Low-temperature preparation of anatase thin films on tantalum

Titanium dioxide thin films were grown on oxidized Ta surfaces using a cyclic layer-by-layer wet chemistry method: successive-ionic-layer-adsorption-and-reaction (SILAR). Film thicknesses varied monotonically and approximately linearly with the number of cycles. As-grown (AG) films were amorphous and rougher (16.2 nm root-mean-square (rms)) than the Ta substrate (10.2 nm rms). After hydrothermal annealing (AN) at a remarkably low temperature of 393 K, the films exhibited anatase crystallites (10 nm dimensions) and reduced roughness (11.8 nm rms). The atomic composition of both AG and AN films was consistent with that of TiO2 containing no more than 4 atom % carbon. A small Si impurity (<1 atom %) was eliminated by using polypropylene beakers and sample holders in the SILAR steps.     

Detection of mechanical effects of adhesive thin films on substrate using the modulated-temperature dilatometry (MT DIL)

The work is aimed to develop the diagnostic method for testing the state of surface coated with the wear-resistant films. Thin wear-resistant ceramic films based on titanium such as TiN, TiCN, TiAlN are deposited on working surface of cutting tools or machine elements in order to improve their tribological properties. The operation life depends mainly on the residual stresses occurring in films and the kinetics of their relaxation as a function of temperature and time. The value of the stresses is influenced by the technological conditions of film deposition and the physical and chemical properties of the substrate and film. The paper has demonstrated the usability of the modulated-temperature dilatometry (MT DIL) for recording the changes in mechanical effects of the adhesive film on the substrate as a function of temperature and time. The substrates where in the shape of cylindrical rod, 30 mm length and 3 mm diameter and of the ribbon 30 mm in length, 2 mm in wide and 120 μm thick. The thickness of the coatings was from 2 to 3 μm. The films deposition were performed using the physical vapour deposition (PVD) technique.     

纳米二氧化钛粉体及薄膜制备的研究进展

本文对近几年有关纳米二氧化钛粉体及薄膜的制备研究进行综述。重点介绍及评述了以无机钛盐和有机钛盐为前驱体制备纳米二氧化钛粉体及利用自组装方法制备二氧钛薄膜的最新研究成果。对今后研究工作的趋势进行了探讨。     

TEM evidence of ultrastructural alteration on Pseudomonas aeruginosa by photocatalytic TiO2 thin films

The antibacterial efficiency of longwave UV-irradiated TiO(2) thin films as well as the ultrastructural damage on bacterial cells was evaluated using Pseudomonas aeruginosa as a model. The quantitative antibacterial efficiency assays showed a bacterial inhibition in the range of 32-72% at different times of irradiation. Transmission electron microscopy (TEM) was used to detect the effect of irradiation of TiO(2) thin films on the ultrastructure of the bacterial cell in order to reveal possible cellular damage. After 40 min irradiation, an abnormal cellular division was observed: instead of a normal septum, an 'elongated bridge' was formed. At a longer irradiation time, wavy structures all around the outer cell membrane were observed, and also some bubble-like protuberances, which expelled inner material. The mechanism of irreversible bacterial cell damage caused by the photocatalytic effect of TiO(2) could be related to abnormal cell division, aside from the reported physicochemical alteration of the cell membrane.     

Low voltage electrowetting using thin fluoroploymer films

This paper investigates the nonideal electrowetting behavior of thin fluoroploymer films. Results are presented for a three phase system consisting of: (1) an aqueous water droplet containing sodium dodecyl sulfate (SDS), (2) phosphorous-doped silicon topped with SiO2 and an amorphous fluoroploymer (aFP) insulating top layer on which the droplet is situated, and (3) a dodecane oil that surrounds the droplet. The presented measurements indicate that the electrowetting equation is valid down to a 6 nm thick aFP film on a 11 nm thick SiO2. At this dielectric thickness, a remarkable contact angle change of over 100 degrees can be achieved with an applied voltage less than 3 V across the system. The data also shows that for this water/surfactant/oil system, contact angle saturation is independent of the electric field, and is reached when the surface energy of the solid-water interface approaches zero.     

