Homogeneous alignment of liquid crystals on low-temperature solution-derived gallium oxide films via IB irradiation method

In this paper, solution-derived gallium oxide (GaO) films are fabricated for the homogeneous alignment of liquid crystals (LCs) after an ion-beam (IB) irradiation process. GaO thin films are prepared under a variety of temperatures and different IB irradiation intensities, and the physicochemical performances of the fabricated GaO thin films are analysed using a UV-vis spectrometer, an atomic force microscope, and X-ray photoelectron spectroscopy. A higher transmittance of 85.40% from GaO thin film is obtained compared with that of polyimide (PI) film (83.52%), which indicates the feasibility for a GaO thin layer to substitute for a conventional PI layer as an alignment layer. LCs are found to align on the GaO thin film after pre-baking at 100°C and homogeneous and uniform low-IB intensity irradiation. We also determined the electro-optical (EO) characteristics of the twisted nematic (TN) cells fabricated with GaO thin layers and found them to be similar to those of cells fabricated with PI layers. Overall, GaO films achieved via the IB irradiation method are promising LC alignment layers due to the method’s low-temperature solution-derived process.     

Electrical properties of gadolinia-doped ceria thin films deposited by sputtering in view of SOFC application

Gadolinia-doped ceria (GDC) remains, up to now, the most promising candidate for replacing yttria-stabilised zirconia (YSZ) as electrolyte for solid oxide fuel cells (SOFC) operating at intermediate temperature. Literature data point out that GDC could be used as electrolyte, anode material, or interlayers for avoiding the chemical interactions occurring at the interfaces. In the present work, GDC thin layers were produced by d.c. reactive magnetron sputtering and deposited over a thickness domain between 450 nm and 5.5 µm. According to our knowledge, the deposition of GDC sputtered layers has never been reported. The physicochemical features of these thin films have been characterised by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Impedance measurements have been carried out in order to determine the electrical properties of electrolyte thin films and in particular their ionic conductivity.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003     

Effect of alignment layer on V-shaped switching in a chiral smectic liquid crystal

The influence of the alignment layer on V-shaped switching in thin homogeneous cells of a chiral smectic liquid crystal were studied by means of electro-optic and switching current measurements.Severalpolyimides withdifferent chemicalstructures wereusedas thealignment layer in thin homogeneous cells; V-shaped switching was observed with some of them and W-shaped switching with others. It was also shown that the switching current constantly flows during the V-shaped transmittance change. In order to clarify this effect of the alignment layer on V-shaped switching, polyimide films with various polarity and thickness were examined. It is concluded that thick alignment layers assist liquid crystal materials in realizing V-shaped switching, even if the materials are not ideal for this process.     

Chemical Composition and Structure of Thin Films Produced by Chemical Vapor Deposition

This paper reports results from studies of the chemical composition and structure of semiconducting, dielectric, and metallic films produced from molecular precursors by the chemical vapor deposition method. A study was made of films of zinc sulfides, mixed copper, cadmium, and zinc sulfides, boron nitride, carbonitride, silicon carbonitride, and iridium films. It is shown that the use of metal compounds with different ligands (zinc and manganese) enables production of zinc sulfide films in which manganese ions are uniformly incorporated into the zinc sulfide crystal lattice to substitute zinc at the lattice sites. For the films of simple and mixed cadmium, copper, and zinc sulfides, the film structure depends on the type of substrate. The thin layers of mixed cadmium and zinc sulfides are asubstitution solution with a hexagonal structure. The thin layers of boron nitride produced from borazine exhibit a nanocrystalline structure and are a mixture of cubic and hexagonal phases. Composite layers were produced from alkylamine boranes and their mixtures with ammonia. Depending on synthesis conditions, the layers are mixtures of hexagonal boron nitride, carbide, and carbonitride or pure boron nitride. Using silyl derivatives of asymmetric dimethylhydrazine containing Si—N and C—N bonds in the starting molecule, we produced silicon carbonitride films whose crystal habit belongs to a tetragonal structure with lattice parameters a = 9.6 and c = 6.4 . The iridium films obtained by thermal decomposition of iridium trisacetylacetonate(III) on quartz substrates in the presence of hydrogen have a polycrystalline structure with crystallite sizes of 50 to 500 . A method for determining grainsize composition was proposed, and grain shapes for the iridium films were analyzed. The influence of substrate temperature on the internal microstructure and growth of the iridium films is demonstrated. At the iridium–substrate interface, a transition layer forms, whose composition depends on the substrate material and deposition conditions.     

