Mesoporosity in silica films studied by a slow positron beam and ellipsometry

Porous silica films were synthesized via a sol–gel method using a nonionic amphiphilic triblock copolymer F127 as the structural template. Mesoporosities of the prepared silica films were investigated by Doppler broadening of positron annihilation radiation (DBAR) spectroscopy, positron annihilation gamma-ray energy spectroscopy based on a slow positron beam, and ellipsometry. For the mesoporous silica films, the variation of positron annihilation line shape parameter reveals that the porosity of the silica films increases with loading more F127, which is also confirmed by a decrease of refractive index n. Little variation in positron 3γ-annihilation fraction is found for the silica films prepared with F127 loading less than 15 wt%, whereas a remarkable increment is seen for the films with higher loading. This indicates the pore percolation in porous silica films occurs around a loading of F127 with 15 wt%.     

Evolution of pores in mesoporous silica films: Porogen loading effect

Mesoporous silica films were synthesized via a sol-gel process under an acidic condition. Various amounts of triblock copolymer F38 were loaded to precursor sols as the pore generator. The evolution of the pores generated by porogen decomposition was investigated as a function of F38 loading by positron annihilation gamma-ray energy spectroscopy and positron annihilation lifetime spectroscopy based on slow positron beams. The threshold of pore percolation is found to be around 10 wt% of F38 loading by positron annihilation gamma-ray energy spectroscopy. Positron annihilation lifetime spectroscopy in the films show that the pore size increases from 1 nm to 3 nm with increasing F38 loading from 5 wt% to 30 wt%.     

Positron annihilation studies of mesoporous silica films using a slow positron beam

Positron annihilation lifetime spectra were measured for mesoporous silica films, which were synthesized using triblock copolymer (EO₁₀₆PO₇₀EO₁₀₆) as a structure-directing agent. Different positron lifetime spectra for the deposited and calcined films indicated the formation of meso-structure after calcination, which was confirmed by Fourier transform infrared (FTIR) spectra and field emission-scanning electron microscopy (FE-SEM) observation. Open porosity or pore interconnectivity of a silica film might be evaluated by a two-dimensional positron annihilation lifetime spectrum of an uncapped film. Pore sizes and their distributions in the silica films were found to be affected by thermal treatments.     

Transparent titania nanotubes of micrometer length prepared by anodization of titanium thin film deposited on ITO

Transparent TiO₂ nanotube arrays of micrometer lengths were prepared by anodization of titanium thin film RF sputtered on indium tin oxide (ITO) which was coated on glass substrate. The sputtering process took place at elevated temperature of 500 °C. The structures of the films were studied using scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the optical properties of the films were investigated using UV-visible spectroscopy. Two types of electrolytes were used in this work: an aqueous mixture of acetic acid and HF solution and a mixture of NH₄F and water dissolved in ethylene glycol. The concentration of NH₄F, voltage and the thickness of the sputtered titanium film were varied to study their effect on the formation of TiO₂ nanotube arrays. It is demonstrated in this work that the nanoporous layer is formed on top of the ordered array of TiO₂ nanotubes. Furthermore, the optical transmittance of TiO₂ nanotubes annealed at 450 °C is much lower than the non annealed TiO₂ nanotubes in the visible wavelength region.     

TiO2/CdSe多层膜结构的制备及光电化学性能研究

采用电化学方法在导电的ITO/TiO₂ 薄膜上沉积了棕红色CdSe薄膜, 并制得TiO₂/CdSe多层膜体系,研究了多层膜的微结构和光电化学性能. 实验表明, CdSe薄膜沿着(111)方向择优生长, 多层膜结构的厚度和紫外-可见光吸收强度随着沉积层数的增加而增加. 通过测定多层膜电极的光电化学性能表明, 二层膜体系的开路电压和短路电流密度最大,光电化学性能最好.     