Low-temperature preparation of highly conductive thin films from acrylic acid-stabilized silver nanoparticles prepared through ligand exchange

The preparation of AcA-stabilized Ag nanoparticles and its application to make highly conductive thin films are reported. The AcA-stabilized Ag nanoparticles were prepared through a ligand exchange of original oleylamine (OLA)-coated Ag nanoparticles with acrylic acid (AcA), which acted as both an antisolvent and a modifying ligand during the ligand exchange process. Efficiencies of the ligand exchange as well as the properties of Ag nanoparticles were analyzed using various techniques including TEM, FT-IR, XPS, TGA, and UV-vis methods. The thin films were fabricated by annealing spin-coated AcA-stabilized Ag nanoparticles. Further, the effects of annealing temperature, time, and film thickness on both the film morphology and electrical conductivity have been investigated. In this work, due to the low boiling temperature of stabilizer (AcA) and adjustment of annealing conditions, high electrical conductivity was obtained for the Ag thin films. For example, when annealing at 175 °C for 30 min, a 70 nm thick film showed a maximum electrical conductivity of 1.12 × 10(5) S cm(-1). A conductive layer on a flexible polymer substrate (e.g., PET) sheet has been successfully prepared by annealing a spin-coated film at 140 °C for 30 min. The combined advantages of long-term stability of the AcA-stabilized Ag nanoparticles, low annealing temperature, and high conductivity of the prepared thin films make this relatively simple method attractive for applications in flexible electronics.     

Oriented thin films from soluble polythiophenes

The degree of orientation of thin films of eight different polymeric structures, belonging to the class of soluble polyalkylthiophenes (PATs) has been studied. Thin films of the polymers, obtained by spin coating onto glass substrates, were oriented by means of the rubbing technique. The degree of orientation is related to the regioregularity of the system: highly regioregular polymers can be oriented, while regiorandom materials are not oriented. The degree of orientation can be improved by thermal annealing of the oriented films. As a result of annealing, which was performed at different temperatures according to the thermal behavior of the polymers, it was possible to increase the polarization ratio for poly(3-decylthiophene) up to 12–13 as detected from the UV-vis spectra in polarized light. Moreover in the investigated PATs, both the key role of molecular weight and its distribution for achieving a high orientation degree has been assessed. Copyright © 2003 John Wiley & Sons, Ltd.     

Oligosilsesquioxanes as versatile building blocks for the preparation of self-assembled thin films

A self-assembly approach to the preparation of nanocomposite siliceous thin films by using oligosilsesquioxanes as building blocks is presented. Poly(styrene-4-sulfonate), PSS, and octa(3-aminopropyl)silsesquioxane, NSi8, were layer-by-layer (LbL) assembled onto planar substrates and polystyrene (PS) particles, thus forming composite multilayers. We have clarified the binding properties of NSi8 to PSS by examining the pH influence on film buildup by microelectrophoresis (zeta-potential) and quartz crystal microgravimetry (QCM). The regular growth of PSS/NSi8 multilayers on planar supports was confirmed by surface plasmon resonance (SPR) spectroscopy and QCM. By applying the LbL coating procedure to spherical templates, we prepared compact, microporous hollow silica spheres by calcining PS spheres coated with (poly(allylamine hydrochloride) (PAH)/PSS)(2)/(NSi8/PSS)(n) (n varying from 3 to 12), at 750 degrees C, because of sintering of the octameric clusters (NSi8). Hollow spheres derived from coatings with n = 3 drastically altered in size (relative to the template core), depending on the size of the PS particles used. The novelty of this method for the nanofabrication of siliceous films stems from the use of well-defined and discrete building blocks, such as NSi8, leading to homogeneous organic-silica composite films as well as individual siliceous particles of variable size and shape.     

