Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

Deposition of transparent conductive mesoporous indium tin oxide thin films by a dip coating process

Cetyltrimethyl ammonium bromide (CTAB) templated mesoporous indium tin oxide (ITO) thin films were deposited on quartz plates by an evaporation-induced self-assembly (EISA) process using a dip coating method. The starting solution was prepared by mixing indium chloride, tin chloride, and CTAB dissolved in ethanol. Five to fifty mole percent Sn-doped ITO films were prepared by heat-treatment at 400 °C for 5 h. The structural, adsorptive, electrical, and optical properties of mesoporous ITO thin films were investigated. Results indicate that the mesoporous ITO thin films have an ordered two-dimensional hexagonal (p6mm) structure, with nanocrystalline domains in the inorganic oxide framework. The continuous thin films have highly ordered pore sizes (>20 Å), high Brunauer-Emmett-Teller (BET) surface area up to 340 m²/g, large pore volume (>0.21 cm³/g), outstanding transparency in the visible range (>80%), and show a minimum resistivity of ρ = 1.2 × 10⁻² Ω cm.     

Preparation of regularly structured nanotubular TiO2 thin films on ITO and their modification with thin ALD-grown layers

Nanotubular titanium dioxide thin films were prepared by anodization of titanium metal films evaporated on indium tin oxide (ITO) coated glass. A facile method to enhance the adhesion of the titanium film to the ITO glass was developed. An optimum thickness of 550 nm for the evaporated titanium was found to keep the film adhered to ITO during the anodization. The films were further modified by growing amorphous titania, alumina and tantala thin films conformally in the nanotubes by atomic layer deposition (ALD). The optical, electrical and physical properties of the different structures were compared. It was shown that even 5 nm thin layers can modify the properties of the nanotubular titanium dioxide films.     

Mesoporous indium oxide synthesized via a nanocasting route

The synthesis of crystalline mesoporous indium oxide by using a mesoporous carbon (CMK-3) as hard template is described. Transmission electron microscopy (TEM) exhibits the presence of mesoporous structure in our sample and the corresponding wide-angle X-ray diffraction (XRD) pattern confirmed the crystalline wall of sample. N₂ adsorption measurement exhibits the synthesized crystalline mesoporous indium oxide possesses a specific surface area of 39 m²/g and the total pore volume of 0.17 cm³/g, and the corresponding pore size distribution curve reveals the presence of a mesopore of 7.0 nm in maximum. Our work demonstrates that the maintenance of the ordered structure of carbon template is very significant for obtaining high quality replicas via the nanocasting route.     

Electrical and optical properties of indium tin oxide films prepared on plastic substrates by radio frequency magnetron sputtering

The influence of deposition power, thickness and oxygen gas flow rate on electrical and optical properties of indium tin oxide (ITO) films deposited on flexible, transparent substrates, such as polycarbonate (PC) and metallocene cyclo-olefin copolymers (mCOC), at room temperature was studied. The ITO films were prepared by radio frequency magnetron sputtering with the target made by sintering a mixture of 90 wt.% of indium oxide (In₂O₃) and 10 wt.% of tin oxide (SnO₂). The results show that (1) average transmission in the visible range (400-700 nm) was about 85%-90%, and (2) ITO films deposited on glass, PC and mCOC at 100 W without supplying additional oxygen gas had optimum resistivity of 6.35 × 10⁻⁴ Ω-cm, 5.86 × 10⁻⁴ Ω-cm and 6.72 × 10⁻⁴ Ω-cm, respectively. In terms of both electrical and optical properties of indium tin oxide films, the optimum thickness was observed to be 150-300 nm.     

Highly-ordered mesoporous titania thin films prepared via surfactant assembly on conductive indium-tin-oxide/glass substrate and its optical properties

Highly ordered mesoporous titanium dioxide (titania, TiO₂) thin films on indium-tin-oxide (ITO) coated glass were prepared via a Pluronic (P123) block copolymer template and a hydrophilic TiO₂ buffer layer. The contraction of the 3D hexagonal array of P123 micelles upon calcination merges the titania domains on the TiO₂ buffer layer to form mesoporous films with a mesochannel diameter of approximately 10 nm and a pore-to-pore distance of 10 nm. The mesoporous titania films on TiO₂-buffered ITO/glass featured an inverse mesospace with a hexagonally-ordered structure, whereas the films formed without a TiO₂ buffer layer had a disordered microstructure with submicron cracks because of non-uniform water condensation on the hydrophobic ITO/glass surface. The density of the mesoporous film was 83% that of a bulk TiO₂ film. The optical band gap of the mesoporous titania thin film was approximately 3.4 eV, larger than that for nonporous anatase TiO₂ (~ 3.2 eV), suggesting that the nanoscopic grain size leads to an increase in the band gap due to weak quantum confinement effects. The ability to form highly-ordered mesoporous titania films on electrically conductive and transparent substrates offers the potential for facile fabrication of high surface area semiconductive films with small diffusion lengths for optoelectronics applications.     