Structural properties of single and multilayer ITO and TiO2 films deposited by reactive pulsed laser ablation deposition technique

Indium tin oxide (ITO) and titanium dioxide (TiO₂) single layer and double layer ITO/TiO₂ films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser. The films were deposited on SiO₂ substrates heated at 200 and 400 °C. ITO and TiO₂ films with uniform thicknesses of about 400 and 800 nm, respectively, over large areas were prepared. X-ray diffraction (XRD) analysis revealed that the ITO films are formed of highly orientated nanocrystals with an average particle size of 10-15 nm. Atomic force microscopy (AFM) observations indicate rough ITO films surfaces with average roughness of 26-30 nm. Pores were also observed. TiO₂ films deposited on the prepared ITO films result less crystalline. Annealing at 300 and 500 °C for three consecutive hours promoted formation of TiO₂ anatase phase, with crystal size of ∼6-7 nm. From the scanning transmission electron microscope (STEM) images, it can be seen that the TiO₂ films deposited onto the prepared ITO films present a relatively high pore sizes with an average pore diameter of ∼40 nm and excellent uniformity. In addition, STEM cross-sectional analysis of our films showed a columnar structure but no evidence of voids in the structure. Therefore, films exhibited large surface area, well suited for dye-sensitized solar cells (DSSC) applications.     

Substrate effects on the oxygen gas sensing properties of SnO2/TiO2 thin films

In this study, SnO₂/TiO₂ thin films are fabricated on SiO₂/Si and Corning glass 1737 substrates using a R.F. magnetron sputtering process. The gas sensing properties of these films under an oxygen atmosphere with and without UV irradiation are carefully examined. The surface structure, morphology, optical transmission characteristics, and chemical compositions of the films are analyzed by atomic force microscopy, scanning electron microscopy and PL spectrometry. It is found that the oxygen sensitivity of the films deposited on Corning glass 1737 substrates is significantly lower than that of the films grown on SiO₂/Si substrates. Therefore, the results suggest that SiO₂/Si is an appropriate substrate material for oxygen gas sensors fabricated using thin SnO₂/TiO₂ films.     

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO2 thin films by DC magnetron sputtering

Titanium dioxide (TiO₂) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO₂ films has been analyzed by X-ray photoelectron spectroscopy. The TiO₂ films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO₂ into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO₂/p-Si have been fabricated. The leakage current density of unbiased films was 1 × 10⁻⁶ A/cm² at a gate bias voltage of 1.5 V and it was decreased to 1.41 × 10⁻⁷ A/cm² with the increase of substrate bias voltage to −150 V owing to the increase in thickness of interfacial layer of SiO₂. Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at −150 V. The capacitance at 1 MHz for unbiased films was 2.42 × 10⁻¹⁰ F and it increased to 5.8 × 10⁻¹⁰ F in the films formed at substrate bias voltage of −150 V. Dielectric constant of TiO₂ films were calculated from capacitance–voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at −150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to −150 V.     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

Characterization of in situ mechanically worked PVD Mg–Ti alloys

Mg–Ti alloys with up to 46?wt%?Ti in solid solution were produced by physical vapour deposition (PVD) with in situ mechanical working. All the alloys exhibited compositional inhomogeneity, columnar microstructures and typical PVD defects. The thermal stability of the solid solutions decreased with increasing Ti content, with the most stable solid solution breaking up above 566?K. The in situ mechanical working reduced porosity by closing pores and flattened surface asperities. The oxide film on the surface of the Mg–8?wt%?Ti alloy was Ti-free. The air formed oxide film on the alloys with a Ti content above 8?wt% was identiffied as a mixture of MgO and TiO₂ covered by Mg(OH)₂ and hydromagnesite at the outermost surface. Magnesium oxide and titanium oxide were also formed at the columnar boundaries that were not affected by the in situ mechanical working. The oxide chemistry was studied using Auger parameter analysis.     

