Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.     

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.     

Photocatalytic characteristics of TiO2 nanotubes with different microstructures prepared under different pulse anodizations

In this work, different positive voltages of a pulsed waveform, time intervals and electrolyte stirring were used to prepare by anodization of pure titanium plates, a series of TiO₂ thin films based on nanotubes with different morphologies and dimensions. Electrolyte stirring results in large size TiO₂ nanotubes with uneven surface morphology and less oriented directions. The titanium plates containing the TiO₂ thin films were further annealed at 450 °C for 30 min under air. It was found that only crystalline anatase was formed under this condition. Both methylene blue degradation and antibacterial tests against Escherichia coli were performed to evaluate the photocatalytic performance of these TiO₂ films. Better methylene blue degradation ability was achieved by TiO₂ nanotubes prepared under electrolyte stirring. However, the antibacterial ability of the annealed TiO₂ nanotubes was affected by their inner diameter rather than their length. It is also concluded that the anodized TiO₂ nanotube arrays fabricated in this work are promising for photo-induced methylene blue degradation and bacteria killing applications.     

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.     

Electrochemical fabrication of complex copper oxide nanoarchitectures via copper anodization in aqueous and non-aqueous electrolytes

Described is the synthesis of various copper oxide nanostructured thin films by anodization of Cu foil in aqueous and ethylene glycol electrolytes containing hydroxide, chloride and/or fluoride ions at room temperature. The nanostructure topology was found to depend on the pH of the anodization electrolyte, KOH concentration, applied voltage and the presence of chloride and fluoride ions. Our results demonstrate the opportunity to grow complex copper oxide nanostructured films possessing sub-micron thick layers by a simple and straightforward electrochemical route. Although no film was observed on the Cu surface when the anodization was carried out at 10 V in KOH solutions with pH ≤ 10, various nanoarchitectures were formed upon increasing the electrolyte pH in the presence of chloride ions. Replacing chloride ions with fluoride ions resulted in the formation of highly porous nanoarchitectures. A simple mechanism for the formation of such porous structures is proposed. Anodizing in ethylene glycol-based electrolytes resulted in the formation of leaf-like nanoarchitectures up to 500 nm in thickness. XPS analysis was performed to study the composition of the formed nanoarchitectures. Vacuum annealing of the material at 280 °C resulted in the formation of porous Cu₂O nanoarchitectures.     

Structure induced optical properties of anodized TiO2 nanotubes

TiO₂ nanotubes were synthesized by means of anodization and investigated for their structure dependent optical properties. The anodization was conducted at operating voltages between 5 and 30 V for 3 h in a neutral, organic electrolyte consisting of 0.3 wt% NH₄F + 2 wt% H₂O + ethylene glycol and the resulting nanotubes were annealed at 450 °C for 2 h in air at atmospheric pressure. It is shown that an increase in the applied anodization voltage yielded an increase in the wall thickness, diameter and length of the nanotubes and that these varying morphologies have a direct influence on the crystallite size of the nanotubes during annealing. Photoluminescence spectra indicated that the optical bandgap of the TiO₂ nanotube film decreased with the increase in the anodization voltage, whereas supplementary Raman spectra showed a decrease in the confinement of the optical phonon modes as the crystallite sizes increased, in coherence with the phonon confinement model. These results present significant insights into the size-dependent properties of these novel nanostructured forms of TiO₂ and play an important role in their implementation in photovoltaic devices, such as the dye-sensitized solar cell.     