分散溶剂对PEMFC催化层中超薄Nafion离聚物质子传导的影响

质子交换膜燃料电池(PEMFC)商业化应用的瓶颈仍然是贵金属催化剂导致的成本问题。然而,目前对于催化层中纳米尺度全氟磺酸离聚物(以Nafion为代表)薄膜中质子传导的问题研究不足,无法完善三相界面的成型规律,进而指导催化层设计。在催化层浆料制备过程中,分散溶剂对Nafion的分散形态有直接影响,可能对催化层成型后附着在催化剂颗粒表面Nafion薄膜的微观结构有潜在影响,进而影响Nafion薄膜的质子传导能力。因此,在本文中利用分子自组装技术模拟催化层离聚物薄膜的聚集过程,于模型基底上制备厚度精确可控的纳米尺度Nafion薄膜,并通过微观测试表征技术探索并建立纳米尺度Nafion离聚物的微观结构模型,阐明分散溶剂对Nafion薄膜微观结构及质子传导的影响。研究发现Nafion薄膜在纳米尺度下的质子电导率比体相膜的质子电导率低一个数量级,使用介电常数较小的醇类溶剂可以使Nafion薄膜形成更有利于质子传导的微观结构,使Nafion薄膜的质子电导率得到提高。相关研究结果为优化PEMFC催化层结构,改善PEMFC催化层中质子传导问题提供给了依据。     

Synthesis, morphology and specific magnetization of the electrodeposited Zn-Ni-P thin films on copper substrate from non-cyanide electrolyte

Thin films of Zn-Ni-P on a copper substrate were synthesized by electrodeposition from chloride baths. It was found that the diffraction reflections of the crystal structure of Zn-Ni-P thin layers occur at thicknesses d ≥ 5 µm. The X-ray diffraction studies results confirm the formation in the Zn-Ni-P films of ZnNi₁₀P₃ compound. The morphology of the obtained films was analyzed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS). The films are continuous and have a typical topography with many homogeneous globular features. EDS confirmed the formation of Zn-Ni-P coating only in 2 samples with Zn:Ni:P atomic ratios of 1:8:4 and 4:8:3, respectively. X-ray Photoelectron Spectroscopy (XPS) revealed the chemistry and the thickness of the studied thin films. At room temperature and thickness d ≥ 5 µm the investigated thin layers exhibit high values of the specific magnetizations in the range (25–37) A m² kg^?1, leading to the potential use in devices, appliances and electronics. The Curie temperature values of the synthesized Zn-Ni-P films were determined. It was found that by heating Zn-Ni-P thin layers of thicknesses d ≥ 5 µm up to a temperature T=900 K an interaction was detected with the copper substrate leading to a lower specific magnetization.      

Stretchable Gas Barrier Achieved with Partially Hydrogen‐Bonded Multilayer Nanocoating

Super gas barrier nanocoatings are recently demonstrated by combining polyelectrolytes and clay nanoplatelets with layer‐by‐layer deposition. These nanobrick wall thin films match or exceed the gas barrier of SiO_x and metallized films, but they are relatively stiff and lose barrier with significant stretching (≥10% strain). In an effort to impart stretchability, hydrogen‐bonding polyglycidol (PGD) layers are added to an electrostatically bonded thin film assembly of polyethylenimine (PEI) and montmorillonite (MMT) clay. The oxygen transmission rate of a 125‐nm thick PEI‐MMT film increases more than 40x after being stretched 10%, while PGD‐PEI‐MMT trilayers of the same thickness maintain its gas barrier. This stretchable trilayer system has an OTR three times lower than the PEI‐MMT bilayer system after stretching. This report marks the first stretchable high gas barrier thin film, which is potentially useful for applications that require pressurized elastomers.