Structural,optical and electrical characteristics of transparent bismuth vanadate films deposited on indium tin oxide coated glass substrates

Bismuth vanadate (BVO) thin films were fabricated on indium tin oxide (ITO) coated glass substrates using pulsed laser ablation technique and investigated their structural, optical and electrical properties. The use of the indium tin oxide coated glass substrate resulted in reducing the leakage current characteristics of crystalline BVO thin films. The X-ray diffraction (XRD) studies confirmed the monophasic nature of the post annealed (500 °C/1 h) films. The atomic force microscopy indicated the homogeneous distribution of crystallites in the as-deposited films. The as-deposited and the post annealed films were almost 90% transparent (380–900 nm) as confirmed by optical transmission studies. Dielectric constant of around 52 was attained accompanied by the low dielectric loss of 0.002 at 10 kHz for post annealed films. The leakage current of the post annealed BVO films on ITO coated glass substrates measured at room temperature was 8.1 × 10⁻⁸ A at an applied electric field of 33 kV/cm, which was lower than that of the films with platinum and SrRuO₃ as the bottom electrodes.     

Fabrication of flexible polymer dispersed liquid crystal films using conducting polymer thin films as the driving electrodes

Conducting polymers exhibit good mechanical and interfacial compatibility with plastic substrates. We prepared an optimized coating formulation based on poly(3,4-ethylenedioxythiophene) (PEDOT) and 3-(trimethoxysilyl)propyl acrylate and fabricated a transparent electrode on poly(ethylene terephthalate) (PET) substrate. The surface resistances and transmittance of the prepared thin films were 500-600 Ω/□ and 87% at 500 nm, respectively. To evaluate the performance of the conducting polymer electrode, we fabricated a five-layer flexible polymer-dispersed liquid crystal (PDLC) device as a PET-PEDOT-PDLC-PEDOT-PET flexible film. The prepared PDLC device exhibited a low driving voltage (15 VAC), high contrast ratio (60:1), and high transmittance in the ON state (60%), characteristics that are comparable with those of conventional PDLC film based on indium tin oxide electrodes. The fabrication of conducting polymer thin films as the driving electrodes in this study showed that such films can be used as a substitute for an indium tin oxide electrode, which further enhances the flexibility of PDLC film.     

Dopamine/TiO2 hybrid thin films prepared by the liquid phase deposition method

Liquid phase deposition method is applied to one-step production of a hybrid material composed by dopamine(DA) and TiO₂ anatase. An optimized amount of the enediol derivative is added to a fluoride titania precursor aqueous solution in order to entrap this modifier within the growing TiO₂, yielding a DA/TiO₂ nanocomposite material. Uniform, well-adhered and brown-colored thin films are deposited on indium tin oxide covered glass substrate. The DA/TiO₂ hybrid material has been characterized by infrared spectroscopy, electronic microscopy, X-ray diffraction and UV-vis spectroscopy. The formation of the hybrid material seems to be reasonably explained by linkage of different TiO₂ nanocrystallites taking advantage of both enediol and amine groups of DA.     

Nano-particle thin films of tin oxides

Nano-particle thin films of tin oxides were deposited on SiO₂ substrates by using radio frequency (RF) magnetron sputtering with various substrate temperatures, sputtering powers and oxygen partial pressures. The tin oxides thin films were then investigated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS data suggested that the deposited tin oxides thin films are almost made up of half of SnO₂ and half of SnO. The oxygen partial pressure nearly does not affect the chemical stoichiometry of the thin films in our deposition conditions. SEM results showed that the tin oxides thin films were formed by nano-particles with size of about 60 nm. Sputtering power has a strong influence on the particle size of the thin films. Increase of sputtering power will enlarge the size of the particles.     

