Applications of Single-site Photocatalysts to the Design of Unique Surface Functional Materials

The isolated and tetrahedrally coordinated metal oxide (Ti, V, Cr, Mo and W-oxides) moieties can be included in the silica matrixes of silica-based microporous zeolite and mesoporous silica materials and named as “single-site photocatalysts”. Under UV-light irradiation these single-site photocatalysts form the charge transfer excited state, i.e., the excited electron–hole pair state which is located quite near to each other in different from the manner observed on semiconducting materials such as TiO₂, and play a significant role in various photocatalytic reactions. These single-site photocatalysts not only can promote photocatalytic reactions but also can be utilized to synthesis of functional materials. The nano-sized metal catalyst and visible-light sensitive binary oxide photocatalyst can be synthesized on the excited single-site photocatalyst under UV-light irradiation. The transparent mesoporous silica thin film with single-site photocatalyst generates the super-hydrophilic surface. In this review, our recent applications of single-site photocatalysts to synthesis of the surface functional materials have been introduced.     

Chemical solution processing and characterization of Ba(Zr,Ti)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> layered thin films

Ba(Zr,Ti)O₃/LaNiO₃ layered thin films have been synthesized by chemical solution deposition (CSD) using metal-organic precursor solutions. Ba(Zr,Ti)O₃ thin films with smooth surface morphology and excellent dielectric properties were prepared on Pt/TiO _x /SiO₂/Si substrates by controlling the Zr/Ti ratios in Ba(Zr,Ti)O₃. Chemically derived LaNiO₃ thin films crystallized into the perovskite single phase and their conductivity was sufficiently high as a thin-film electrode. Ba(Zr,Ti)O₃/LaNiO₃ layered thin films of single phase perovskite were fabricated on SiO₂/Si and fused silica substrates. The dielectric constant of a Ba(Zr_0.2Ti_0.8)O₃ thin film prepared at 700°C on a LaNiO₃/fused silica substrate was found to be approximately 830 with a dielectric loss of 5% at 1 kHz and room temperature. Although the Ba(Zr_0.2Ti_0.8)O₃ thin film on the LaNiO₃/fused silica substrate showed a smaller dielectric constant than the Ba(Zr_0.2Ti_0.8)O₃ thin film on Pt/TiO _x /SiO₂/Si, small temperature dependence of dielectric constant was achieved over a wide temperature range. Furthermore, the fabrication of the Ba(Zr,Ti)O₃/LaNiO₃ films in alternate thin layers similar to a multilayer capacitor structure was performed by the same solution deposition process.     

PZT铁电薄膜底电极制备工艺的研究

利用磁控溅射方法在Si(001)基片上制备Ti/Pt底电极,其厚度大概分别为20、100 nm,其中Ti电极作为缓冲层,随后在上面溅射PZT铁电薄膜.研究了不同电极的制备工艺对电极形貌、取向以及对PZT铁电薄膜的制备带来的影响.结果表明,底电极的溅射温度以及退火温度对于底电极起着至关重要的作用,同时具有良好(111)取向的、致密性较好的底电极对于PZT铁电薄膜的生长具有重要的影响.     

UV-light and visible-light photochromism of inorganic–organic multilayer films based on polyoxometalate and poly(acrylamide)

Novel UV-light and visible-light photochromic inorganic–organic multilayers composed of polyoxometalates (phosphomolybdic acid (PMoA)) and poly(acrylamide) (PAM) were prepared by the layer-by-layer (LbL) self-assembly method. The grown process, composition, surface topography, and photochromic properties and mechanism of the multilayer films were investigated by ultraviolet–visible (UV–vis) spectra, Fourier transform infrared spectra (FT-IR), atomic force microscopy (AFM), electron resonance spectra (ESR), and X-ray photoelectron spectra (XPS). Irradiation with UV-light or visible-light, the transparent films changed from colorless to blue and showed reversible photochromism. PMoA/PAM LbL films had higher photochromic efficiency under UV-light irradiation than visible-light irradiation. The bleaching process occurred when the films were in contact with O₂ in the dark or heated in air. The photochromic process of PMoA/PAM LbL film was in accordance with radical mechanism.     

Preparation of ordered mesoporous TiO2 thin film and its application in methanol catalytic combustion

Ordered mesoporous titania thin films were synthesized by evaporation induced self‐assembly process in the presence of Pluronic block copolymers P123 (EO₂₀‐PO₇₀‐EO₂₀). The influence of several experimental parameters, including aging humidity, aging temperature, substrate properties and methods for organic templates removal, on the mesostructure of titania thin films was investigated in details. The mesoporous titania thin film supported Pt catalyst was prepared, and its methanol catalytic combustion performance was studied. The results showed that mesoporous titania thin film is an active support for catalyst. Mesoporous titania thin film supported platinum catalysts yields 70% methanol conversion at room temperature and 100% conversion at 100 °C. Copyright © 2013 John Wiley & Sons, Ltd.     

