Effect of porosity on the Seebeck coefficient of mesoporous TiO2 thin films

Mesoporous TiO₂ films were prepared by using titanium tetraisopropoxide as the titania precursor and triblock copolymer as the structure directing agent. The synthesized mesoporous TiO₂ film was confirmed to have the ordered pore structure with rutile phase by small angle and wide angle X-ray diffraction analyses. The mesoporous TiO₂ film has the porosity range from 21.6 to 35.6%, and its Seebeck coefficient was changed according to its porosity, up to −88.6 μV/K. From the obtained Seebeck coefficient, the ordered mesoporous TiO₂ film was found to be a good candidate of thermal sensing layer of thin film thermal sensor.     

Synthesis of anodic films in the presence of aniline and TiO2 nanoparticles on AA2024-T3 aluminium alloy

Coatings, comprising an inner porous anodic alumina film and an outer polyaniline/TiO₂ nanoparticle layer, were electrochemically synthesised on an AA2024-T3 aluminium alloy by single-step, anodic polarisation in an oxalic acid-based electrolyte. The morphology and composition of the coatings were examined by TEM, SEM and XPS, with the size and zeta-potential of the TiO₂ nanoparticles in the oxalic acid solution also measured. Observation of the growth of the coating during of anodic polarisation revealed that a distinct, two-layered coating is formed from the early stages of polarisation, with the anodic film forming at a constant rate and the outer layer developing at a rate that decreases markedly with times beyond about 30 min. Nanoparticles, agglomerated in the electrolyte, migrate to the anode due to the negative zeta-potential and form the nanoparticle-containing layer at the surface of anodic film. Such particles are not incorporated in the pores due to agglomeration and disordered film porosity at the outer layer of the anodic film.     

Preparation of sub-micron size anatase TiO<Subscript>2</Subscript> particles for use as light-scattering centers in dye-sensitized solar cell

The sub-micron size anatase TiO₂ particles with size about 0.2-0.3 μm were synthesized with basic peptizing agent and hydrothermal method and added into TiO₂ film as light scattering center. The addition of the sub-micron size anatase TiO₂ particles enhanced light scattering and dye adsorption abilities of the TiO₂ film. When the weight proportion of the sub-micron size/nano-size TiO₂ particles in the TiO₂ film attained to 1.25/10, the highest energy conversion efficiency about 7.41% was obtained, which was 23% enhancement comparing with the TiO₂ film containing pure nano-size TiO₂ particles. It presented an efficient way for improving the photovoltaic performance of dye-sensitized solar cell.     

Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Nitrogen and europium doped TiO2 anodized films with applications in photocatalysis

Micro-arc oxidation method is a useful process for mesoporous titanium dioxide films. In order to improve the photocatalytic activity of the TiO₂ film, N-Eu co-doped titania catalyst was synthesized by micro-arc oxidation in the H₂SO₄/Eu(NO₃)₃ mixture solution.The specific surface area and the roughness of the anodic titania film fabricated in the H₂SO₄/Eu(NO₃)₃ electrolyte, were increased compared to that of the anodic TiO₂ film prepared in H₂SO₄ solution. The absorbance response of N-Eu titania film shows a higher adsorption onset toward visible light region, and the incorporated N and Eu ions during anodization as a dopant in the anodic TiO₂ film significantly enhanced the photocatalytic activity for dye degradation. After dye decomposition test for 3 h, dye removal rates for the anodic TiO₂ film were 60.7% and 90.1% for the N-Eu doped titania film. The improvement of the photocatalytic activity was ascribed to the synergistic effects of the surface enlargement and the new electronic state of the TiO₂ band gap by N and Eu co-doping.     