Photopatterning in poly-L-lysine thin films using UV-enhanced hydrophilicity

Deep UV lithography on poly-L-lysine thin films was used to generate microarrays with enhanced hydrophilicity. This was manifested as adsorption of ambient humidity from air by areas exposed to UV fluence around 5 J/cm2 and was made visible by phase-contrast microscopy. Kinetics of adsorption was investigated by a novel technique involving fabrication of submicrometer hydrophilicity grating by two-beam UV interferometry. In an aqueous colloidal medium, gold and polystyrene microspheres preferentially attach to areas that are relatively less hydrophilic, i.e., those areas not exposed to UV light. This observation provides a method for fabricating micro- and nanoporous arrays with controlled porosity. The technique is demonstrated with microspheres of sizes between 250 nm and 10 microm.     

Hydrogen profiling in thin films using coincident ERD

By using the coincident measurement, an ERD method has been established and used for hydrogen profiling in thin foils. In the present study, 6 MeV has been used as incident particle, the scattered and the recoiled proton from one collision were coincidentally detected at 150 (proton) and 173.9 (). This method has been used for hydrogen profiling of 5.6 m Mylar and 8.6 m aluminium foils. Because of the coincident measurement, the background is largely reduced, and its minimum detection limit is about 0.5% (atomic), lower than the conventional ERD method. The measured depth resolution in 5.6 m Mylar is 0.6 m. It is possible to use this method for hydrogen profiling in thin foils of several micron thickness.     

Creation of highly functional thin films using electrochemical nanotechnology

This overview describes the results of our recent study of the application of electrochemical nanotechnology to the fabrication of magnetic recording materials, interconnects in ultra-large-scale integrated (ULSI) devices, energy storage materials, and on-chip biosensors. It is important to note that electrochemical processes play significant roles in developing and fabrication such sophisticated materials and devices. In the field of magnetic recording, electrodeposition methods for preparing CoNiFe and CoFe soft magnetic thin films with a high saturation magnetic flux density were newly developed, and the significant issues for obtaining those films are highlighted. In the area of ULSI interconnects, we developed a technique using a self-assembled monolayer (SAM) for direct bonding of the interconnect layer to SiO2, and proposed a novel electroless deposition method for fabricating a diffusion barrier layer. In the field of batteries, electrodeposited SnNi alloy was proposed as a future anode material for Li batteries, and electrochemical MEMS processes were shown to be useful for fabricating micro-sized direct methanol fuel cells (DMFCs) as portable batteries for electronics applications. In the area of chemical sensors, we developed a new process for fabricating field effect transistors (FETs) modified with SAMs for on-chip biosensing applications.     

Protein UTLC-MALDI-MS using thin films of submicrometer silica particles

Slides for ultra thin-layer chromatography (UTLC) were made by coating nonporous silica particles, chemically modified with polyacrylamide, as 15 μm films on glass or silicon. Three proteins, myoglobin, cytochrome c and lysozyme, are nearly baseline resolved by the mechanism of hydrophilic interaction chromatography. A plate height as low as 3 μm, with 3900 plates, is observed in 14 mm. Varying silica particle diameter among 900, 700 and 350 nm showed that decreasing particle diameter slightly improves resolution but slows the separation. Matrix-assisted laser desorption/ionization (MALDI)-MS of the proteins after separation is demonstrated by wicking sufficient sinapinic acid into the separation medium.     

Visualization of latent fingerprints using Prussian blue thin films

Herein,a facile and effective approach was proposed for visualizing latent fingerprints(LFPs) on two kinds of conductive surfaces by spatially selective electrochemical deposition of Prussian blue(PB) thin films.This strategy exploited the fingerprint residue as an insulating mask and the PB thin films were only generated on the bare surface including the valleys between the papillary ridges,which produced a negative image of LFPs with high resolution up to the third level information.The surface morphology of PB films was characterized by the field emission scanning electron microscopy(FE-SEM).This enhancement technique showed promising performance in selected materials of practical interest.     

Sulfated glycopolymer thin films - preparation, characterization, and biological activity

The impact of heparinoid characteristics on model surfaces obtained from immobilization of sole sulfate groups as well as sulfated glycosides, sulfated cellulose, and definite heparin has been investigated. The obtained layers were physico-chemically characterized regarding film thickness, chemical composition, wettability, and surface morphology. Antithrombin adsorption, studied by fluorescence labeling, revealed a strong dependence on the presence of glycosidic structures and on the molecular weight of the grafted saccharide. On contact with whole blood, the coatings resulted in a diminished plasmatic and cellular coagulation in vitro, which did not reflect well the antithrombin binding. Therefore, more complex activating pathways are discussed.     