     

Magnetostatic Coupling in CoFe2O4/Pb(Zr0.53Ti0.47)O3 Magnetoelectric Composite Thin Films of 2-2 Type Structure

CoFe₂O₄/Pb(Zr_0.53Ti_0.47)O₃ (CFO/PZT) magnetoelectric composite thin films of 2-2 type structure had been prepared onto Pt/Ti/SiO₂/Si substrate by a sol-gel process and spin coat-ing technique. The structure of the prepared thin film is substrate/PZT/CFO/PZT/CFO. Two CFO ferromagnetic layers are separated from each other by a thin PZT layer. The upper CFO layer is magnetostatically coupled with the lower CFO layer. Subsequent scan-ning electron microscopy (SEM) investigations show that the prepared thin films exhibit good morphologies and compact structure, and cross-sectional micrographs clearly display a multilayered nanostructure of multilayered thin films. The composite thin films exhibit both good magnetic and ferroelectric properties. The spacing between ferromagnetic layers can be varied by adjusting the thickness of intermediate PZT layer. It is found that the strength of magnetostatic coupling has a great impact on magnetoelectric properties of composite thin films, i.e., the magnetoelectric voltage coefficient of composite thin film tends to increase with the decreasing of pacing between two neighboring CFO ferromagnetic layers as a result of magnetostatic coupling effect.     

Amorphous iron formation due to low energy heavy ion implantation in evaporated <Superscript>57</Superscript>Fe thin films

Thin films prepared by vacuum evaporation of ⁵⁷Fe and subsequent low energy ion implantation were investigated by conversion electron Mössbauer spectroscopy and AFM measurements. A sextet with Mössbauer parameters of δ = 0.1 mm/s and B = 26 T appearing in the CEM spectra was identified as amorphous iron. Passivation and phosphonation of the thin films revealed the high affinity of amorphous iron in chemical reactions.     

Quartz crystal microbalance electrode modified with thermoresponsive crosslinked and non-crosslinked <Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide polymers. Response to changes in temperature

Electrochemical quartz crystal microbalance (EQCM) electrode was modified with environmentally sensitive polymers. The polymer layers on the electrode were composed of either crosslinked or non-crosslinked thermoresponsive poly(N-isopropylacrylamide). For anchoring thin gel films on the electrode surface, the electrochemically induced free radical polymerization (EIFRP) was employed. The electroreduction of the peroxydisulfate anion led to generation of free radical. This radical initiated the free radical polymerization process that led to the formation of a thin gel layer attached to the electrode surface. To monitor in situ the growth of the polymer film the changes in resonant frequency of the quartz crystal were recorded. A significant decrease in the frequency (growth of the layer) was seen in the potential range where the reduction of peroxydisulfate anion took place. The morphology of the layers was examined with a scanning electron microscopy (SEM). The phenomenon of volume phase transition (shrinking/swelling process) in the gel layers initiated by a change in temperature was investigated. Unexpected big, sharp, and of negative sign minima appeared at the change-in-frequency vs. temperature plots. These minima were not seen in the plots obtained for the polymers without linker. That situation should be useful in the investigation of chemical interactions proceeding under the conditions of volume phase transition. The influence of volume phase transition on the transport of a member of a model red-ox system, ferro- and ferricyanide couple, and therefore on height of its voltammetric response was examined. The changes in electrochemical properties of the layers induced by volume phase transition were monitored with electrochemical impedance spectroscopy.     

Micro-morphological investigations on wettability of Al-incorporated c-Si thin films using statistical surface roughness parameters

The tunable surface properties of Al-incorporated c-Si and/or homogeneous c-Si (i.e., absorber layer) thin films are investigated with the help of 3D surface topography, statistical analysis, and contact angle measurement. The absorber layers are developed by ion irradiation on c-Al/a-Si films, which results the crystallization of Si in bilayer films, and the top unreacted Al layers were chemically etched off by wet selective etching. The 3D surface topography and statistical analysis is performed on the atomic force microscopy images of the absorber film surface. The analyses suggest that the surfaces are highly complex and irregular isotropic. The surface roughness and irregularity is found to be decreasing with increasing ion fluence. Variation of contact angle with statistical parameters suggest that the wettability of the absorber surface strongly depends on the surface statistical parameters. The surfaces are hydrophobic in nature, and hydrophobicity is found to decrease with increasing ion fluence. The hydrophobic nature of low reflective absorber surface suggests that the film may be useful as a photon absorber layer for advance solar cell applications.     