Fabrication of mesoporous titania aerogel film via supercritical drying

Using a supercritical drying method, fluorine-doped tin oxide (FTO) glass was coated with a mesoporous titania aerogel film prepared from titania sols with viscosity between 10 and 60 cP that had been spin coated, immersed in IPA solution, and aged at least 3 weeks. Mesoporous titania aerogel film has an anatase structure, and an average porosity of 76%. It is hydrophilic, and its mechanical strength is improved by heat treatment at over 400 °C for 2 h. After heat treatment, the film retains its anatase structure and has a porosity of 68%. Dye-sensitized solar cells were fabricated using these mesoporous titania aerogel films. The thickness of the film was about 1 μm and the highest photo conversion efficiency, obtained when the film was heat treated at 450 °C for 2 h, was 3.71%.     

Heat treatable indium tin oxide films deposited with high power pulse magnetron sputtering

In this study, indium tin oxide (ITO) films were prepared by high power pulse magnetron sputtering [D. J. Christie, F. Tomasel, W. D. Sproul, D. C. Carter, J. Vac. Sci. Technol. A, 22 (2004) 1415. [1]] without substrate heating. The ITO films were deposited from a ceramic target at a deposition rate of approx. 5.5 nm?m/min kW. Afterwards, the ITO films were covered with a siliconoxynitride film sputtered from a silicon alloy target in order to prevent oxidation of the ITO film during annealing at 650 °C for 10 min in air. The optical and electrical properties as well as the texture and morphology of these films were investigated before and after annealing. Mechanical durability of the annealed films was evaluated at different test conditions. The results were compared with state-of-the art ITO films which were obtained at optimized direct current magnetron sputtering conditions.     

Effect of aluminum doping on the high-temperature stability and piezoresistive response of indium tin oxide strain sensors

Ceramic strain sensors based on reactively sputtered indium tin oxide (ITO) thin films doped with aluminum are being considered to improve the high-temperature stability and response. Ceramic strain sensors were developed to monitor the structural integrity of components employed in aerospace propulsion systems operating at temperatures in excess of 1500 °C. Earlier studies using electron spectroscopy for chemical analysis (ESCA) studies indicated that interfacial reactions between ITO and aluminum oxide increase the stability of ITO at elevated temperature. The resulting ESCA depth files showed the presence of two new indium-indium peaks at 448.85 and 456.40 eV, corresponding to the indium 3d5 and 3d3 binding energies. These binding energies are significantly higher than those associated with stoichiometric indium oxide. Based on these studies, a combinatorial chemistry approach was used to screen large numbers of possible concentrations to optimize the stability and performance of Al-doped ceramic strain sensors. Scanning electron microscopy was used to analyze the combinatorial libraries in which varying amounts of aluminum were incorporated into ITO films formed by cosputtering from multiple targets. Electrical stability and piezoresistive response of these films were compared to undoped ITO films over the same temperature range.     

Controlled Deposition of Silver Nanoparticles in Mesoporous Single‐ or Multilayer Thin Films: From Tuned Pore Filling to Selective Spatial Location of Nanometric Objects

Silver nanoparticle assemblies are embedded within mesoporous oxide thin films by an in situ mild reduction leading to nanoparticle–mesoporous oxide thin‐film composites (NP@MOTF). A quantitative method based on X‐ray reflectivity is developed and validated with energy dispersive spectroscopy in order to assess pore filling. The use of dilute formaldehyde solutions leads to control over the formation of silver nanoparticles within mesoporous titania films. Inclusion of silver nanoparticles in mesoporous silica requires more drastic conditions. This difference in reactivity can be exploited to selectively synthesize nanoparticles in a predetermined layer of a multilayered mesoporous stack leading to complex 1D‐ordered multilayers with precise spatial location of nanometric objects. The metal oxide nanocomposites synthesized have potential applications in catalysis, optical devices, surface‐enhanced Raman scattering, and metal enhancement fluorescence.     

High thermal stability thick wall mesoporous titania thin films

Mesoporous TiO₂ thin films were prepared by using tetrabutyl titanate as the inorganic precursor and triblock copolymer (Pluronic F127) as the structure directing agent. The obtained mesostructured TiO₂ thin film exhibits a high thermal stability, which can sustain 600 °C thermal treatment. The small angle XRD and wide angle XRD patterns indicate that the samples have mesoporous channel and are composed of anatase. The corresponding TEM images show that the homogeneous mesostructure and very thick pore walls (about 9–13 nm) are formed in the obtained thin films, which could be responsible for the high thermal stability of the framework. In addition, the samples have narrow pore diameter distribution and a mean pore size of 7.4 nm.     

