Preparation, crystal structure, and photocatalytic activity of TiO2 films by chemical vapor deposition

Photocatalytic activities of TiO₂ films were experimentally studied. TiO₂ films with different crystal structures (amorphous, anatase, rutile) were prepared by a Low Pressure Metal Organic Chemical Vapor Deposition (LPMOCVD) at different reaction temperatures and also by a Sol-Gel method using TTIP (Titanium Tetra Iso-Pro-poxyde). The Effect of CVD preparation method, CVD reaction conditions, crystal structure and wave-length of UV light on the photocatalytic decomposition rate of methylene blue in aqueous solution were studied. First, the characteristics of CVD preparation of TiO₂ films, such as the CVD film growth rate, crystal structure and morphology of the grown TiO₂ films, were experimentally studied as a function of CVD reaction temperature. Secondly, photocatalytic activities of TiO₂ films were evaluated by using two types of photo-reactors. The results indicated that TiO₂ films prepared by CVD exhibit higher photocatalytic activity than a catalyst prepared by the Sol-Gel method. Among the CVD grown TiO₂ films, anatase and rutile showed high photocatalytic activities. However, amorphous TiO₂ films showed lower activities. The activity of the photocatalysts of anatase films was excellent under all types of UV-lamps. The activity of CVD-prepared anatase films was four to seven times higher than that of photocatalyst films prepared by the Sol-Gel method.     

Apatite formation on titania–vaterite powders in simulated body fluid

Titania–hydroxyapatite composites were prepared by soaking compacts of a powder mixture consisting of crystalline titania and calcium carbonate (vaterite) to form apatite in simulated body fluid (SBF). The apatite crystal formed on compacts in SBF at 37 °C within 2 days. The apatite-forming ability of the mixtures was much higher than that of titania crystals such as anatase or rutile on their own. Calcium carbonate (vaterite), which has high solubility in the aqueous solution, plays an important role in the apatite formation; the dissolution is suggested to increase the supersaturation of the apatite in SBF. Formation of titanium hydroxide groups, which may induce the apatite formation, is drastically promoted on the powder-compacts by the soaking in SBF, independently of the structures of the titania crystals (anatase or rutile). The apatite formation on the compact of the titania–calcium carbonate (vaterite) powder mixture containing the anatase phase occurs in a shorter period than that on the one of titania (rutile)–calcium carbonate (vaterite). Crystalline titania (anatase phase) is suggested to be particularly effective in inducing the apatite nucleation.     

Growth of amorphous,anatase and rutile phase TiO2 thin films on Pt/TiO2/SiO2/Si (SSTOP) substrate for resistive random access memory (ReRAM) device application

Memory structures play a basic role in providing integrated circuits of powerful processing capabilities. Even most powerful processors have nothing to offer without an accompanying memory and importantly, the development of mobile devices is dependent on the continual improvement of memory technology. Herein, we report the synthesis of TiO₂ thin films on SSTOP (Pt/TiO₂/SiO₂/Si) substrate via physical vapour deposition process for the first time. The layers consisted of Si, SiO₂, TiO₂ and Pt, hence the SSTOP shorthand is used throughout the text. Three different phases of TiO₂ thin films were obtained, i.e. amorphous, anatase and rutile phases, by controlling the reaction parameters which were examined by x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), atomic force microscopy (AFM) and Raman-scattering spectroscopy in order to understand the crystallographic, morphological, compositional and scattering properties. The detailed studies confirmed the formation of various crystal phases of titania. The grown thin films on SSTOP substrates were further utilized to fabricate resistive random access memory (ReRAM) devices and the initial electrical screening was performed on capacitor-like structures which were prepared using platinum top electrodes (diameter = 250 μm) on a 14 × 14 array metal contact mask. Current-Voltage (I–V) measurements were implemented employing a range of current compliances (IC). The detailed electrical characterizations revealed that the forming field for a switchable unipolar device was found to be greatest on rutile titania and lowest on the amorphous titania phase. Similarity, the resistive contrast was greatest on the rutile titania phase and lowest on the anatase titania phase.     

Thermally stable and photocatalytically active titania for ceramic surfaces

The most photocatalytically active titania modification anatase must be stabilised to achieve high photocatalytic activity in ceramic processes at temperatures above 1000 °C. Thermally stable TiO₂ powders were prepared by the addition of silica and boehmite nanoparticles and deposited on corundum substrates and lead-free glazes. The powders and coatings were fired at increasing temperatures, and stabilisation of the anatase phase was achieved up to 1200 °C. In general, thermal stability was found to be lower when coated on substrates compared to the powder alone, and the extent of reduction depended on the chemical composition of the substrate. Only a slight modification of the titania electronic structure was found, indicating only weak interactions between silica and titania. Based on these results it is possible to assume an amorphous silica and alumina shell encases the titania particles which prevents grain growth and the anatase to rutile phase transformation.     

