Structure and glass transition of amorphous materials composed of titanium-oxo oligomers chemically modified with benzoylacetone.

Titanium-n-butoxide was hydrolyzed in the presence of benzoylacetone, and the resulting solution was concentrated and dried at 120 or 140 °C to obtain transparent amorphous materials. High-energy X-ray diffraction measurement was conducted at the SPring-8 facility, and the reduced pair distribution function, G(r) was calculated by Fourier transform of the total structure factor, S(Q). The G(r) value suggested that the materials are composed of TiO6 octahedra linked by corner- and edge-sharing. Low temperature thermomechanical analysis (TMA) and differential scanning calorimetry (DSC) were conduced on the materials, where a deflection was detected both in the TMA and DSC curves, revealing the glass transition of the materials. Combined with the previous work based on infrared absorption spectroscopy and gel permeation chromatography, the materials are demonstrated to be a new class of glassy materials composed of linked metal-oxygen polyhedra chelated with organic molecules. The materials are innovative due to the high refractive indices that originate in the metal-oxo oligomers and to the shapability given by their thermoplastic properties.

Comparison of In-Plane Stress Development in Sol-Gel- and Nanoparticle-Derived Mesoporous Metal Oxide Thin Films.

By using an evaporation-induced self-assembly (EISA) process, mesoporous metal oxide thin films are prepared via molecular precursors undergoing a sol-gel transition or by using nanoparticle dispersions as the starting materials. Both methods are employed together with PIB50-b-PEO45 as the structure-directing agent to produce porous TiO2 and ZrO2 thin films with spherical mesopores of around 14 nm in diameter. These nanoparticle- and sol-gel-derived films were investigated in terms of the intrinsic in-plane stress development during the heat treatment up to 500 °C to evaluate the impact of solvent evaporation, template decomposition and crystallization on the mechanical state of the film. The investigation revealed the lowest intrinsic stress for the nanoparticle-derived mesoporous film, which is assigned to the combination of the relaxing effects of the utilized diblock copolymer and the interparticular gaps between the precrystalline nanoparticles. Furthermore, the residual in-plane stress was studied after annealing steps ranging from 300 to 1000 °C and cooling down to room temperature. Here, TiO2 nanoparticle-derived mesoporous films possess a lower residual stress than the sol-gel-derived mesoporous films, while in the case of ZrO2 films, sol-gel-derived coatings reveal the smallest residual stress. The latter is based on the lower thermal expansion coefficient of the dominant monoclinic crystal phase compared to that of the silicon substrate. Hence, the present crystal structure has a strong influence on the mechanical state. The observation in this study helps to further understand the stress-related mechanical properties and the formation of mesoporous metal oxides.

Evaporation-Driven Deposition of ITO Thin Films from Aqueous Solutions with Low-Speed Dip-Coating Technique.

We suggest a novel wet coating process for preparing indium tin oxide (ITO) films from simple solutions containing only metal salts and water via evaporation-driven film deposition during low-speed dip coating. Homogeneous ITO precursor films were deposited on silica glass substrates from the aqueous solutions containing In(NO3)3·3H2O and SnCl4·5H2O by dip coating at substrate withdrawal speeds of 0.20-0.50 cm min-1 and then crystallized by the heat treatment at 500-800 °C for 10-60 min under N2 gas flow of 0.5 L min-1. The ITO films heated at 600 °C for 30 min had a high optical transparency in the visible range and a good electrical conductivity. Multiple-coating ITO films obtained with five-times dip coating exhibited the lowest sheet (ρS) and volume (ρV) resistivities of 188 Ω sq-1 and 4.23 × 10-3 Ω cm, respectively.

Transferability and Adhesion of Sol-Gel-Derived Crystalline TiO2 Thin Films to Different Types of Plastic Substrates.

Anatase thin films were prepared on various plastic substrates by our recently developed sol-gel transfer technique. Polycarbonate (PC), poly(methyl methacrylate) (PMMA), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyether ether ketone (PEEK), and polyvinylidene chloride (PVDC) were employed as plastic substrates. A Si(100) substrate was first coated with a polyimide (PI)/polyvinylpyrrolidone (PVP) mixture layer, and an alkoxide-derived titania gel film was deposited on it by spin-coating. The resulting titania gel film was heated to 600 °C, during which the PI/PVP layer decomposed and the gel film was converted into a 60 nm thick anatase film. The anatase film was then transferred from the Si(100) substrate to the plastic substrate. This was achieved by heating the plastic/anatase/Si(100) stack in a near-infrared image furnace to 120-350 °C, depending on the type of plastic substrate, under unidirectional pressure. The anatase film cracked during transfer to PE, PP, PEEK, and PVDC substrates but did not crack during transfer to PC, PMMA, and PET substrates. The fraction of the total film area that was successfully transferred was assessed with the aid of image analysis. This fraction tended to be large for plastics with C═O and C-O groups and small for those without these groups. The film/substrate adhesion assessed by cross-cut tape tests also tended to be high for plastics with C═O and C-O groups and low for those without these groups. The adhesion to plastics without C═O or C-O groups could be enhanced and their transfer area fraction increased by oxidizing the native plastic surface by ultraviolet-ozone treatment prior to transfer.

