Influence of the target composition on reactively sputtered titanium oxide films

Titanium dioxide thin films have many interesting properties and are used in various applications. High refractive index of titania makes it attractive for the glass coating industry, where it is used in low-emissivity and antireflective coatings. Magnetron sputtering is the most common deposition technique for large area coatings and a high deposition rate is therefore of obvious interest. It has been shown previously that high rate can be achieved using substoichiometric targets. This work deals with reactive magnetron sputtering of titanium oxide films from TiO_x targets with different oxygen contents.The deposition rate and hysteresis behaviour are disclosed. Films were prepared at various oxygen flows and all films were deposited onto glass and silicon substrates with no external heating. The elemental compositions and structures of deposited films were evaluated by means of X-ray photoelectron spectroscopy, elastic recoil detection analysis and X-ray diffraction. All deposited films were X-ray amorphous. No significant effect of the target composition on the optical properties of coatings was observed. However, the residual atmosphere is shown to contribute to the oxidation of growing films.     

Electrochemical fabrication of polyaniline films containing gold nanoparticles deposited on titanium electrode for electro-oxidation of ascorbic acid

Polyaniline films prepared on titanium were employed as substrate for the electrodeposition of gold. The modified electrode was used as anode for the electro-oxidation of ascorbic acid. The electrochemical behavior and electro-catalytic activity of Au/PAni/Ti electrode were characterized by cyclic voltammetry. The morphology of the polyaniline film and gold coating on PAni/Ti electrode were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) techniques, respectively. Results indicated that gold nanoparticles were homogeneously dispersed on the surface of polyaniline film. The electro-oxidation of ascorbic acid is found to proceed more facile on Au/PAni/Ti electrode than on bare gold electrode. The irreversible oxidation current of ascorbic acid exhibits a linear dependence on the ascorbic acid concentration in the range of 1–5 mM.     

Nanoporous titanium oxide synthesized from anodized Filtered Cathodic Vacuum Arc Ti thin films

This paper describes the formation of self-organized nanopores in thin films of titanium prepared using a Filtered Cathodic Vacuum Arc (FCVA) deposition system. The post-deposition anodization was performed using 0.5% (wt) NH₄F in ethylene glycol and an aqueous based solution containing 0.5% (wt) NH₄F and 1 M (NH₄)₂SO₄ electrolytes. Homogenously distributed nanopores with dimensions in the range of 10 to 20 nm were obtained. Nanoporous TiO₂ thin films were obtained after annealing the anodized samples at 600 °C for 4 h. Scanning electron microscopy (SEM) and Raman spectroscopy were used to characterize these nanoporous films. Raman measurements revealed that the rutile TiO₂ polymorph dominates these structures along with imperfect titanium oxidation resulting in the formation of defect structures, particularly when aqueous electrolyte was used for the anodization.     

In-situ preparation of multi-layer TiO2 nanotube array thin films by anodic oxidation method

The multi-layer TiO₂ nanotube array thin films have been formed by anodic oxidation method via adjusting the outer voltage during oxidation process in glycerol electrolyte containing 0.3% NH₄HF₂. The diameter of the nanotube array increases with the outer voltage, and the length of nanotube in every layer increases with the anodic oxidation time. These multi-layers bring new possibilities to tailor the properties of the TiO₂ nanotube array thin films formed via anodic oxidation method. Further, such multi-layer structure provide a new approach to evaluate the growth rate of TiO₂ nanotube, which will help us to understand more deeply the formation mechanism of the TiO₂ nanotubes. The growth rate of TiO₂ nanotube array is respectively 1.2 and 3.6 μm/h under the anodic voltage of 30 V and 60 V. These multi-layer TiO₂ nanotube array thin films may exhibit lots of potential applications in photoelectrochemical fields.     

Influence of cobalt ion implantation on optical properties of titanium dioxide thin films

Nano-crystalline TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. In this study, the deposited TiO₂ coating with a grain size of 13 ± 2 nm was uniform without aggregation. Co ion implantation into the as-calcined TiO₂ thin films was conducted with fluences of 1 × 10¹⁵-1 × 10¹⁶ doses/cm² at 40 keV. In addition to the emission of TiO₂, the photoluminescence study showed the presence of another Co-related optical center at 405 nm in the Co-implanted TiO₂ thin films. Due to the strong capability of forming impurity compounds between the energetic cobalt ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