Improved electrochromical properties of sol-gel WO3 thin films by doping gold nanocrystals

In this investigation, the effect of gold nanocrystals on the electrochromical properties of sol-gel Au doped WO₃ thin films has been studied. The Au-WO₃ thin films were dip-coated on both glass and indium tin oxide coated conducting glass substrates with various gold concentrations of 0, 3.2 and 6.4 mol%. Optical properties of the samples were studied by UV-visible spectrophotometry in a range of 300-1100 nm. The optical density spectra of the films showed the formation of gold nanoparticles in the films. The optical bandgap energy of Au-WO₃ films decreased with increasing the Au concentration. Crystalline structure of the doped films was investigated by X-ray diffractometry, which indicated formation of gold nanocrystals in amorphous WO₃ thin films. X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of the samples. XPS analysis indicated the presence of gold in metallic state and the formation of stoichiometric WO₃. The electrochromic properties of the Au-WO₃ samples were also characterized using lithium-based electrolyte. It was found that doping of Au nanocrystals in WO₃ thin films improved the coloration time of the layer. In addition, it was shown that variation of Au concentration led to color change in the colored state of the Au-WO₃ thin films.     

Phase sensitivity of Raman spectroscopy analysis of CVD titania thin films

Photocatalytic titania thin films deposited on float glass by chemical vapor deposition were analyzed by transmission electron microscopy, atomic force microscopy, Raman spectroscopy, and X-ray diffraction. Raman spectroscopy results indicate its phase sensitivity in the presence of trace amount of anatase. This suggests a preferable method of using Raman spectroscopy to characterize mixed phases of titania thin films, especially when titania coatings are deposited on other crystalline oxide materials, for example, tin oxide.     

Eu-doped indium tin oxide thin films fabricated by sol-gel technique

We have fabricated Eu-doped indium tin oxide thin films via the conventional sol-gel technique, and confirmed that the doped Eu atoms were chemically incorporated into the indium tin oxide lattice by substituting the In sites. Optical spectra indicated that the Eu-doped films were free of any impurities leading to additional vibrational effects. Valence states of Eu ions in our Eu-doped indium tin oxide films were discussed in connection with Eu concentration.     

Reflectance of surfactant-templated mesoporous silica thin films: Simulations versus experiments

In this study, cubic and hexagonal mesoporous amorphous silica thin films were synthesized using evaporation-induced self-assembly process followed by calcination leaving highly ordered spherical or cylindrical pores in a silica matrix. The films featured pores with diameter between 4 and 11 nm, lattice parameter from 7.8 to 24 nm, and porosity between 22% and 45%. All films were dehydrated prior to reflectance measurements except for one film which was fully hydrated. The present study compares the spectral reflectance measured experimentally between 400 and 900 nm with that computed numerically by solving three-dimensional Maxwell's equations in mesoporous silica thin films with the same morphology as those synthesized. The matrix was assumed to have the same optical properties as bulk fused silica. The pore optical properties were either those of air or liquid water whether the film was dehydrated or hydrated, respectively. Excellent agreement was found between experimental and numerical reflectance for both cubic and hexagonal mesoporous silica films. This study experimentally validates our simulation tool and offers the prospect of ab-initio design of nanocomposite materials with arbitrary optical properties without using effective medium approximation or mixing rules.     

Surface characterization of Ag-ITO cermet films prepared by a new sol-gel method

Incorporation of Ag nanocrystal into indium tin oxide films (Ag-ITO) could enhance the conductivity of transparent oxide thus attracts more and more interest. Ag-ITO films were prepared by a modified sol-gel method. The surface structure was investigated by X-ray diffraction, X-ray diffuse scattering, and X-ray photoelectron spectroscope techniques. The results showed that stannous chloride worked well as the reduction agent of silver and ion donor source, resulting in high quality nanocomposite thin films. The embedment of silver nanoparticles decreased the crystallization temperature and inhibited the growth of indium oxide. Ag-ITO films have a hierarchical structure. Furthermore, the nanocomposite films were densified and homogenized through prolonging the thermal duration time. XPS results confirmed that a small amount of silver oxide appeared.