Preparation and characterization of patterned copper sulfide thin films on n-type TiO2 film surfaces

Micro-arrayed patterns of p-type copper sulfide (Cu_xS) thin films with positive and negative features were deposited onto the surfaces of n-type TiO₂ semiconductor films via a selective nucleation and growth process from aqueous solution. The surface functional molecules of the UV photo-oxidised patterned SAMs were utilized to direct the nucleation and growth of Cu_xS crystallites. The resultant Cu_xS/TiO₂ composite films with negative and positive Cu_xS patterns on the TiO₂ film surface were investigated using SEM, XRD, XPS and a 3D Surface Profiler. It is demonstrated that regular and compact patterned films of Cu₂S crystallites had been deposited onto the n-type TiO₂ surface, with sharp edges demarcating the boundaries between the patterned Cu₂S region and the TiO₂ film region. The UV-vis spectra for three Cu₂S/TiO₂ films exhibit a wide absorption between 300 nm and 450 nm. The maximum wavelength differences in the spectra of Cu₂S/TiO₂ films and TiO₂ film were attributed to the added absorption of Cu₂S films at 302 nm and the unchanged adsorption of TiO₂ films. The absorption intensities of the Cu₂S/TiO₂ films could be varied in the UV-vis range using the Cu₂S patterned features (positive, negative).     

Methylene blue photoelectrodegradation under UV irradiation on Au/Pd-modified TiO2 films

In this work TiO₂ thin films were modified with gold/palladium (Au/Pd) bimetallic paticles by sputtering method. TiO₂ films were deposited on ITO (SnO₂:In) by Doctor Blade method and post-anneling. The properties of the films were studied through measurements of XRD (X-ray diffraction) and AFM (atomic force microscopy). The degradation of methylene blue was studied by UV-irradiated pure TiO₂ and Au/Pd-modified TiO₂ in aqueous solution. Langmuir-Hinshelwood model was used to obtain kinetic information. Photocatalytic study indicated that Au/Pd-modified TiO₂ photocatalytic activity was better than TiO₂ pure; the best half-life time for Au/Pd-modified TiO₂ in photodegradation was 2.8 times smaller than TiO₂ pure; finally the efficiency in methylene blue photodegradation was improved from 23% to 43% when Au/Pd-modified TiO₂ films were used.     

TiO2 thick films supported on reticulated macroporous Al2O3 foams and their photoactivity in phenol mineralization

TiO₂ thick films deposited on macroporous reticulated Al₂O₃ foams with pore size of 10 ppi and 15 ppi were prepared using dip coating from slurries of Aeroxide^® P25 nanopowder and precipitated titania. All prepared films have sufficiently good adhesion to the surface of the substrate also in case of strongly cracked films. No measurable release of deposited TiO₂ after repeated photocatalytic cycles was observed. The photocatalytic activity was characterized as the rate of mineralization of aqueous phenol solution under irradiation of UVA light by TOC technique. The best activity was obtained with Aeroxide^® P25 coated Al₂O₃ foam with the pore size of 10 ppi, annealed at 600 °C. The optimal annealing temperature for preparation of films from precipitated titania could be determined at 700 °C. Films prepared by sol-gel deposition technique were considerably thinner compared to coatings made of suspensions and their photocatalytic activity was significantly smaller.     

Acoustic and optical phonons in EVOH–TiO2 nanocomposite films: Effect of aggregation

Films of an organic–inorganic nanocomposite material formed by a polymeric matrix (ethylene–vinyl alcohol copolymer—EVOH) and nanometric TiO₂ particles (ca. 10 nm) have been obtained with photo-catalytic properties in the elimination of pathogens. Optical spectroscopy experiments have been performed in order to characterize the films and evaluate their properties as a function of TiO₂ doping in the range between 0.25 and 13 wt%. Anatase TiO₂ nanoparticles seem to be well-dispersed up to 2% but aggregation for higher doping originates the two different regimes observed in the acoustic modes as well as in the optical absorption in the visible spectral range.     

