing the sample with X-ray synchrotron radiation under grazing incidence (GISAXS) is employed for the characterization of the preparation route, as scattering allows accessing the structure inside the multilayers. The tailored titania morphology is preserved during the preparation route towards the functional multilayer stack of a photovoltaic demonstration cell. Two clearly distinguishable structures originate from the substrate and the titania templated by the triblock copolymer; hence the other layers induce no additional structures. Therefore, this investigation provides the evidence that the effort spent to tailor the morphology is justified by the preservation of the self-encapsulated titania morphology that is created by the structure-directing agent throughout the functional multilayer stack build-up.

Electronic properties of hybrid organic/inorganic semiconductor pn-junctions.

Hybrid inorganic/organic semiconductor heterojunctions are candidates to expand the scope of purely organic or inorganic junctions in electronic and optoelectronic devices. Comprehensive understanding of bulk and interface doping on the junction's electronic properties is therefore desirable. In this work, we elucidate the energy level alignment and its mechanisms at a prototypical hybrid pn-junction comprising ZnO (n-type) and p-doped N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (α-NPD) as semiconductors, using photoelectron spectroscopy. The level alignment can be quantitatively described by the interplay of contact-induced band and energy level bending in the inorganic and organic component away from the interface, and an interface dipole due to the push-back effect. By adjusting the dopant concentration in α-NPD, the position of the frontier energy levels of ZnO can be varied by over 0.5 eV and that of α-NPD by over 1 eV. The tunability of this pn-junction's energy levels evidences the substantial potential of the hybrid approach for enhancing device functionality.

Role of Nickel Nanoparticles in High-Performance TiO2 /Ni/Carbon Nanohybrid Lithium/Sodium-Ion Battery Anodes.

Super-small sized TiO2 nanoparticles are in situ co-composited with carbon and nickel nanoparticles in a facile scalable way, using difunctional methacrylate monomers as solvent and carbon source. Good control over crystallinity, morphology, and dispersion of the nanohybrid is achieved because of the thermosetting nature of the resin polymer. The effects of the nickel nanoparticle on the composition, crystallographic phase, structure, morphology, tap density, specific surface area, and electrochemical performance as both lithium-ion and sodium-ion battery anodes are systematically investigated. It is found that the incorporation of the in situ formed nickel nanoparticles with certain content effectively enhances the electrochemical performance including reversible capacities, cyclic stability and rate performance as both lithium-ion and sodium-ion battery anodes. The experimental I-V profiles at different temperatures and theoretical calculations reveal that the charge carriers are accumulated in the amorphous carbon regions, which act as scattering centers to the carriers and lower the carrier mobility for the composite. With increasing nickel content, the mobility of the charge carriers is significantly increased, while the number of the charge carriers maintains almost constant. The nickel nanoparticles provide extra pathways for the accumulated charge, leading to reduced scatterings among the charge carriers and enhanced charge-carrier transportation.

Printed Thin Magnetic Films Based on Diblock Copolymer and Magnetic Nanoparticles.

Printing techniques have been well established for large-scale production and have developed to be effective in controlling the morphology and thickness of the film. In this work, printing is employed to fabricate magnetic thin films composed of polystyrene coated maghemite nanoparticles (γ-Fe2O3 NPs) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer. By applying an external magnetic field during the print coating step, oriented structures with a high content of nanoscale magnetic particles are created. The morphology of the magnetic films and the arrangement of NPs within the polymer matrix are characterized with real and reciprocal space techniques. Due to the applied magnetic field, the magnetic NPs self-assemble into microscale sized wires with controlled widths and separation distances, endowing hybrid films with a characteristic magnetic anisotropy. At the nanoscale level, due to the PS coating, the NPs disperse as single particles at low NP concentrations. The NPs self-assemble into nanosized clusters inside the PS domains when the NP concentration increases. Due to a high loading of uniformly dispersed magnetic NPs across the whole printed film, a strong sensitivity to an external magnetic field is achieved. The enhanced superparamagnetic property of the printed films renders them promising candidate materials for future magnetic sensor applications.

In Situ Monitoring the Uptake of Moisture into Hybrid Perovskite Thin Films.

Solution-processed hybrid perovskites are of great interest for use in photovoltaics. However, polycrystalline perovskite thin films show strong degradation in humid atmospheres, which poses an important challenge for large-scale market introduction. With in situ grazing incidence neutron scattering (GISANS) we analyzed water content, degradation products, and morphological changes during prolonged exposure to several humidity levels. In high humidity, the formation of metastable hydrate phases is accompanied by domain swelling, which transforms the faceted crystals to a round-washed, pebble-like form. The films incorporate much more water than is integrated into the hydrates, with smaller crystals being more affected, making the degradation strongly dependent on film morphology. Even at low humidity, water is adsorbed on the crystal surfaces without the formation of crystalline degradation products. Thus, although production in an ambient atmosphere is of interest for industrial production it might lead to long-term degradation without appropriate countermeasures like postproduction drying below 30% RH.