Rapid preparation of smooth nanocellulose films using spray coating

Spraying of nanocellulose (NC) on a solid surface to prepare films is an alternative technique to vacuum filtration, which requires a long drainage time and produces films which can sometimes be difficult to separate from the filter. This letter reports a rapid preparation technique for nano-cellulose films using a bench scale system spray coating nanocellulose suspension onto stainless steel plates. After spraying NC suspension onto a smooth steel plate travelling on a constant velocity conveyor, the films can be dried directly on the plates using standard laboratory procedures, saving processing time and effort. By adjusting the suspension consistency, we were able to reproducibly make films with a basis weight ranging from 52.8 ± 7.4 to 193.1 ± 3.4 g/m² when spraying on to a plate moving at a velocity of 0.32 cm/s. The operator preparation time for the nanocellulose film was 1 min, independent of the sample basis weight, which compares to production times reported in the literature of 10 min using filtration techniques. The films made by spray coating showed higher thickness, but comparable uniformity, to those made by vacuum filtration. Optical profilometry measurements showed that over a 1 cm × 1 cm inspection area that the surface roughness (RMS) of the NC film is only 389 nm on the spray coated side in contact with the steel plates, compared to 2087 nm on the outside surface. Thus, the reduction in preparation time for producing the nanocellulose film recommends this spray coating technique as a rapid and flexible method to produce NC films at the laboratory scale.     

A wet chemical preparation of transparent conducting thin films of Ga-doped ZnO nanoparticles

Crystalline gallium doped zinc oxide (GZO) nanopowders were synthesized using hydrothermal treatment processing. The doping concentration affected the phase structure as well as the shape of the nanopowder from nano rod-like structure to nanoparticulate one. The specific BET surface area increases with increasing the gallium doping concentration. Transparent conducting films were deposited on borosilicate glass substrate by spin coating using sols containing GZO nanoparticles dispersed in 1-propanol. The films are crystalline with a hexagonal structure. The effect of Ga doping concentration, sintering temperature and thickness of the layers has been investigated. The lowest resistivity achieved was 6.4 × 10^?2 Ω cm for a thickness of 150 nm. The films present a transmittance in the visible range as high as 90 %.     

Colored thin films prepared from hydrogel microspheres

Ordered 2-D structures composed of poly(N-isopropylacrylamide) (PNIPAM) microgel particles that had regularity on a sub-micrometer length scale were prepared. By using sterically stabilized PNIPAM microgel particles as components, the ordered array was formed by a self-assembly process. The particle array was prepared by depositing a droplet of the microgel dispersion on a substrate. Atomic force microscopy observation of the resulting thin films revealed that they comprised a monolayer particle array. The periodic structure of the array produced iridescent colors due to optical diffraction. Since a homogeneous particle array can be prepared simply by drying the dispersion, this particle dispersion may be considered as a new ink whose color is generated from the microstructure in the films produced.     

Sol–gel preparation and properties of hydroxypropylcellulose–titania hybrid thin films

Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC₃H₇ ⁱ )₄ was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO₂/(HPC + TiO₂) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC₃H₇ ⁱ )₄ is converted into TiO₂. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where cracking did not occur at higher HPC contents even when the substrate was bent.     

Elastic properties of thin adhesive interlayers

The effect of the geometrical and physical parameters of the filler (substrate) and the polymer matrix (adhesive) on the modulus of elasticity of discrete models of composites and adhesive compounds is studied. Emphasis is placed on investigation of the elasticity of the layer of adhesive (binding agent) positioned between hard substrates. Elasticity moduli of the epoxy polymer in the state of a thin layer and in the block (in the form of a free rod) upon their simultaneous fabrication in the process of polymer curing are compared. The results of theoretical solution of the problem of the dependence of the interlayer elasticity modulus and the layered composite on thickness, Poisson’s ratios, elasticity moduli, and other parameters of the adhesive and the substrate are presented. The solution in the closed form was obtained owing to the application of the contact-layer method.