Photoactivity of anatase–rutile TiO2 nanotubes formed by anodization method

Titania (TiO₂) nanotubes were prepared by anodizing titanium (Ti) foils in an electrochemical bath consisting of 1 M glycerol with 0.5 wt.% NH₄F.The pH of the bath was kept constant at 6 and the anodization voltage was varied from 5 V, 20 V to 30 V. It is found that the morphology of the anodized titanium is a function of anodization voltage with pits-like oxide formed for the sample made at 5 V and samples made at 20 V and 30 V consisted of well-aligned nanotubes growing perpendicularly on the titanium foil. However, the nanotubes formed on the samples made at 30 V were not uniform in terms of the nanotubes' diameter and wall thickness. Regardless of the anodization voltage, as anodised samples were amorphous. The crystal structure evolution was studied as a function of annealing temperatures and was characterised by X-ray diffraction and Raman spectroscopy analyses. Crystallization of the nanotubes to anatase phase occurred at 400 °C while rutile formation occurred at 700 °C. Disintegration of the nanotube arrays was observed at 600 °C and the structure completely vanished at 700 °C. TiO₂ nanotube annealed at 400 °C and containing 100% anatase revealed the highest photocatalytic activity for the degradation of methyl orange. Consequently, these results indicate that diameter, wall thickness, crystal structure and degree of crystallinity of the TiO₂ nanotube arrays are the important factors influencing the efficiency of the photocatalytic activity.     

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.     

Photocatalytic activities of TiO2 thin films prepared on Galvanized Iron substrate by plasma-enhanced atomic layer deposition

Titanium dioxide (TiO₂) thin films were prepared on Galvanized Iron (GI) substrate by plasma-enhanced atomic layer deposition (PE-ALD) using tetrakis-dimethylamido titanium and O₂ plasma to investigate the photocatalytic activities. The PE-ALD TiO₂ thin films exhibited relatively high growth rate and the crystal structures of TiO₂ thin films depended on the growth temperatures. TiO₂ thin films deposited at 200 °C have amorphous phase, whereas those with anatase phase and bandgap energy about 3.2 eV were deposited at growth temperature of 250 °C and 300 °C. From contact angles measurement of water droplet, TiO₂ thin films with anatase phase and Activ™ glass exhibited superhydrophilic surfaces after UV light exposure. And from photo-induced degradation test of organic solution, anatase TiO₂ thin films and Activ™ glass decomposed organic solution under UV illumination. The anatase TiO₂ thin film on GI substrate showed higher photocatalytic efficiency than Activ™ glass after 5 h UV light exposure. Thus, we suggest that the anatase phase in TiO₂ thin film contributes to both superhydrophilicity and photocatalytic decomposition of 4-chlorophenol solution and anatase TiO₂ thin films are suitable for self-cleaning applications.     

Influence of metal plasma ion implantation on photo-sensitivity of anatase TiO2 thin films

Nano-scale TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. The Ti(IV) butoxide-based TiO₂ thin films were optimized for transforming into the high-purity crystalline anatase phase when calcined at 500 °C. To further enhance the photo-catalysis sensitivity of TiO₂ thin films for use in visible light environments, a metal plasma ion implantation process was implemented to modify the band gap electron configuration of Ti. Various transition metal atoms such as Ni, Cu, V, and Fe were ionized and accelerated at 20 keV to impinge on the surface of TiO₂ substrates at a dosage of 5 × 10¹⁵ ions/cm². ESCA analysis confirmed the binding energy shift of Ti by 0.8-1.2 eV, which accounted for the increased effective positive charge of Ti, resulting in more effective electron trapping capability and, thus, the electron-hole pair separation. In addition, the absorption spectroscopy demonstrated that optical absorption in the visible light regime occurred in specimens implanted with transition metal ions, likely due to the formation of extra impurity energy levels within the original TiO₂ band gap energy structure. Among all tested implant materials, the band gap energy of TiO₂ was effectively reduced by Cu and Fe ion implantation by 0.9-1.0 eV, which was sufficient enough to excite valence electrons over the band gap in visible light environments. The feasibility of the metal-doped TiO₂ thin films for effective applications under visible light irradiation was further confirmed by using super-hydrophilicity contact-angle measurement.     