Fabrication of porous TiO2 film via hydrothermal method and its photocatalytic performances

Porous anatase (TiO₂) films were fabricated onto stainless steel substrates with Ti(OC₄H₉)₄ as a precursor via hydrothermal process. The crystallization and porous structure of TiO₂ film were dependent on the time and temperature of the hydrothermal reaction. A TiO₂ film with orderly porous structure and high crystallization was obtained upon treatment at 150 °C for 2 h. The grain size of TiO₂ is ca. 6 nm, and pore diameter is ca. 10 nm. Diffusion of Fe into the porous TiO₂ film occurred; Fe also diffused onto the surface of the film with the extension of hydrothermal reaction time or increase of the reaction temperature. The diffusion reaction has a large effect on the formation of porous TiO₂ film as well as its interface texture. However, it does not change the crystal phase of the TiO₂. The resultant TiO₂ film showed high photocatalytic activity towards degradation of gaseous formaldehyde.     

Optical properties of titanium dioxide nanoparticles/3-(2-benzothiazolyl)-7-N,N-diethylaminocoumarin/polymethyl methacrylate composite films

3-(2-benzothiazolyl)-7-N,N-diethylaminocoumarin organic laser dye-polymethyl methacrylate (PMMA) composite films doped with inorganic titanium dioxide (TiO₂) particles are fabricated by spin-coating technique. TiO₂ nanoparticles exhibit a strong influence on optical properties of the organic laser dye/PMMA composite films. The refractive index and absorbance (absorption intensity) of organic laser dye/PMMA composite film with micro- and nanoparticles of TiO₂ are reduced, compared to those without TiO₂ particles. The organic laser dye/PMMA composite film with TiO₂ nanoparticles has the lowest refractive index and absorbance values. Photoluminescence intensities of all systems exhibit a maximum peak around the excitation wavelength, close to that of the organic laser dye, at 450 nm and the minimum around the excitation wavelength of 350 nm. Photoluminescence intensity of the organic laser dye/PMMA composite film with TiO₂ microparticles is always the lowest at all excitation wavelengths. However, the photoluminescence intensity of the organic laser dye/PMMA composite film with TiO₂ nanoparticles has the highest value at excitation wavelengths of 330 and 380 nm, while the photoluminescence intensity of composite film without TiO₂ particles is more than that with nanoparticles at other excitation wavelengths.     

Preparation of TiO2 paste using poly(vinylpyrrolidone) for dye sensitized solar cells

The surface morphology of titanium oxide (TiO₂) films as a photoanode in dye sensitized solar cells plays a vital role in converting light to electricity. Therefore, TiO₂ films were prepared using TiO₂ paste with different compositions of poly(vinylpyrrolidone) (PVP) as a binder to optimize their physico-chemical properties. The paste was prepared with commercial TiO₂ powder mixed with acetylacetone, PVP, 4-octylphenol polyethoxylate, acetic acid and ethanol. The chemical composition remains the same for all pastes except PVP. The quantity of the PVP was optimized in such a way that it provides a thick film with a good network connection. The impact of the quantity of PVP in the TiO₂ paste was analyzed. The prepared TiO₂ film structure was characterized by X-ray diffraction. The surface morphology was analyzed by scanning electron microscopy. The electrochemical performance of the prepared TiO₂ as a photoanode was also investigated. Among the four different photoanodes, the cells fabricated with a TiO₂ film prepared with 0.4 g of PVP exhibited the highest power conversion efficiency of 6.77%, short-circuit photocurrent density and open circuit voltage of 12.38 mA/cm² and 0.77 V, respectively.     

Reactivity of platinum nanoaggregates on various types of supports in catalytic decomposition of hydrazine in acid solutions