Morphology and Microstructure of As-Synthesized Anodic TiO2 Nanotube Arrays

The as-grown structure of electrochemically synthesized titania nanotube arrays is investigated by scanning electron microscope (SEM) in combination with transmission electron microscope (TEM) as well as X-ray diffraction (XRD). The analysis reveals a preferred growth direction of the nanotubes relative to the substrate surface and the well control on the nanotube arrays morphology. The crystal structure of the anatase phase is detected and exists in the tube walls without any thermal treatment, which makes it possible to realize the application of as-formed TiO₂ nanotubes avoiding the degradation of the nanotube structures when sintering. In addition, a new growth, layered model of the anodic TiO₂ nanotubes is presented to obtain further understanding of the growth mechanism.     

A pH sensor based on the TiO2 nanotube array modified Ti electrode

In this paper, a novel solid state pH sensor was fabricated by anodization of titanium substrate electrode. The relationship between pH sensitivity and hydrophilicity or surface morphology of TiO₂ film was investigated. Amorphous TiO₂ nanotube has better pH response than anatase TiO₂ nanotube. After being irradiated by ultraviolet light (UV), the potential response of the electrode modified by amorphous TiO₂ nanotube was close to Nernst equation (59 mV/pH). SEM, XRD, and XPS were used to characterize electrodes. Possible mechanism was discussed by analyzing surface hydroxyl groups, crystal structure and hydrophilicity of the electrodes. The electrode has been used to detect some kinds of soft drinks and shows good response.     

Non-isothermal crystallization kinetics of nano-sized amorphous TiO2 prepared by facile sonochemical hydrolysis route

The synthesized nano-sized amorphous TiO₂ was successfully obtained by sonochemical hydrolysis of titanium tetraisopropoxide (TTIP). The microstructure and amorphous feature of TiO₂ were examined by X-ray diffraction (XRD) as well as high-resolution transmission electron microscope (HRTEM). Moreover, the selected area electron diffraction (SAED) pattern confirmed the amorphous nature of the obtained titania (TiO₂) powder. The thermal behavior of the obtained titania powder was studied using differential scanning calorimetry (DSC) measurements and thermogravimetry (TG) analysis. The transformation characterization of amorphous to anatase titania phase was carried out using the obtained exothermic peaks for anatase crystallization under the investigated non-isothermal conditions of the DSC measurements at constant heating rates (5, 10, 15 and 20?°C/min). The investigated transformation of amorphous to anatase titania was introduced using model-free isoconversional approach. The crystallization kinetics together with its dimensionality were studied to identify the growth of the anatase phase. The obtained results showed the independency of the activation energy of crystallization on the crystallized fraction and it has been found around 202.4?±?7.5 $\mathrm{KJ}/\mathrm{mol}$. Moreover, the dimensionality of crystal growth found to be in one direction that is identifying the crystallization process by dominated nucleation is the surface nucleation. The growth mechanism was discussed in view of the expected homogeneous formation of a large number of seed nuclei during sonochemical reaction.     

Effect of surfactant in a modified sol on the physicochemical properties and photocatalytic activity of crystalline TiO<Subscript>2</Subscript> nanoparticles

This study describes the effect of amphiphilic organic molecules (surfactants) in a sol on the physicochemical properties and photocatalytic activity of crystalline TiO₂ nanoparticles prepared via a simple sol–gel route at high temperatures from 400 to 800 °C. Addition of polyoxyethylenesorbitan surfactant and polyethylene oxide and polypropylene oxide triblock copolymer as particle size inhibitors and pore directing agents into a stable titania sol affected the physicochemical properties of TiO₂ nanoparticles such as their crystallographic structure, morphology, and defect structure. With the addition of the surfactants, the ratio of anatase and rutile crystal phases of TiO₂ was controlled and an active anatase crystal phase was maintained during heat treatment up to 800 °C. Decrease in the sintering rate and inhibition in crystal growth were also observed, which resulted in higher surface area and inhibition of crystallite aggregation. Bulk defects in TiO₂ were reduced while surface defects were increased as a result of the addition of surfactants. These physicochemical properties of TiO₂ nanoparticles were correlated with photocatalytic degradation of 4-chlorophenol in water. The results revealed that high crystallinity, anatase crystal phase, high specific surface area, surface defects, and segregated morphology of TiO₂ nanoparticles, which were induced by the addition of surfactants, were more advantageous for enhancing photocatalytic destruction of the model organic compound tested in the study.     