Nanostructured surface changes of Ti-35Ta-xZr alloys with changes in anodization factors

The purpose of this study was to investigate the changes of the nanostructured surface of Ti-35Ta-xZr alloys for dental application resulting from changes in anodization factors. TiO₂ nanotubes were formed on Ti-35Ta-xZr alloys by anodization in H₃PO₄-containing NaF solutions. Anodization was carried out using a scanning potentiostat. Microstructures of the alloys were examined by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD). Microstructures of the Ti-35Ta-xZr alloys were changed from α" phase to β phase, and morphologies changed from a needle-like to an equiaxed structure, with increasing Zr content. As the Zr content increased from 3 to 7 to 15 wt.%, the average thickness of the TiO₂ nanotubes increased from 4.5 μm to 6.1 μm to 9.0 μm. When the anodizing potential was increased from 3 V to 10 V, the thickness of the nanotube layers increased from about 0.5 μm to 9.5 μm. As the anodization time increased from 30 min to 180 min at 10 V, the nanotube thickness increased from 4 μm to 9.5 μm. The amorphous oxide phase in the nanotubes transformed to anatase and rutile phases of TiO₂ by heat treatment above 300 °C.     

Preparation of anatase TiO2 thin films by vacuum arc plasma evaporation

Anatase titanium dioxide (TiO₂) thin films with high photocatalytic activity have been prepared with deposition rates as high as 16 nm/min by a newly developed vacuum arc plasma evaporation (VAPE) method using sintered TiO₂ pellets as the source material. Highly transparent TiO₂ thin films prepared at substrate temperatures from room temperature to 400 °C exhibited photocatalytic activity, regardless whether oxygen (O₂) gas was introduced during the VAPE deposition. The highest photocatalytic activity and photo-induced hydrophilicity were obtained in anatase TiO₂ thin films prepared at 300 °C, which correlated to the best crystallinity of the films, as evidenced from X-ray diffraction. In addition, a transparent and conductive anatase TiO₂ thin film with a resistivity of 2.6 × 10^− 1 Ω cm was prepared at a substrate temperature of 400 °C without the introduction of O₂ gas.     

Dye-sensitized solar cells with TiO2 nanocrystalline films prepared by conventional and rapid thermal annealing processes

Titanium oxide (TiO₂) thin films are prepared by the sol-gel method and annealed at 600 °C by conventional (CTA) and rapid thermal annealing (RTA) processes on fluorine-doped tin oxide -coated glass substrates for application as the work electrode for the dye-sensitized solar cells (DSSC). TiO₂ thin films are crystallized using a conventional furnace and the proposed RTA process at annealing rates of 5 °Cmin⁻¹ and 600 °Cmin⁻¹, respectively. The TiO₂ thin films are characterized by X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller analysis. Based on the results, the TiO₂ films crystallized by RTA show better crystallization, higher porosity and larger surface area than those of CTA. The short-circuit photocurrent and open-circuit voltage values increased from 5.2 mAcm⁻² and 0.6 V for the DSSC with the CTA-derived TiO₂ films to 8.3 mAcm⁻² and 0.68 V, respectively, for the DSSC containing RTA-derived TiO₂ films.     

A Two-step anodization to grow high-aspect-ratio TiO2 nanotubes

High-aspect-ratio TiO₂ nanotubes with small diameter are favored in dye-sensitized solar cells for large dye loading provided by high surface areas. However, long TiO₂ nanotubes with small diameter are difficult to grow under usual anodizing conditions due to unavoidable chemical dissolution of the top portion of the as-fashioned tubes. In the present work, two kinds of double-layered TiO₂ nanotube arrays were prepared by changing voltage from high to low (i.e., from 30 V to 15 V) or from low to high (i.e., from 15 V to 30 V). It is found that the top layer can serve as a sacrificial layer to protect the continuous growth of the bottom layer from chemical dissolution. Accordingly, the two-step anodization from high voltage to low voltage is proposed to produce high-aspect-ratio TiO₂ nanotubes with small diameter underneath a sacrificial top layer.     