Platinized catalysts on various types of supports were tested in the catalytic decomposition of hydrazine in HClO₄ and HNO₃ solutions, where the process follows different pathways. In HClO₄, the activity of the catalysts supported on a Termoksid ceramic material is higher than that of the catalysts supported on amorphous silica gel. In nitric acid solutions, the trend is reverse. Peptization of the ceramic supports in acid solutions increasing in the order 75% TiO₂-25% SnO₂ < 75% TiO₂-25% ZrO₂ ? TiO₂ < ZrO₂ was observed. In perchloric acid solutions, the catalyst specific activity in the hydrazine adsorption-dissociative decomposition increases with decreasing size of platinum crystallites on the support. In nitric acid solutions, where the hydrazine decomposition proceeds as its catalytic oxidation with nitric acid, the catalyst specific activity decreases with a decrease in the size of the catalyst crystallites, i.e., the catalyst centers located on large crystallites are more active. The results obtained were attributed to the energetic heterogeneity of the surface Pt atoms and various mechanisms of the hydrazine catalytic decomposition in various media.     

New approach for generating Cu2O/TiO2 composite films for solar cell applications

In this paper, Cu₂O was studied as a photon absorber for solar cell applications. Cu₂O was deposited on a TiO₂ film using the electrochemical deposition (ECD) method. Based on the physical appearance of the samples, the particles of Cu₂O seemed to penetrate the TiO₂ film and were primarily deposited near the TiO₂/substrate interface rather than on the TiO₂ film surface. This method could be one way to generate a p-n bulk-heterojunction interface. The film was confirmed to be a Cu₂O/TiO₂ composite via X-ray diffraction measurements. The top electrode was formed by evaporating indium for I-V characterization, and the fabricated cell showed photovoltaic properties.     

Nanoscale investigation on large crystallites in TiO2 nanotube arrays and implications for high-quality hybrid photodiodes

Anodized TiO₂ nanotube arrays fabricated on a TiO₂ thin film on conducting glass substrates can be readily implemented in diverse applications like hybrid solar cells. In this study, we concentrate on morphologies with inner tube diameter being around 30 nm which is in dimension of the exciton diffusion length of common organic hole conductors. Cross-sectional preparation of the intact tube array in correlation with transmission electron microscopy has been performed to get local information on the TiO₂ nanotubes and their arrangements, depending on anodization voltage. Crystallites have been found to be anatase and in size of several hundred nanometers along tube walls with increasing length for increasing anodization voltages. Inter-tube connections with similar crystal orientations of adjacent tubes are found. These give rise to large areas of uniform orientation. Thus, the number of grain boundaries within the film is low compared to the reported values for different TiO₂-polymer material systems. Using the arrays, hybrid TiO₂ solar cells were fabricated, which show high fill factors indicating good electron transport. The results suggest high electron mobility and are encouraging for a utilization of the nanotube arrays in next generation photovoltaics.     

Synthesis of nanocrystalline TiO2 thin films by liquid phase deposition technique and its application for photocatalytic degradation studies

A transparent, high purity titanium dioxide thin film composed of densely packed nanometer sized grains has been successfully deposited on a glass substrate at 30°C from an aqueous solution of TiO₂-HF with the addition of boric acid as a scavenger by liquid phase deposition technique. From X-ray diffraction measurement, the deposited film was found to be amorphous and turns crystalline at 500°C. The deposited film showed excellent adherence to the substrate and was characterized by homogeneous flat surface. TiO₂ thin films can be used as a photocatalyst to clean up organohalides, a class of compound in pesticides that pollute the ground water. Photocatalytic degradation experiments show that indanthrene golden orange dye undergoes degradation efficiently in presence of TiO₂ thin films by exposing its aqueous solution to ultraviolet light. The suitable surface structure and porosity increases the photocatalytic activity. It was also observed that hemin doped TiO₂ thin films break up organohalides at a surprisingly high rate under visible light.     