Field emission from the structure of well-aligned TiO2/Ti nanotube arrays

Well-aligned TiO₂/Ti nanotube arrays were synthesized by anodic oxidation of titanium foil in 0.5 wt.% HF in various anodization voltages. The images of filed emission scanning electron microscopy indicate that the nanotubes structure parameters, such as diameter, wall thickness and density, can be controlled by adjusting the anodization voltage. The peaks at 25.3° and 48.0° of X-ray diffraction pattern illuminate that the TiO₂ nanotube arrays annealed at 500 °C are mainly in anatase phase. The filed emission (FE) properties of the samples were investigated. A turn-on electric field 7.8 V/µm, a field enhancement factors approximately 870 and a highest FE current density 3.4 mA/cm² were obtained. The emission current (2.3 mA/cm² at 18.8 V/µm) was quite stable within 480 min. The results show that the FE properties of TiO₂/Ti have much relation to the structure parameters.     

Mesoporous TiO2 thin films embedded with Au nanoparticles for the enhancement of the photocatalytic properties

Mesoporous TiO₂ thin films were prepared by hydrothermal-oxidation of titanium metal thin films, which were obtained by DC magnetron sputtering technique. Gold nanoparticles, which were prepared by reduction of HAuCl₄, were embedded into the holes of the mesoporous TiO₂ films by capillary method followed by annealing in air up to 400 °C. The size of pore of TiO₂ films is about 100 nm and that of Au nanoparticles is about 10 nm in average. The morphology of the films was analyzed by field emission scanning electron microscope (FE-SEM) and scanning probe microscopes (SPMs). Subsequently, the photocatalytic performances of the obtained nanosystems in the decomposition of methylene blue solution are discussed. The obtained results show that the dispersion of Au nanoparticles on the mesoporous TiO2 matrix will help enhancing the photocatalytic activity with respect to pure TiO₂ under visible light irradiation.     

A novel application of iron oxide nanoparticles for detection of hydrogen peroxide in acid rain

Determining the concentration of hydrogen peroxide (H₂O₂) is of great importance in food, pharmaceutical, environmental and clinical analyses. Horseradish peroxidase (HRP), an enzyme specifically catalyzing the oxidative reaction of H₂O₂ to develop color reaction, has been widely used for measuring H₂O₂ concentration. However, owing to the instability and high cost of this enzyme, discovering efficient mimics of peroxidase has been important to conquer these disadvantages of protein catalyst. Recently we have found that Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs) possess intrinsic peroxidase-like activity, which can catalyze oxidation of various peroxidase substrates in the presence of H₂O₂. Based on this finding, we developed a spectrometric method using Fe₃O₄ MNPs as a catalyst to determine H₂O₂ in rainwater. Our data show that the Fe₃O₄ MNPs are efficient catalysts to determine H₂O₂ in rainwater. Compared to HRP, the Fe₃O₄ MNPs are reusable and economical and these characteristics make the particles a board range of applications in determining H₂O₂ in the rainwater.     

Hydrothermal growth of rutile TiO2 nanorod films on titanium substrates

Rutile TiO₂ nanorod films have been successfully prepared on titanium substrate via a hydrothermal method using Tetra-n-butyl titanate as Ti source in the presence of concentrated hydrochloric acid. The effect of Ti substrate annealing treatment and adding of additional alkali metal chlorides in hydrothermal solution on the growth of TiO₂ nanorod films has been studied using scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and water contact angle measurement. The growth mechanism of the TiO₂ nanorods on Ti substrate has also been discussed. It has shown that the initial rutile film transformed from anatase promotes the nucleation and epitaxial growth of rutile TiO₂ nanorods. The superior wettabilities of the TiO₂ nanorods resulted from treatments of vacuum and ultraviolet show great potential for applications in orthopaedic, dental implants, and possible photocatalysis.     

Surface characterization of titanium hydride powder

Titanium hydride is well known for its stability in air because of formation of thin TiO₂ oxide layer on top of TiH₂ powder particles. Formation of the oxide layer is directly related to high affinity of Ti to oxygen and it can be formed in few seconds also on top of TiH₂ particles in low vacuum. On the other hand, thickness of TiO₂ layer on the formed TiH₂ powder is in the range of 130 nm. Existence of oxide layer on top of powder particles was confirmed with AES, XPS and EDXS cross section line scans. Formation of thin oxide was confirmed also with calculations based on chemical and TG analyses.     

Mineralization of flagella for nanotube formation

Flagella isolated from Salmonella typhimurium were used as a template for the formation of TiO₂ nanotubes, which was accomplished through recent advances in low temperature ceramic film processing. TiO₂ is precipitated onto or attracted to the flagellar surface in aqueous solution. The mechanism of mineral film formation is similar to that of biominerals in nacre, sea urchin spine, and sponge spicule. This process is advantageous over other mineralization processes, as no genetic modification of the flagella is necessary and the mineralization is done at low temperature in aqueous solution.     