Preparation, dielectric and ferroelectric properties of Pb5Ge3O11 and Pb5Ge2.85Si0.15O11 thin films fabricated by sol-gel process

Lead germanate-silicate (Pb₅Ge_2.85Si_0.15O₁₁) ferroelectric thin films were successfully fabricated on Pt/Ti/SiO₂/(100)Si substrates by the sol-gel process. The thin films were fabricated by multi-coating at preheating temperatures of 350 and 450 °C. After annealing the thin films at 600 °C, the films exhibited c-axis preferred orientation. The degree of c-axis preferred orientation of the thin films preheated at 350 °C was higher than that of films preheated at 450 °C. Grain growth was influenced by the annealing time. The thin films exhibited a well-saturated ferroelectric P-E hysteresis loop when preheated at 350 °C and annealed at 600 °C for 1.5 h. The values of the remanent polarization (Pr) and the coercive field (Ec) were approximately 2.1 μC/cm² and 100 kV/cm, respectively.     

Preparation of anatase TiO2 thin films for dye-sensitized solar cells by DC reactive magnetron sputtering technique

Anatase titanium dioxide (TiO₂) thin films are prepared by DC reactive magnetron sputtering using Ti target as the source material. In this work argon and oxygen are used as sputtering and reactive gas respectively. DC power is used at 100 W per 1 h. The distance between the target and substrate is fixed at 4 cm. The glass substrate temperature value varies from room temperature to 400 °C. The crystalline structure of the films is determined by X-ray diffraction analysis. All the films deposited at temperatures lower than 300 °C were amorphous, whereas films obtained at higher temperature grew in crystalline anatase phase. Phase transition from amorphous to anatase is observed at 400 °C annealing temperature. Transmittances of the TiO₂ thin films were measured using UV-visible NIR spectrophotometer. The direct and indirect optical band gap for room temperature and substrate temperature at 400 °C is found to be 3.50, 3.41 eV and 3.50, 3.54 eV respectively. The transmittance of TiO₂ thin films is noted higher than 75%. A comparison among all the films obtained at room temperature showed a transmittance value higher for films obtained at substrate temperature of 400 °C. The morphology of the films and the identification of the surface chemical stoichiometry of the deposited film at 400 °C were studied respectively, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The surface roughness and the grain size are measured using AFM.     

Gas sensing mechanism of TiO2-based thin films

Two classes of thin film gas sensors have been studied: TiO₂ doped with Cr or Nb and TiO₂-SnO₂ mixed systems. Thin films have been prepared by the reactive sputtering from mosaic targets. It is demonstrated that titanium dioxide doped with Nb and Cr should be considered as a bulk sensor. Its performance is governed by the diffusion of point defects, i.e. very slow diffusion of Ti vacancies for TiO₂: 9.5 at% of Nb and fast diffusion of oxygen vacancies in the case of TiO₂: 2.5 at% Cr sensor. The corresponding response times are 55 min for TiO₂: 9.5 at% of Nb and 20 s for TiO₂: 2.5 at% Cr. In turn, sensors based on TiO₂-SnO₂, particularly those of the SnO₂-rich composition, belong to the group of surface sensors.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

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.     

Synthesis and electrophoretic deposition of hydrothermally synthesized multilayer TiO2 nanotubes on conductive filters

TiO₂ nanotubes were synthesized by the decomposition of titanium isopropoxide in water and the calcination at 450 °C for 2 h to form TiO₂ nanoparticles. The synthesized TiO₂ in anatase form nanoparticles were processed hydrothermally in 10 M NaOH solution at 130 °C for 24 h to obtain multilayer TiO₂ nanotubes. TEM analysis revealed that the diameters of the tubes were around 10 nm and they are in the length of 100 nm. Subsequently, colloidal suspensions containing 1% wt. Of TiO2 nanotubes were prepared with TEA and butanol and electrophoretic deposition (EPD) experiments were conducted in order to obtain coatings on Ni and carbon filters using a deposition time of 10 min. and an applied voltage of 65 V. It is also shown that multilayer TiO₂ nanotubes having outer diameter around 10 nm and inner diameters of 4.3 nm can be produced using the described technique. EPD is also shown to be an effective technique to coat three dimensional components, such as Ni and C filters for various applications including water and air purification systems.