Ag surfactant effects of TiO2 films prepared by sputter deposition

The surfactant effect of Ag on the thin film structure of TiO₂ by radio frequency magnetron sputtering has been investigated. Comparisons between the atomic force microscopy images revealed that the surface roughness of TiO₂ film mediated by Ag was smaller than that of the TiO₂ film without Ag. The surface segregation effect of Ag was confirmed using X-ray photoelectron spectroscopy. The results of X-ray diffraction revealed that the initial deposition of a 0.4 nm thick Ag surfactant layer onto a Fe buffer layer prior to the deposition of the TiO₂ film reduced the rutile (110) growth and enhanced the anatase (100) growth. It was concluded that Ag was an effective surfactant for changing the thin film structure of TiO₂ on the Fe buffer layer. The photocatalytic effect of the fabricated TiO₂ film was also investigated using the remote oxidation process. TiO₂ films with the Ag surfactant exhibited higher photocatalytic activity than conventionally deposited TiO₂ films.     

Ag surfactant effects of TiO2 films prepared by sputter deposition

The surfactant effect of Ag on the thin film structure of TiO₂ by radio frequency magnetron sputtering has been investigated. Comparisons between the atomic force microscopy images revealed that the surface roughness of TiO₂ film mediated by Ag was smaller than that of the TiO₂ film without Ag. The surface segregation effect of Ag was confirmed using X-ray photoelectron spectroscopy. The results of X-ray diffraction revealed that the initial deposition of a 0.4 nm thick Ag surfactant layer onto a Fe buffer layer prior to the deposition of the TiO₂ film reduced the rutile (110) growth and enhanced the anatase (100) growth. It was concluded that Ag was an effective surfactant for changing the thin film structure of TiO₂ on the Fe buffer layer. The photocatalytic effect of the fabricated TiO₂ film was also investigated using the remote oxidation process. TiO₂ films with the Ag surfactant exhibited higher photocatalytic activity than conventionally deposited TiO₂ films.     

Synthesis,Characterization and Photocatalytic Activity of TiO_2 Film/Bi_2O_3 Microgrid Heterojunction

TiO2 film modified by Bi2O3 microgrid array was successfully fabricated by using a microsphere lithography method.The structure and morphology of TiO2 film,Bi2O3 film and TiO2 film/Bi2O3 microgrid heterojunction were characterized through X-ray diffraction,atomic force microscopy and scanning electron microscopy.The optical transmittance spectra and the photocatalytic degradation capacity of these samples to rhodamine B were determined via ultraviolet-visible spectroscopy.The results indicated that the coupled system showed higher photocatalytic activity than pure TiO2 and Bi2O3 films under xenon lamp irradiation.The enhancement of the photocatalytic activity was ascribed to the special structure,which could improve the separation of photo-generated electrons and holes,enlarge the surface area and extend the response range of TiO2 film from ultraviolet to visible region.     

Preparation and photoelectrochemical performance of TiO2/HS-CH2-COOH/Cu3Se2 composite film

In this paper, the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes were fabricated on conducting glass plates. Cu₃Se₂ nanoparticles were used as the sensitizer and the bi-functional modifier HS-CH₂-COOH was used at the interface between Cu₃Se₂ and TiO₂ films to improve the properties of the film photoanode. The characterization results show that the sol-gel prepared anatase TiO₂ film has a compact and uniform surface, while the tetragonal Cu₃Se₂ film has a coarse surface which is made up of uniform elongated particles. The photoelectrochemical experimental results indicate that the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes have a good photovoltaic property.     

Templated titania films with meso- and macroporosities

Porous TiO₂ films with both mesoporosity and macroporosity were fabricated by a templated sol–gel method for applications, such as dye-sensitized solar cells (DSC), photocatalysis and catalysis. With the incorporation of differently sized pores, the resultant structures exhibit high surface areas and possess interpenetrating aligned pore channels, which are believed to be beneficial for applications where diffusion of reactants to interior surface can be rate limiting. Both liquid and solid TiO₂ precursors can be applied for large area coating in this process. Almost crack-free films were produced by templated coating of pre-synthesized TiO₂ nanoparticles. The measured specific surface area and porosity of synthesized films were in the range of 33–137 m²/g and 61–80%, respectively, depending on the size of the selected template.     