Vacuum thermal treated electroless NiP-TiO2 composite coatings

Composite NiP-TiO₂ layers were prepared by simultaneous electroless deposition of Ni-P and TiO₂ on steel substrate, from a solution in which TiO₂ particles were kept in suspension by stirring. Deposits were characterized for its structure, morphology and hardness. It was found that the chemical composition of Ni-P matrix has been influenced by the incorporation of TiO₂ particles. TiO₂ particle incorporation increases with increase in their bath concentrations (0.5-2.0 g/l). An improvement (up to 20%) in microhardness was observed in both as plated and vacuum heat-treated composite coatings compared to Ni-P coatings. Electroless deposited composite coatings exhibit an amorphous structure of the nickel matrix in which crystalline titanium oxide is incorporated. Vacuum heat treatment leads to the formation of a crystalline layer in which the Ni and Ni₃P crystallites appear apart from those of the TiO₂ (anatase). Potentiodynamic polarization measurements made on these deposits in 3.5 wt.% sodium chloride solution showed decrease in the corrosion resistance for the as-plated and heat-treated composite coatings.     

Relationship between valence of titania and apatite mineralization behavior in simulated body environment

Titania-based materials are attractive for hard tissue repair due to their bone-bonding ability induced by apatite formation in the body environment. Various surface treatments have therefore been developed to produce a hydrated titania layer on Ti and its alloys. Titania takes various valences, such as TiO (Ti²⁺) and Ti₂O₃ (Ti³⁺), as well as typical TiO₂ (Ti⁴⁺); however, there is no comprehensive study of structural effects on the apatite-forming ability of these titanias. In this study, we investigated apatite formation on titania powders with various valences in simulated body fluid. Anatase- and rutile-type TiO₂ formed apatite in simulated body fluid within 7 days, but TiO and Ti₂O₃ did not. In contrast, when the titania powders were treated with NaOH solution, the surface converted to tetravalent titania and all samples formed apatite. It is proposed that the surface electrical states of TiO and Ti₂O₃ are strongly affected by their bulk conductivity and that these behaved like pure Ti metal, which has poor apatite-forming ability. Apatite formation was favorable when the titania had a high absolute value and exhibited high fluctuations of zeta potential during initial stages in simulated body fluid, owing to adsorption of large amounts of Ca²⁺ and HPO₄²⁻.     

Electrochemical synthesis of silica-doped high aspect-ratio titania nanotubes as nanobioceramics for implant applications

The preparation of silica-doped high aspect-ratio TiO₂ nanotubes and their apatite-forming ability were demonstrated in this study. The high aspect-ratio TiO₂ nanotube layers were produced by electrochemical anodic oxidation of Ti in chloride-containing electrolytes. Nanotubes were doped with different concentrations of silica particles through anodization in NaCl electrolyte containing different concentrations of water glass (24 g/L or 48 g/L Na₂SiO₃). The biomimetic apatite deposition behavior was evaluated under simulated body fluid (SBF) with an ion concentration nearly equal to human blood plasma. The experimental results collectively demonstrate the successful silica doping of the resultant nanotube layers with significant abundant OH groups on their surfaces. The results of hydroxyapatite (HA) growth on nanotubes clearly show that the silica doping greatly enhances the fast nucleation and growth of HA, especially for the tubes in their “as-formed” amorphous state, which usually require a long time for apatite induction. The nanotubes doped with high silica content combined with an anatase or a mixture of anatase and rutile led to the formation of very thick and continuous apatite layers with a thickness of ∼7 μm in 21 days. In contrast, to the tubes doped with a low concentration of silica (grown in an electrolyte containing 24 g/L Na₂SiO₃), the HA deposited in the form of closely packed spheroid particles and never developed into continuous films. This effect could be attributed to the critical active-site density (silanol groups, >Si-OH), which provides the sterochemical match for apatite growth. Finally, the results of this study provide, for the first time, evidence for the dependence of HA morphology/microstructure on the crystallographic structure and the density of active sites (>Si-OH groups).     