Influence of annealing on the structure and stoichiometry of europium-doped titanium dioxide thin films

This work presents the influence of annealing on the structure and stoichiometry of europium (Eu)-doped titanium dioxide (TiO₂). Thin films were fabricated by magnetron sputtering from a metallic Ti-Eu target in oxygen atmosphere and deposited on silicon and SiO₂ substrates. After deposition the selected samples were additionally annealed in air up to 1070 K.Film properties were examined by means of X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) and the results were analyzed together with the undoped TiO₂ thin films prepared under similar technological conditions.XRD results showed that depending on the Eu content, as-deposited thin films consisted of the TiO₂-anatase or TiO₂-rutile.An additional annealing will result in the growth of anatase crystals up to 35 nm, but anatase to rutile phase transformation has not been recorded. AFM images display high quality and a dense nanocrystalline structure. From the XPS Ti2p spectra the 4+oxidation state of Ti was confirmed. The O1s XPS spectra displayed the presence of an O²⁻ photoelectron peak accompanied by an additional broader peak that originates from hydroxyl species chemisorbed at the sample surface. It has been found that Eu dopant increases the OH⁻ content on the surface of prepared TiO₂:Eu thin films. The calculated O/Ti ratio was in the range of 1.85-2.04 depending on the sample.     

Nanocrystalline titanium dioxide sensitised with natural dyes for eco-friendly solar cell application

Indigenously available natural dyes have been used as natural sensitisers for dye-sensitised solar cells (DSSCs) in this study. The chlorophyll extract from Azadirachta indica (Neem) leaves and anthocyanin extract from poinsettia bracts were obtained using ethanol. Nanoparticles of TiO₂ having an average size of 80 nm were deposited on fluorine-doped tin oxide (FTO) coated glass using the electrophoretic deposition method. Counter electrode was prepared by spraying conductive graphite over FTO glass substrates. A sandwich-type cell was assembled, and the fill factor and the power conversion efficiency were measured under a light source simulating AM 1.5 with an intensity of 100 mW/cm². DSSCs containing chlorophyll and anthocyanin exhibited open circuit voltages of 404 and 406 mV with fill factors of 40.1% and 45.8%, respectively. The mixture of the two natural dyes as sensitiser for DSSCs gave the best photovoltaic conversion efficiency of approximately 1%.     

The multi-staged formation process of titanium oxide nanotubes and its thermal stability

The multi-staged formation process of titanium oxide nanotubes was investigated in detail under a hydrothermal treatment. During the synthesis procedure, an intermediate stage (tree-like structures) was observed before the formation of the titanium oxide layered structures. The layered structure of titanium oxide generally was considered to exfoliate directly from raw TiO₂ materials through the alkaline hydrothermal treatment. The rolling process of the layered structures of titanium oxide was confirmed by TEM observation after the alkaline hydrothermal treatment for the raw TiO₂ materials, followed by washing with 4 M HNO₃ aqueous solution. The thermal stability of the tube products was investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). The result showed that both the morphology and crystal phase of titanium oxide nanotubes could be retained even after calcination at 650 °C.     

The role of the TiO2 nanotube array morphologies in the dye-sensitized solar cells

Arrays of TiO₂ nanotubes were fabricated by the anodization of Ti foils and then used in assembling dye-sensitized solar cells (DSSCs). The role of the morphologies of the TiO₂ nanotubes in the photovoltaic performances of the DSSCs was studied in terms of the surface topography and the tube length. The necessity of removing the nanoporous films from the surface of the nanotube arrays for good DSSC performance has been demonstrated. Also, it has been shown that appropriately increasing the tube length was an effective measure for enhancing both the short-circuit current density and the conversion efficiency of the DSSCs.     

Nano-structured TiO2 films by plasma electrolytic oxidation combined with chemical and thermal post-treatments of titanium, for dye-sensitised solar cell applications

This paper demonstrates a new method to grow nano-structured TiO₂ over a plasma electrolytically oxidised titanium surface. Microstructural characterisation by employing a variety of transmission electron microscopy techniques was carried out to explore the nano-scale structural changes due to the alkaline and thermal treatments. Photovoltaic performance was measured and this revealed the effect of microstructural changes. Such coatings can be considered potential candidates for the electrode material in a dye-sensitised solar cell (DSSC). The experimental results show that a titania layer with a 3D network ‘nano-flaky’ surface can be successfully prepared. The obtained nano-flakes are around 100 to 200 nm across and have a thickness of less than 10 nm. These completely cover the outermost surface as well as the inner pores and voids. The formed nano-flaky structure is amorphous and provides a larger surface area for dye absorption to increase the efficiency of assembled DSSC. Thermal annealing treatment causes the transformation of the amorphous nano-flakes into anatase nano-crystallites and further enhances the photovoltaic efficiency of the assembled DSSC.     