Evaporation-Driven Deposition of WO3 Thin Films from Organic-Additive-Free Aqueous Solutions by Low-Speed Dip Coating and Their Photoelectrochemical Properties.

We prepared tungsten trioxide (WO3) photoelectrode films from organic-additive-free aqueous solutions by a low-speed dip-coating technique. The evaporation-driven deposition of the solutes occurred at the meniscus during low-speed dip coating, resulting in the formation of coating layer on the substrate. Homogeneous WO3 precursor films were obtained from (NH4)10W12O41·5H2O aqueous solutions and found to be crystallized to monoclinic WO3 films by the heat treatment at 400-700 °C. All the films showed a photoanodic response irrespective of the heat treatment temperature, where a good photoelectrochemical stability was observed for those heated over 500 °C. The highest photoanodic performance was observed for the WO3 film heated at 700 °C, where the IPCE (incident photon-to-current efficiency) was 36.2% and 4.6% at 300 and 400 nm, respectively.

Spontaneous Pattern Formation Induced by Bénard-Marangoni Convection for Sol-Gel-Derived Titania Dip-Coating Films: Effect of Co-solvents with a High Surface Tension and Low Volatility.

Evaporation-driven surface tension gradient in the liquid layer often causes the convective flow, i.e., Bénard-Marangoni convection, resulting in the formation of cell-like patterns on the surface. Here, we prepared sol-gel-derived titania films from Ti(OC3H7(i))4 solutions by dip coating and discussed the effect of the addition of co-solvents with a high surface tension and low volatility on the spontaneous pattern formation induced by Bénard-Marangoni convection. Propylene glycol (PG, with a surface tension of 38.6 mN m(-1)) and dipropylene glycol (DPG, with a surface tension of 33.9 mN m(-1)) were added to the coating solutions containing 2-propanol (2-Pr, with a surface tension of 22.9 mN m(-1)) for controlling the evaporation-driven surface tension gradient in the coating layer on a substrate. During dip coating at a substrate withdrawal speed of 50 cm min(-1) in a thermostatic oven at 60 °C, linearly arranged cell-like patterns on a micrometer scale were spontaneously formed on the titania gel films, irrespective of the composition of coating solutions. Such surface patterns remained even after the heat treatment at 200 and 600 °C, where the densification and crystallization of the titania films progressed. The width and height of the cell-like patterns increased with increasing PG and DPG contents in the coating solutions, where the addition of PG resulted in the formation of cells with a larger height than DPG.

Superior properties of silica thin films prepared from perhydropolysilazane solutions at room temperature in comparison with conventional alkoxide-derived silica gel films.

Preparation of silica thin films from perhydropolysilazane (PHPS) at room temperature has attracted much attention because it provides a new way to realize silica thin films in a variety of technologies where any high temperature processes should be avoided. Although silica gel films can also be prepared from alkoxides at room temperature by conventional sol-gel method, they are believed to have low mechanical and chemical durability. However, even such alkoxide-derived silica gel films have possibilities to become more durable via condensation reaction and densification when aged at room temperature. In order to clarify whether or not PHPS-derived silica thin films have critical superiority on properties, the hardness and chemical durability were compared between PHPS- and alkoxide-derived silica thin films, where PHPS films were exposed to the vapor from aqueous ammonia at room temperature for PHPS-to-silica conversion. Alkoxide-derived silica gel films were found to be densified and hardened when stored in air at room temperature, which resulted in pencil hardness even higher than 9H on Si(100) substrates. However, the ultra-microindentation tests demonstrated that the PHPS-derived films are definitely harder than the alkoxide-derived ones. The PHPS-derived films were also found to have higher chemical durability in water and in aqueous ammonia. Such higher mechanical and chemical durability of the PHPS-derived films was ascribed to their higher density, i.e., more highly condensed states, which was evidenced in infrared absorption spectra. Hard coating performance on plastic substrates was also studied, and the PHPS-derived films were demonstrated to have much higher adhesive strength on polymethylmethacrylate substrates. The in-plane stress measurement demonstrated that the PHPS-derived films have much lower or even negligible tensile stress, which may be one of the causes for such higher adhesive strength.

Ceramic thin films on plastics: a versatile transfer process for large area as well as patterned coating.

A versatile technique for fabricating ceramic thin films on plastics has been proposed. The technique comprises (i) the deposition of a gel film by spin- or dip-coating on a silicon substrate coated beforehand with a release layer, (ii) the firing of the gel film into a ceramic film, and (iii) its transfer onto plastics by melting or softening the plastics surface. Reflective anatase and electrically conductive indium-tin-oxide (ITO) thin films were prepared on acrylic resin and polycarbonate substrates. Patterned ITO thin films could also be fabricated on plastics by using a mother silicon substrate with periodic grooves.