Aluminium-doped TiO2 nanotubes with enhanced light-harvesting properties

Titanium dioxide (TiO₂) application in light-harvesting processes is hindered by its wide band gap. Strategies such as morphology shifts from nanoparticles to nanotubes and doping of fabricated nanostructures are widely used to address this issue. Combining both approaches, this work successfully synthesizes, for the first time, aluminium-doped TiO₂ nanotubes via a single-step anodization method at three distinct potentials (20, 40 and 60 V). SEM images revealed the successful formation of remarkably thin layers of TiO₂ nanotubes produced at 40 and 60 V. X-ray diffractograms and Raman spectra suggest the successful insertion of aluminium into the anatase lattice. Diffuse reflectance confirmed the doping process through a marked effect on the absorbance of visible light for the higher voltages, as well as through a reduction in the optical band gap. For utilization purposes, the photoelectrochemical performance of 40 V Al–TiO₂ was able to deliver a comparable response to that of a compact TiO₂ layer of the same thickness. The current density developed by the 60 V sample was increased by 120% in comparison to the undoped material, despite having an absorbance much lower than that of the latter. Overall, synthesizing an Al-doped TiO₂ nanotubular structure has proven to be a great strategy in the development of materials for application in advanced light-harvesting electrodes.     

Tailoring high-surface-area nanocrystalline TiO2 polymorphs for high-power Li ion battery electrodes

The crystallization and morphology of brookite and anatase titania (TiO₂) were controlled using the urea-mediated hydrolysis/precipitation route in the presence of the Ti³⁺ ions. Without the strong complexing agents and the non-hydrothermal conditions, simple alterations to the urea concentration led to the synthesis from brookite nanorods to anatase nanoflowers at a low temperature below 100 °C, whereas the BET specific surface area evolved from 102 to 268 m² g⁻¹, respectively. A possible formation mechanism was also proposed for these TiO₂ nanostructures. The excellent reversible capacity and rate capability were achieved for the anatase nanoflowers because of the small crystallite size and significantly large surface area.     

Anatase–rutile transformation in doped titania under argon and hydrogen atmospheres

Abstract

Pure titania pulp containing amorphous titania was heated at different temperatures and times. Above 650°C anatase phase was evolved and between 900 and 1000°C, anatase–rutile transformation occurred. The anatase–rutile transformation in TiO₂ in the presence of different transition metal oxides, namely Fe₂O₃, Cr₂O₃, NiO, CuO and MnO₂ under argon and hydrogen atmospheres was investigated. The different phases of TiO₂ were determined using powder X-ray diffraction (XRD). The anatase–rutile transformation temperature was found to be lowered in the presence of transition metal oxides. The transformation temperature was found to vary much in argon and hydrogen atmospheres compared to air in the presence of the metal oxides. Also the method of preparation of metal oxide doped TiO₂ influences rutilation. Other methods such as chemical analysis, surface area measurements and crystallite size calculation were used for the characterisation of the samples. The surface area of heated samples was found to be decreased while crystallite size increased due to rutilation on heating. The samples were also observed under a scanning electron microscope to characterise the microstructural changes associated with each thermal treatment and atmosphere. The morphology of doped titania changes much on heating due to phase modification. The atmosphere of heating also has important effect on deciding the morphology of rutilated titania.     

Effect of molar ratio of TiO2/SiO2 on the properties of particles synthesized by flame spray pyrolysis

Titania (TiO₂)–silica (SiO₂) nanoparticles were synthesized from sprayed droplets of a mixture of TEOS and TTIP by flame spray pyrolysis (FSP). The effect of molar ratio between TEOS and TTIP in the mixture on the particle properties such as particle morphology, average particle diameter, specific surface area, crystal structure, etc., were determined using TEM, XRD, BET, and FT-IR. A UV-spectrometer was also used to measure the absorption spectrum and the band gap energy of the product particles. As the molar ratio of TEOS/TTIP increased by increasing TEOS concentration at the fixed TTIP concentration, the average particle diameter of the mixed oxide nanoparticles increased with maintaining uniform dispersion between TiO₂ and SiO₂, and crystal structure was transformed from anatase to amorphous. The band gap energy of the TiO₂–SiO₂ nanoparticles increased with respect to the increase of the molar ratio due to the decrease of width of UV-absorption spectrum. Photocatalytic activity of TiO₂–SiO₂ composite particles decreased with the concentration of TEOS.     