Platinum Films with Controlled 3‐Dimensional Nanoscopic Morphologies and Their Effects on Surface Enhanced Raman Scattering

The synthesis of Pt thin films with a controlled nanoscopic architecture that can support surface enhanced Raman scattering (SERS) is reported. The syntheses are achieved by replicating the pores of a type of mesoporous silica thin film whose pore structure could be described as a regular array of vertical channels of ～9 nm in diameter and their interconnections, forming a 3‐dimensional pore network. Electrochemical deposition into the pores followed by the removal of the templates produced Pt films composed of arrays of vertically standing Pt nanorods with narrow gaps between them. The 3‐dimensional nanostructure increases the surface area and enables the Pt film to absorb visible light. SERS studies of rhodamine 6G and benzenethiol on such Pt films as substrates reveals that the control of the nanostructure is critical for the SERS effect.     

The diffusion of Pt in BST films on Pt/Ti/SiO2/Si substrate by sol-gel method

Barium strontium titanate (Ba_0.65Sr_0.35TiO₃) ferroelectric thin films have been prepared by sol-gel method on Pt/Ti/SiO₂/Si substrate. The X-ray diffraction (XRD) pattern indicated that the films were a polycrystalline perovskite structure and the atomic force microscope (AFM) image showed that the crystallite size and the root mean square roughness (RMS) were 90 nm and 3.6 nm, respectively. The X-ray photoelectron spectrum (XPS) images showed that Pt consisting in BST thin films was the metallic state, and the Auger electron spectroscopy (AES) analysed the Pt concentration in different depth profiles of BST thin films. The result displayed that the Pt diffusion in BST thin film is divided into two regions: near the BST/Pt interface, the diffusion type was volume diffusion, and far from the interface correspondingly, the diffusion type became grain boundary diffusion. In this paper, the previous researcher’s result was used to verify our conclusion.     

Comparison of the influence of titanium and chromium adhesion layers on the properties of sol–gel derived NKN thin films

Lead-free (Na_0.5K_0.5)NbO₃ (NKN) thin films were prepared on Pt/X/SiO₂/Si substrates (with the adhesion promoters X = Ti, Cr) by a sol–gel process with and without post-annealing treatment. The effect of the diffusion of the adhesion layer elements Ti and Cr into the NKN film was analysed by secondary ion mass spectrometry, scanning electron microscopy pictures, X-ray diffraction (XRD), and leakage current measurements. It turned out that Cr diffuses into the films to a higher extent than Ti. The high amount of Cr diffusion led to the formation of a secondary phase, as seen in the XRD pattern, and to pore formation on the surface of the NKN films. In contrast, the films with Ti adhesion layer were single phase NKN without pore formation. Also, the leakage current measurements showed a strong influence of the Cr diffusion. The leakage current of the films with Cr adhesion layer was about four orders of magnitude higher than that of the films with Ti adhesion layer. The study shows the strong influence of the adhesion layer of the substrate on the properties of NKN films.     

Preparation and photochromism of Keggin-type molybdphosphoric acid/silica mesoporous composite thin films

Using tetraethoxysilane and 3-aminopropyltriethoxysilane as the silica sources, amino-functionalized organic/inorganic hybrid mesoporous silica thin films with 2-dimensional hexagonal structure have been synthesized by evaporation induced self-assembly process in the presence of cetyltrimethyl ammonium bromide templates under acid conditions. The Keggin-type molybdphosphoric acid (PMo) is incorporated into the mesoporous silica thin films with amino-groups by wetness impregnation, and the PMo/silica mesoporous composite thin films are obtained. The results of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and Fourier transform infrared (FTIR) spectra indicate the PMo molecules maintain Keggin structure and are homogeneously distributed inside mesopores. The composite thin films possess excellent reversible photochromic properties, and change from colorless to blue under ultraviolet irradiation. The photochromic mechanism of the composite thin films is studied by ultraviolet-visible (UV-vis), electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS) spectra. It is shown that intervalence charge transfer (IVCT) and ligand-to-metal charge transfer (LMCT) are the main reasons of photochromism. PMo anions interact strongly with amino-groups of the mesoporous suface via hydrogen bond and electrostatic force. After ultraviolet irradiation, the charge transfer occurs by reduction of heteropolyanions accompanying the formation of heteropolyblues with multivalence Mo(VI, V), and the bleaching process of composite thin films is closely related to the presence of oxygen.     