Energetic negative ions in titanium oxide deposition by reactive sputtering in Ar/O2

The flux of energetic negative ions was measured during the preparation of TiO₂ in Ar/O₂ as a function of oxygen partial pressure. The Ti surface was so active that the small amount of O₂ contained in Ar was sufficient to oxidize the target surface. Ti target is also oxidized as similarly to the other metals such as Zr and Zn. Oxide islands form, which coalesce and cover the target surface with an oxide layer. The thickness of the Ti oxide layer on the target surface increased with increasing target current and Ar/O₂ gas pressure, which increased the oxygen flux incident on the target. This is due to the high reactivity of the Ti surface with oxygen. The data revealed that the flux of energetic negative ions in reactive sputtering of Ti in Ar/O₂ is fairly small compared with the sputtering of Zr and Zn. This indicates that the generation rate of negative ions on the Ti target during the reactive sputtering is very small.     

Electrospun nylon-6 spider-net like nanofiber mat containing TiO2 nanoparticles: A multifunctional nanocomposite textile material

In this study, electrospun nylon-6 spider-net like nanofiber mats containing TiO₂ nanoparticles (TiO₂ NPs) were successfully prepared. The nanofiber mats containing TiO₂ NPs were characterized by SEM, FE-SEM, TEM, XRD, TGA and EDX analyses. The results revealed that fibers in two distinct sizes (nano and subnano scale) were obtained with the addition of a small amount of TiO₂ NPs. In low TiO₂ content nanocomposite mats, these nanofiber weaves were found uniformly loaded with TiO₂ NPs on their wall. The presence of a small amount of TiO₂ NPs in nylon-6 solution was found to improve the hydrophilicity (antifouling effect), mechanical strength, antimicrobial and UV protecting ability of electrospun mats. The resultant nylon-6/TiO₂ antimicrobial spider-net like composite mat with antifouling effect may be a potential candidate for future water filter applications, and its improved mechanical strength and UV blocking ability will also make it a potential candidate for protective clothing.     

The optical properties of nanoporous structured titanium dioxide and the photovoltaic efficiency on DSSC

This study examined the characterization of nanoporous structured titanium dioxide and its application to dye-sensitized solar cells (DSSCs). TEM revealed nanopore sizes of 10.0 nm with a regular hexagonal form. When nanoporous structured TiO₂ was applied to DSSC, the energy conversion efficiency was enhanced considerably compared with that using nanometer sized TiO₂ prepared using a hydrothermal method. The energy conversion efficiency of the DSSC prepared from nanoporous structured TiO₂ was approximately 8.71% with the N719 dye under 100 mW cm⁻² simulated light. FT-IR spectroscopy showed that the dye molecules were attached perfectly to the surface and more dye molecules were absorbed on the nanoporous structured TiO₂ than on the nano-sized TiO₂ particles prepared using a conventional hydrothermal method. Electrostatic force microscopy (EFM) showed that the electrons were transferred rapidly to the surface of the nanoporous structured TiO₂ film.     

Facile synthesis of copper oxide nanotubes decorated by TiO2 nanoparticles,optical and photocatalytic activity in water

Copper oxide nanotubes decorated by TiO₂ nanoparticles (CNTNs) were fabricated by simple three-step method. First, deposition of copper onto cellulose fibres, then thermal oxidation of copper and cellulose fibres and last simply mixing copper oxide nanotubes and TiO₂ nanoparticles (NPs). Scanning electron microscopy, transmission electron microscopy and X-ray diffraction showed that the synthesised nanotubes were monoclinic-structured polycrystalline CuO with diameter and wall thickness of approximately 50～100 nm and 20～25 nm, respectively. Moreover, the diameter of the TiO₂ NPs is about 20～30 nm. Optical properties of the solutions containing copper oxide nanotubes decorated by TiO₂ NPs were studied. Discrete dipole approximation was used for the calculation of absorption, scattering and extinction cross sections of the deposited CNTNs on a glass substrate. Our simulation results show that there are good agreements between the experimental date and the simulation results. Moreover, the photocatalytic tests were done by methyl orange under visible light (λ = 633 nm) irradiation for prepared samples.