Ultra-porous titanium oxide scaffold with high compressive strength

Highly porous and well interconnected titanium dioxide (TiO₂) scaffolds with compressive strength above 2.5 MPa were fabricated without compromising the desired pore architectural characteristics, such as high porosity, appropriate pore size, surface-to-volume ratio, and interconnectivity. Processing parameters and pore architectural characteristics were investigated in order to identify the key processing steps and morphological properties that contributed to the enhanced strength of the scaffolds. Cleaning of the TiO₂ raw powder removed phosphates but introduced sodium into the powder, which was suggested to decrease the slurry stability. Strong correlation was found between compressive strength and both replication times and solid content in the ceramic slurry. Increase in the solid content resulted in more favourable sponge loading, which was achieved due to the more suitable rheological properties of the ceramic slurry. Repeated replication process induced only negligible changes in the pore architectural parameters indicating a reduced flaw size in the scaffold struts. The fabricated TiO₂ scaffolds show great promise as load-bearing bone scaffolds for applications where moderate mechanical support is required.     

New roots to formation of nanostructures on glass surface through anodic oxidation of sputtered aluminum

New processes for the preparation of nanostructure on glass surfaces have been developed through anodic oxidation of sputtered aluminum. Aluminum thin film sputtered on a tin doped indium oxide (ITO) thin film on a glass surface was converted into alumina by anodic oxidation. The anodic alumina gave nanometer size pore array standing vertically on the glass surface. Kinds of acids used in the anodic oxidation changed the pore size drastically. The employment of phosphoric acid solution gave several tens nanometer size pores. Oxalic acid cases produced a few tens nanometer size pores and sulfuric acid solution provided a few nanometer size pores. The number of pores in a unit area could be changed with varying the applied voltage in the anodization and the pore sizes could be increased by phosphoric acid etching. The specimen consisting of a glass substrate with the alumina nanostructures on the surface could transmit UV and visible light. An etched specimen was dipped in a TiO₂ sol solution, resulting in the impregnation of TiO₂ sol into the pores of alumina layer. The TiO₂ sol was heated at ∼400 °C for 2 h, converting into anatase phase TiO₂. The specimens possessing TiO₂ film on the pore wall were transparent to the light in UV–Visible region. The electro deposition technique was applied to the introduction of Ni metal into pores, giving Ni nanorod array on the glass surface. The removal of the barrier layer alumina at the bottom of the pores was necessary to attain smooth electro deposition of Ni. The photo catalytic function of the specimens possessing TiO₂ nanotube array was investigated in the decomposition of acetaldehyde gas under the irradiation of UV light, showing that the rate of the decomposition was quite large.     

TiO2/Si nanowires hybrid system for efficient photocatalytic degradation of organic dye

Herein, titanium dioxide (TiO₂)-coated vertically aligned silicon nanowires (SiNWs/TiO₂) were fabricated and evaluated for photocatalytic degradation of organic dyes. Aligned SiNWs arrays were prepared by facile metal-assisted chemical-etching process with varying the etching time that was followed by TiO₂ nanoparticles coating using sputtering technique. The TiO₂ film crystallized in pure anatase phase with an average crystalline size of 50 nm, as was elucidated with X-ray diffraction studies. SEM analysis showed nanowires with varying lengths from 2.5 to 13.5 µm and confirmed the homogenous surface decoration with TiO₂. The homogeneous distribution of TiO₂ nanoparticles on nanowires was co-evidenced with Energy-Dispersive X-ray spectroscopy (EDX) and Raman spectra analysis. The developed SiNWs/TiO₂ was exploited for photocatalytic degradation of methylene blue; the role of hydrogen peroxide was also elucidated. The highest photocatalytic efficiency of 96% was achieved for SiNWs/TiO₂ with optimum nanowire length of 3.5 μm. The developed photocatalyst was found to be almost stable even after 190 days (~?5 months) and could be used as reusable and easily removable photocatalysts. The current study highlighted the SiNWs/TiO₂/H₂O₂ system as excellent candidate for water remediation applications.