Cross‐Linked Multilayers of Poly(vinyl amine) as a Single Component and Their Interaction with Proteins

Novel multilayer thin films that consist solely of cross‐linked single component layers are generated by a selective cross‐linking of the poly(vinyl amine) (PVAm) layers in [PVAm/poly(acrylic acid) (PAA)]_n thin films constructed either on silica particles or silicon wafers, followed by the removal of PAA. The surface topography of the (PVAm)_n multilayer thin films, before and after the adsorption of human serum albumin (HSA), has been studied by atomic force microscopy on the freeze‐dried films. The decrease of the average roughness of the film after the adsorption of HSA showed the protein was adsorbed into the (PVAm)_n film making these films potential reservoirs for proteins.

     

Development of Heteropolysiloxane Coatings on Electrogalvanized Steel

The development of heteropolysiloxane coatings on electrogalvanized steel by sol-gel processing has been studied from the sol state to the solid state using techniques such as 29Si NMR, SIMS, XPS, and the three point flexure test. It was possible, from the results obtained, to propose a simplified model for the coatings which brings into play two layers of differing molecular structure: an extremelly thin internal layer and an outer layer, respectively called the anchoring and volume layers.     

Layer‐by‐Layer Spin Self‐Assembled Hole Injection Layers Containing a Perfluorinated Ionomer for Efficient Polymer Light‐Emitting Diodes

Deposition of hole injection layers including a perfluorinated ionomer has been demonstrated using layer‐by‐layer spin self‐assembly for enhanced device efficiency and lifetime in PLEDs. We show that the LBL spin self‐assembled thin films enable to control work functions of indium‐tin oxide anodes by changing the PFI concentration and that a resulting green‐emitting device has an enhanced luminescence efficiency and 18 times longer half lifetime than a device using a conventional HIL. We also fabricate a gradient of energy levels by the LBL self‐assembly of the PFI that results in a work function of 5.74 eV, which can be used to improve carrier injection even for an emitting layer whose ionization potential is over 5.7 eV.

     

Molecular characteristics and surface layer structure of poly(siloxane imides)

The effects of spontaneous ordering of molecular chains of poly(siloxane imide) block copolymers in the surface layers of thin films on glass and gold supports have been studied by the oblique polarized beam and photoelasticity methods. The effective thermodynamic rigidity of molecular chains of the block copolymers (the statistical segment length) has been found to be A = 10.4 × 10^?7 cm. The orientational ordering of molecular chains in poly(siloxane imide) surface layers is characterized by small values of the orientational order parameter (S ₀ ～ 0.007). This finding is explained by the microphase separation of the block copolymers. The evaporated gold layer contributes to the effect of surface birefringence owing to formation of the ordered system composed of islets—clusters of gold atoms.     

Combinatorial Mapping of Substrate Step Edge Effects on Diblock Copolymer Thin Film Morphology and Orientation

We have used a combinatorial gradient technique to map precisely how the terrace structure and microdomain lattice alignment in a thin film of a sphere‐forming diblock copolymer are affected by both the thickness of the copolymer film and the height of a series of parallel step edges fabricated on the substrate. We find that for film thicknesses slightly incommensurate with integer numbers of sphere layers, the step edges act as nucleation sites for regions with one more or one fewer layers of spheres. We also find that for our system, the hexagonal lattice formed by a single layer of spheres on the low side of a step edge is aligned along the direction of the step edge only where the film on the high side is sufficiently thin to support only a wetting layer of copolymer material. This work will guide the tuning of film thickness and step height in future studies and applications of graphoepitaxy in block copolymer films.

     

Electrodeposited carbon-supported nickel sulfide thin films with enhanced stability in acid medium as hydrogen evolution reaction electrocatalyst

A single-step electrochemical deposition of NiS thin films incorporating various carbon nanomaterials as support is described. Advantages of this method are as follows: It is simpler and can be easily scaled up, the precursors employed are cheaper, and the deposition method is energy effective requiring no further heat treatments. Benefits of carbon nanomaterials as catalyst support are manifold including high conductivity and stability. The carbon-supported thin films exhibit high hydrogen evolution activity, low Tafel slopes, and improved double layer capacitance. A remarkable enhancement in the stability of the thin films in the acid medium has been observed. Specifically, NiS/carbon nanofibers have shown the highest activity, lowest Tafel slope, and retained more than 90% of its initial activity after the stability tests.