Magnetoelectric Bi3.25Nd0.75Ti3O12–La0.6Ca0.4MnO3 composite thin films derived by SOL–GEL method

Magnetoelectric (ME) Bi_3.25Nd_0.75Ti₃O₁₂–La_0.6Ca_0.4MnO₃ (BNT–LCMO) composite thin films were deposited on Pt/Ti/SiO₂/Si(100) substrates by a simple SOL–GEL method and spin-coating process with two different deposition sequences: BNT/LCMO/Pt/Ti/SiO₂/Si(BLP) and LCMO/BNT/Pt/Ti/SiO₂/Si(LBP). Our results show the composite thin films exhibit both good ferroelectric and magnetic properties, as well as a ME effect. BLP thin films have larger maximum ME voltage coefficient values than LBP structured thin films. The deposition sequence has a notable effect on the ferroelectric and magnetic properties and ME coupling behavior of the bi-layer thin films.     

纳米ZnO薄膜的制备及其可见光催化降解甲基橙

采用溶胶-凝胶方法制备ZnO透明溶胶, 在铝箔上涂膜后经500 ℃处理制得具有可见光响应的纳米ZnO薄膜光催化剂. 以甲基橙模拟有机污染物, 在可见光下研究了薄膜的降解性能, 结果表明, 用一片有效面积为200 cm2的ZnO/Al薄膜作为催化剂, 甲基橙的降解率达到96.3％, 比ZnO负载在玻璃上制得的ZnO/glass薄膜催化剂活性高得多. 采用扫描电镜与原子力显微镜对ZnO/Al薄膜制备条件进行了表征, 结果发现多孔ZnO/Al薄膜比致密ZnO/Al薄膜具有更高的活性, 实验制备的具有高活性的ZnO/Al薄膜颗粒平均直径为52.2 nm. 采用本方法制备的ZnO/Al薄膜是一种具有应用前景的, 能在可见光下降解有机物的有效光催化剂.     

Mesoporous TiO2−xAy (A = N,S) as a visible-light-response photocatalyst

Mesoporous TiO_2?xA_y (A = N, S) thin films were fabricated using thiourea as a doping resource by a combination of sol-gel and evaporation-induced self-assembly (EISA) processes. The results showed that thiourea could serve two functions of co-doping nitrogen and sulfur and changing the mesoporous structure of TiO₂ thin films. The resultant mesoporous TiO_2?xA_y (A = N, S) exhibited anatase framework with a high porosity and a narrow pore distribution. The formation of the O–Ti–N and O–Ti–S bonds in the mesoporous TiO_2?xA_y (A = N, S) were substantiated by the XPS spectra. A new bandgap in visible light region (520 nm) corresponding to 2.38 eV could be formed by the co-doping. After being illuminated for 3 h, methyl orange could be degraded nearly completely by the co-doped sample under both ultraviolet irradiation and visible light illumination. While pure mesoporous TiO₂ could only degrade 60% methyl orange under UV illumination and showed negligible photodegradation capability in the visible light range. Furthermore, the photo-induced hydrophilic activity of TiO₂ film was improved by the co-doping. The mesoporous microstructure and high visible light absorption could be attributed to their good photocatalytic acitivity and hydrophilicity.     

Preparation of TiO2 Thin Film Photocatalysts by Dip Coating Using a Highly Viscous Solvent

TiO₂ thin film photocatalysts coated onto soda lime glass were prepared by a dip coating process using a highly viscous solvent. The source of the TiO₂ was tetraisopropyl orthotitanate, and -terpineol was used as the solvent. Two types of thin film preparation procedures based on dip coating (a sol-gel system and thermal decomposition system) were used to prepare the samples. TiO₂ thin films were obtained after calcination at 450°C for 1 hour. The film thickness obtained with a single dipping was proportional to the viscosity of the dip coating solutions. The obtained thin films were transparent with a thickness of 1 m. The crystal form of the obtained photocatalyst films was anatase alone. The thin films were formed with aggregated nano-sized TiO₂ single crystals (7–15 nm). The photocatalytic activity of the TiO₂ thin films, as evaluated by the photooxidation of NO (1 ppm) in dry air, was as high as our previous TiO₂ thin films prepared by the sol-gel method.     