Scalable in Situ Synthesis of Li4Ti5O12/Carbon Nanohybrid with Supersmall Li4Ti5O12 Nanoparticles Homogeneously Embedded in Carbon Matrix.

Li4Ti5O12 (LTO) is regarded as a promising lithium-ion battery anode due to its stable cyclic performance and reliable operation safety. The moderate rate performance originated from the poor intrinsic electron and lithium-ion conductivities of the LTO has significantly limited its wide applications. A facile scalable synthesis of hierarchical Li4Ti5O12/C nanohybrids with supersmall LTO nanoparticles (ca. 17 nm in diameter) homogeneously embedded in the continuous submicrometer-sized carbon matrix is developed. Difunctional methacrylate monomers are used as solvent and carbon source to generate TiO2/C nanohybrid, which is in situ converted to LTO/C via a solid-state reaction procedure. The structure, morphology, crystallinity, composition, tap density, and electrochemical performance of the LTO/C nanohybrid are systematically investigated. Comparing to the control sample of the commercial LTO composited with carbon, the reversible specific capacity after 1000 cycles at 175 mA g-1 and rate performance at high current densities (875, 1750, and 3500 mA g-1) of the Li4Ti5O12/C nanohybrid have been significantly improved. The enhanced electrochemical performance is due to the unique structure feature, where the supersmall LTO nanoparticles are homogeneously embedded in the continuous carbon matrix. Good tap density is also achieved with the LTO/C nanohybrid due to its hierarchical micro-/nanohybrid structure, which is even higher than that of the commercial LTO powder.

Si/Ag/C Nanohybrids with in Situ Incorporation of Super-Small Silver Nanoparticles: Tiny Amount, Huge Impact.

Silicon (Si) has been regarded as one of the most promising anodes for next-generation lithium-ion batteries (LIBs) due to its exceptional capacity, appropriate voltage profile, and reliable operation safety. However, poor cyclic stability and moderate rate performance have been critical drawbacks to hamper the practical application of Si-based anodes. It has been one of the central issues to develop new strategies to improve the cyclic and rate performance of the Si-based lithium-ion battery anodes. In this work, super-small metal nanoparticles (2.9 nm in diameter) are in situ synthesized and homogeneously embedded in the in situ formed nitrogen-doped carbon matrix, as demonstrated by the Si/Ag/C nanohybrid, where epoxy resin monomers are used as solvent and carbon source. With tiny amount of silver (2.59% by mass), the Si/Ag/C nanohybrid exhibits superior rate performance compared to the bare Si/C sample. Systematic structure characterization and electrochemical performance tests of the Si/Ag/C nanohybrids have been performed. The mechanism for the enhanced rate performance is investigated and elaborated. The temperature-dependent I-V behavior of the Si/Ag/C nanohybrids with tuned silver contents is measured. Based on the model, it is found that the super-small silver nanoparticles mainly increase charge carrier mobility instead of the charge carrier density in the Si/Ag/C nanohybrids. The evaluation of the total electron transportation length provided by the silver nanoparticles within the electrode also suggests significantly enhanced charge carrier mobility. The existence of tremendous amounts of super-small silver nanoparticles with excellent mechanical properties also contributes to the slightly improved cyclic stability compared to that of simple Si/C anodes.

Signal and sensitivity enhancement through optical interference coating for DNA and protein microarray applications.

Optical inteference (OI) coated slides with unique optical properties were utilized in microarray analyses, demonstrating their enhanced detection sensitivity over traditional microarray substrates. The OI coating is comprised of a proprietary multilayered, dielectric, thin-film interference coating located beneath the functional coating (aminosilane or epoxysilane). It is designed to enhance the fluorescence in the Cy3 and Cy5 channel by increasing the light absorption of the dyes by about 6-fold and by redirecting emitted fluorescence into the detector during scanning, resulting in a theoretical limit of about 12-fold signal amplification. Two-color DNA microarray experiments conducted on the OI slides showed over 8-fold signal amplification, conservation of gene expression ratios, and increased signal-to-noise ratio when compared to control slides, indicating enhanced detection sensitivity. Protein microarray assays also exhibited over 8-fold signal amplification at three different target concentrations, demonstrating the versatility of the OI slides for different microarray applications. Further, the DNA and protein assays performed on the OI slides exhibited excellent detection sensitivity even at the low target amounts essential for diagnostic applications. The OI slides are compatible with commonly used protocols, printers, scanners and other microarray equipment. Therefore, the OI slides offer an attractive alternative to traditional microarray substrates, where enhanced detection sensitivity is desired.