Spontaneous formation of linearly arranged microcraters on sol-gel-derived silica-poly(vinylpyrrolidone) hybrid films induced by Bénard-Marangoni convection.

Complex, sophisticated surface patterns on micrometer and nanometer scales are obtained when solvent evaporates from solutions containing nonvolatile solutes dropped on a solid substrate. Such evaporation-driven pattern formation has been utilized as a fabrication process of highly ordered patterns in thin films. Here, we suggested the spontaneous pattern formation induced by Bénard-Marangoni convection triggered by solvent evaporation as a novel patterning process of sol-gel-derived organic-inorganic hybrid films. Microcraters of 1.0-1.5 µm in height and of 100-200 µm in width were spontaneously formed on the surface of silica-poly(vinylpyrrolidone) hybrid films prepared via temperature-controlled dip-coating process, where the surface patterns were linearly arranged parallel to the substrate withdrawal direction. Such highly ordered micropatterns were achieved by Bénard-Marangoni convection activated at high temperatures and the unidirectional flow of the coating solution on the substrate during dip-coating.

Spontaneous formation of linear striations and cell-like patterns on dip-coating titania films prepared from alkoxide solutions.

Linear striations and cell-like patterns were spontaneously formed on the dip-coating titania films prepared titanium tetraisopropoxide (Ti(OC(3)H(7)(i))(4)) solutions. Such unique patterns on micrometer scale were arranged parallel to the substrate withdrawal direction. The values of R(Z) (10 point height of irregularities) and S (mean spacing of local peaks) of the patterns increased with increasing film thickness depending on the substrate withdrawal speed for dip-coating, the viscosity of the coating solutions, and the distance from the top edge of films. The shape of patterns changed from linear striations to cell-like patterns with increasing viscosity of the coating solutions. Although the heat treatment at 600 degrees C reduced the height (R(Z)) of stripes and cells without the change in spacing (S), the visibility of patterns was enhanced by the increase in refractive index due to the crystallization of films.

Preparation of silica coatings heavily doped with spiropyran using perhydropolysilazane as the silica source and their photochromic properties.

Silica coatings doped with spiropyran (SP) were prepared using xylene solutions of perhydropolysilazane (PHPS) as the silica source, where the SP-doped PHPS coatings were prepared by spin-coating and the PHPS-to-silica conversion was achieved by exposing the coatings to the vapor from aqueous ammonia at room temperature. The films could be heavily doped with SP at SP/(SP + PHPS) mass ratio as high as 0.2. The as-deposited SP-doped PHPS films were transparent and light-yellow, which turned to red as the PHPS-to-silica conversion proceeded, where the absorbance at 500 nm increased. When the films were stored in air in the dark for 73 h after the exposure treatment, the absorbance at 500 nm further increased, where the film turned from red to dark red. The SP-doped silica coatings thus obtained showed reversible photochromic reaction, where the absorbance at 500 nm decreased and increased when the films were irradiated with visible and ultraviolet light, respectively. The pencil hardness of the films was higher than 9H at a load of 1 kg, while significant amount of SP was leached out when the films were soaked in xylene.

Photoelectrochemical properties of Fe2O3-Nb2O5 films prepared by sol-gel method.

Fe2O3-Nb2O5 coating films of various Nb/(Fe + Nb) mole ratios were prepared on nesa silica glass substrates from Fe(NO3)3.9H2O - NbCl5 - CH3(CH2)2CH2OH - CH3COOH solutions by the sol-gel method. The photoanodic properties were studied in a three-electrode cell with an aqueous buffer solution of pH = 7 as the supporting electrolyte. The crystalline phases identified were alpha-Fe2O3 (Nb/(Fe + Nb) = 0), alpha-Fe2O3 + FeNbO4 (Nb/(Fe + Nb) = 0.25), FeNbO4 (Nb/(Fe + Nb) = 0.5), FeNbO4 + Nb2O5 (Nb/(Fe + Nb) = 0.75), and Nb2O5 (Nb/(Fe + Nb) = 1). When the Nb/(Fe + Nb) mole ratio increased from 0 to 0.25, the crystalline phases changed from alpha-Fe2O3 to alpha-Fe2O3 + FeNbO4, the photoanodic current under white light illumination increased, and the photoanodic current under monochromatized light illumination increased in both visible and ultraviolet regions. When the Nb/(Fe + Nb) ratio increased over 0.25, the crystalline phases changed to FeNbO4, FeNbO4 + Nb2O5, or Nb2O5, and the photoanodic current decreased. The sample consisting of alpha-Fe2O3 and FeNbO4 (Nb/(Fe + Nb) = 0.25) exhibited photoresponse extending to 600 nm and an IPCE of 18% at a wavelength of 325 nm.