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Graphical abstract NiS/carbon thin films were fabricated through a highly energy-efficient method as active and highly stable electrocatalysts in acid medium for hydrogen evolution reaction.

     

Synthesis of Bi2O3 and Bi4(SiO4)3 Thin Films by the Sol-Gel Method

Bi2O3 thin films were prepared by dipping silica slides in ethanolic solutions of tris(2,2-6,6-tetramethylheptane-3, 5-dionato)bismuth(III) [Bi(dpm)3] [1] and heating in air at temperatures 500°C. Bi4(SiO4)3 homogeneous thin films were obtained from the reaction of the bismuth oxide coating with the silica glass substrate at temperatures higher than 700°C. For heat treatments at temperatures between 600°C and 700°C, Bi2SiO5 coatings were obtained. The composition and microstructure evolution of the films were determined by Secondary Ion-Mass Spectrometry (SIMS), X-Ray Photoelectron Spectroscopy (XPS) and Glancing Angle X-Ray Diffraction (GA-XRD). The synthesis procedure was reproducible and allowed the control of the Bi2O3 phase composition. Moreover, the thin film annealing parameters were correlated with the formation of bismuth silicates, among which Bi4(SiO4)3 (BSO) is very appealing for the production of fast light-output scintillators [2].     

Sol–gel titania coating on unmodified and surface-modified polyimide films

Sol–gel coating of metal oxides on polymer substrates is a useful process to fabricate various organic–inorganic hybrid materials under mild conditions. However, this process is hardly applicable to pristine polyimide (PI) films because their surfaces do not display effective functional groups for metal oxide coatings. In this study, we firstly examined direct sol–gel coating of titania thin layers on unmodified PI film surfaces. The results confirmed homogeneous, ultrathin titania layer coating and showed that the thickness and microscopic morphology of the titania layers were affected by titanium alkoxide concentrations in the spin coating solutions. We next investigated titania layer coating on surface-modified PI films that prepared using alkaline hydrolysis, which generated carboxylic acid groups on the film surfaces. Optimal hydrolysis time was determined using FT-IR spectroscopy and contact angle measurements. After sol–gel titania coating on the hydrolyzed PI film surfaces, the Scotch tape test was conducted to evaluate adhesion strength between the titania layers and PI film surfaces. Morphological observations of the sample surfaces after the tests clearly showed that surface modification of PI films increased titania layer adhesions. Effect of hydrothermal treatments on film formability and adhesion strength between titania-PI film interfaces was also evaluated.     

Surface-near analyses of ultra thin silicon nitride layers by NRA, channeling RBS, FT IR ellipsometry and AFM

Homogeneous ultra thin silicon nitride layers (SiN_x layers) close to the surface have been produced by 10 keV ¹⁵N ₂ ⁺ molecular ion implantation and an ion current density of 10 A/cm², into single crystal silicon at room temperature. Stoichiometric SiN_x layers with thicknesses of about 28 nm (analyzed by NRA) were obtained at fluences of 1.5×10¹⁷ at/cm². NRA analyses of samples annealed by EB-RTA at T=1150° C for 15 s indicated that the N/Si ratio and the layer thickness did not change drastically. FT IR ellipsometry analyses indicated the existence of Si₃N₄ bonds in as-implanted specimens. A disordered Si layer (d-Si, typically 15 nm thick) underneath the implantation region caused by the ion implantation was found by channeling RBS analyses. The d-Si layer partly recrystallized during EB-RTA showing a thickness of 6 nm afterwards. The SiN_x layers showed no decomposition and detachment after EB-RTA. Due to EB-RTA, however, the smooth surface of the as-implanted specimens changed into a surface with remaining whisker-like structures surrounded by circular recesses as shown by AFM analyses. A model for the growth of these whisker-liker structures caused by low energy ion implantation and EB-RTA is presented on the basis of the thickness of the SiN_x layer, the existence of the d-Si layer and the special annealing process.