Quantum confinement effects of CdTe nanocrystals sequestered in TiO2 matrix: effect of oxygen incorporation

Thin films of TiO₂ with high volume fraction (40–55%) and crystallite size (6–40 nm) of CdTe nanoparticles had been prepared by rf magnetron sputtering from a composite TiO₂:CdTe target at room temperature and 373 K. A detailed optical properties of nanocrystalline CdTe:TiO₂ films as-deposited and after thermal treatment (300 °C) are studied. The absorbance of the TiO₂ films with CdTe nanocrystallite dispersions depends both on the nanocrystallite size and volume fraction. The blue-shifts of the optical absorption edge concurrent with the CdTe nanocystal size reduction for as-deposited and after thermal treatment of nanocrystalline CdTe:TiO₂ thin films with respect to the bulk semiconductor agrees quite well with the strong quantum confinement theory. A slight deviation in absorption edge values than the predicted values from the strong quantum confinement model can be attributed to change in interplanar distance due to oxygen incorporation and inhomogeneous size distribution of CdTe nanocrystallites in these films.     

The influence of titanium on the properties of zinc oxide films deposited by radio frequency magnetron sputtering

TiO₂-doped zinc oxide thin films were deposited on glass substrates by radio frequency (RF) magnetron sputtering with TiO₂-doped ZnO targets in an argon atmosphere. The structural properties of TiO₂-doped ZnO films doped with different TiO₂ contents were investigated. The experimental results show that polycrystalline TiO₂-doped ZnO films had the (0 0 2) preferred orientation. The deposition parameters such as the working pressure and substrate temperature of TiO₂-doped ZnO films were also investigated. The crystalline structure of the TiO₂-doped ZnO films gradually improved as the working pressure was lowered and the substrate temperature was raised. The lowest electrical resistivity for the TiO₂-doped ZnO films was obtained when the Ti addition was 1.34 wt%; its value was 2.50 × 10⁻³ Ω cm, smaller than that found in previous studies. The transmittance of the TiO₂-doped ZnO films in the visible wavelength range was more than 80%. The optical energy gap was related to the carrier concentration, and was in the range of 3.30-3.48 eV.     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术，分别沉积Ti和Ti/Al膜，经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序，分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27     

多孔TiO2/Al/SiO2纳米复合结构的紫外光吸收特性研究

在SiO₂玻璃衬底上用脉冲激光沉积(PLD)技术,分别沉积Ti和Ti/Al膜,经电化学阳极氧化成功制备了多孔TiO₂/SiO₂和TiO₂/Al/SiO₂纳米复合结构. 其中TiO₂薄膜上的微孔阵列高度有序,分布均匀. 实验研究了Al过渡层对多孔TiO₂薄膜光吸收特性的影响. 结果表明：无Al过渡层的多孔TiO₂薄膜其紫外吸收峰在27 关键词： 2薄膜')" href="#">多孔TiO₂薄膜 阳极氧化 紫外光吸收     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

Mechanically induced changes in amylose structure and effect on thermal behavior in the presence of TiO2 nanoparticles

Thermal behavior of amylose/TiO₂ films under ultrasonic irradiation was investigated, and the final product of each process was applied to prepare amylose/TiO₂ nanocomposite films. The effects of different degradation techniques on thermal behavior, crystallinity, and molecular weight distribution of amylose were surveyed. The evaluations of structural changes and thermal behaviors were performed by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetry analysis, FT-IR spectroscopy, and scanning electron microscopy. The XRD results clarified that the crystalline shape of amylose molecules formed is an A-type crystal due to the sonophotocatalytic processing, while the FT-IR spectra does not approve any chemical change in amylose structure. The DSC data submitted a broad endothermic peak for amylose. In the case of high loading of nanoparticles, the endothermic analysis results and diffraction peaks for the sonophotocatalytic process were not significant. This indicates that the length of amylose chains through the sonophotocatalytic degradation became smaller. An increase at the loading of TiO₂ improved the hydrophilic properties of amylose/TiO₂ films, which leads to the modification of water absorption behavior. Mechanical properties of amylose/TiO₂ films were affected by the uniform dispersion of TiO₂ in the polymer matrix.