The (100) orientation evolution and temperature-dependent electrical properties of Bi(Zn1/2Ti1/2)O3–PbTiO3 ferroelectric films

The 0.2Bi(Zn_1/2Ti_1/2)O₃–0.8PbTiO₃ (0.2BZT–0.8PT) ferroelectric thin film was successfully fabricated on Pt(111)/Ti/SiO₂/Si substrates by a sol–gel method. The result indicates that the film exhibits the (100) preferred orientation and has a relatively dense and uniform microstructure with a thickness of ~230 nm. The formation mechanism of the oriented films was ascribed to the growth of the (100) oriented PbO layer at ~450 °C during a layer-by-layer crystallization process. Temperature-dependent electrical properties of the 0.2BZT–0.8PT films were investigated, showing that the film has a potential for high temperature applications.     

Effect of Pt loading on the photocatalytic reactivity of titanium oxide thin films prepared by ion engineering techniques

Platinum-loaded titanium oxide thin-film photocatalysts were prepared by using an ionized cluster beam (ICB) deposition method and a RF magnetron sputtering (RF-MS) deposition method as dry processes. From the results of the photocatalytic oxidation of acetaldehyde with O₂ under UV light irradiation, small amounts of Pt loading (less than 10 nm film thickness) were found to dramatically enhance the photocatalytic reactivity. However, when TiO₂ thin films were loaded with relatively larger amounts of Pt (more than 30 nm as the film thickness), the photocatalytic reactivity became lower than for the pure TiO₂ thin films. Moreover, investigations of the ratio of Pt loaded onto the surface of the thin film catalysts by XPS measurements revealed that the small amounts of Pt loaded exist as very small clusters working to efficiently enhance the charge separation, whereas, large amounts of Pt covers the entire surface of the TiO₂ thin films, resulting in a decrease of the photocatalytic reactivity.     

Comparison of properties of titanium aluminium nitride film produced by using two different types of Ti–Al target

This work aims to study the influence of two different types of Ti–Al target (sintered and melted) which have same nominal composition (50 at% Ti, 50 at% Al) on the properties of thin films coated by using arc ion plating (AIP) method. The hardness of the melted target was of higher value than that of the sintered target. The property of the film is related to the microstructure and phase analysis of both types of target that have quite different phases. Ti and Al metals were found as major phases and TiAl₂ as minor phase in the sintered target but only TiAl compound was found in the melted target. After film coating at the same operation parameters, it was found that although the phase structures of the sintered and melted targets were quite different, the coated thin films using these targets showed the same phase structure of Ti_0.5 Al_0.5 N. However, the microstructure of films coated by using the sintered target showed higher density of droplets and pores than those of film produced by using the melted target. As a result, the hardness and adhesion strength of thin film produced by using the melted target were slightly higher than those values of film produced by using the sintered target. Copyright © 2009 John Wiley & Sons, Ltd.     

Microstructure and ferroelectric properties of r.f. magnetron sputtering derived PZT thin films deposited on interlayer (PbO/TiO2)

Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO₂/Si and interlayer/Pt/Ti/SiO₂/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb_1.1Zr_0.53Ti_0.47O₃ target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO₂) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (_r=475.97, tanδ=0.0591, P_r=23 μC/cm²). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.     

Highly polarized luminescence from optical quality films of a semiconducting polymer aligned within oriented mesoporous silica

In this Communication, we show that nanometer scale control of semiconducting polymer chain conformation is possible using host/guest chemistry in highly ordered and macroscopically oriented thin films of mesoporous silica. This control leads to a thin film composite material that is optically transparent, densely filled with polymer, and has highly polarized optical properties. Calculations of absorption and emission anisotropies further indicate full incorporation of the polymer into the nanoscale pore spaces. Such materials could serve as a useful tool for further investigations of polymer photophysics, as well as for device applications.     

Remarkable birefringence in a TiO2-SiO2 composite film with an aligned mesoporous structure

Mesoporous titania-silica composite films with highly aligned cylindrical pores are prepared by the sol-gel method using a substrate with structural anisotropy. The strong alignment effect of a rubbing-treated polyimide film on a substrate provides a narrow alignment distribution in the plane of the film regardless of the fast condensation rate of titania precursors. The collapse of the mesostructure upon the surfactant removal is effectively suppressed by the reinforcement of the pore walls with silica by exposing the as-deposited film to a vapor of a silicon alkoxide. The existence of a silica layer on the titania pore wall is proved from the distributions of Ti and Si estimated by the elemental analysis in high resolution electron microscopy. The obtained mesoporous titania-silica composite film exhibits a remarkable birefringence reflecting the highly anisotropic mesoporous structure and the high refractive index of titania that forms the pore wall. The Δn value estimated from the optical retardation and the film thickness is larger than 0.06, which cannot be achieved with the conventional mesoporous silica films with uniaxially aligned mesoporous structure even though the alignment of the pores in the films is perfect. These inorganic films with mesoscopic structural anisotropy will find many applications in the field of optics as phase plates with high thermal/chemical/mechanical stabilities.     

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.