Wetting angles and photocatalytic activities of illuminated TiO2 thin films

TiO₂ thin films have been prepared by physical vapour deposition (PVD) and plasma enhanced chemical vapour deposition (PECVD) to study the UV-induced photo-activity of this material. Wetting angle variations and photo-catalytic activity for the degradation of dyes upon UV illumination have been compared for thin films with different crystalline structure (amorphous, rutile and anatase), microstructure (columnar, compact, etc.) and porosities as estimated from the values of their refraction indices and their direct assessment with a quartz crystal monitor. The surface of the thin films became superhydrophilic upon UV light irradiation and then it recovered its original state by keeping the samples in the dark. Wetting angle decays follow very similar kinetics for amorphous and crystalline films, independently of their actual porosities. By contrast the photo-catalytic activity was very dependent on the crystalline structure of the films (anatase > rutile > amorphous) and on their porosities. The different behaviour depicted by the films with regard to these two properties suggests that they respond to different though related mechanisms and that they cannot be considered as equivalent when trying to prove the photo-activity of TiO₂.     

Effects of tungsten thickness and annealing temperature on the electrical properties of W-TiO2 thin films

TiO₂ thin films were prepared by RF magnetron sputtering onto glass substrates and tungsten was deposited onto these thin films (deposition time 15-60 s) to form W-TiO₂ bi-layer thin films. The crystal structure, morphology, and transmittance of these TiO₂ and W-TiO₂ bi-layer thin films were investigated. Amorphous, rutile, and anatase TiO₂ phases were observed in the TiO₂ and W-TiO₂ bi-layer thin films. Tungsten thickness and annealing temperature had large effects on the transmittance of the W-TiO₂ thin films. The W-TiO₂ bi-layer thin films with a tungsten deposition time of 60 s were annealed at 200 °C-400 °C. The band gap energies of the TiO₂ and the non-annealed and annealed W-TiO₂ bi-layer thin films were evaluated using (αhν)^1/2 versus energy plots, showing that tungsten thickness and annealing temperature had major effects on the transmittance and band gap energy of W-TiO₂ bi-layer thin films.     

Synthesis and enhanced photocatalytic activity of molybdenum,iron, and nitrogen triple-doped titania nanopowders

A novel Mo, Fe, and N triple-doped rutile TiO₂ nanopowder was synthesized with simple HNO₃ assisted hydrothermal treatment. Powders synthesized were characterized by using x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) surface area analysis techniques. Mo doping initiated the formation of a structure composed of a mixture of anatase and rutile with some modifications in morphology; but Mo, Fe, and N triple-doped titania powders are composed of entirely rutile structures. XPS analysis confirmed that Mo dissolved in the structure, replacing Ti atoms and forming some MoO₃ partially crystallized nano regions on the surface. Existence of Fe in the TiO₂ crystal lattice was confirmed by ICP analysis. Fe doping had an influence on the crystal structure and morphology. N was found to be dissolved in the co-doped structure by HNO₃ catalyzer autogenously. Methylene blue degradation testing and band gap measurements were performed by using UV–vis photospectroscopy and diffuse reflector apparatus in order to evaluate the photocatalytic performance of the powders. Dopant elements decreased band gap energy steadily. An enhanced photoactivity was reached by Mo, Fe, and N triple-doping as compared with that of undoped, and mono doped TiO₂ powders under UV-light irradiation. Possible reasons for the enhancement in photocatalytic activity are outlined.     

Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties

Nanosized anatase TiO₂-coated kaolin composites were prepared by the chemical deposition method starting from calcined kaolin and TiCl₄. The resultant TiO₂ nanoparticles on the kaolin surfaces existed in anatase phase after calcination at 200, 400, and 900 °C for 1 h, respectively. The surfaces of the kaolin powders were uniformly coated by a monolayer of TiO₂ nanoparticles. The higher calcination temperature was beneficial to formation of well crystallized anatase TiO₂ nanoparticles. The light scattering indexes of the TiO₂-coated calcined kaolin composites were two times higher than that of the kaolin substrate. XPS analysis shows that TiO₂ coating layers anchored at the kaolin surfaces via the Ti-O-Si and Ti-O-Al bonds.     

Effects of annealing temperature on the photocatalytic activity of N-doped TiO2 thin films

The effects of annealing temperature on the photocatalytic activity of nitrogen-doped (N-doped) titanium oxide (TiO₂) thin films deposited on soda-lime-silica slide glass by radio frequency (RF) magnetron sputtering have been studied. Glancing incident X-ray diffraction (GIAXRD), Raman spectrum, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-vis spectra were utilized to characterize the N-doped TiO₂ thin films with and without annealing treatment. GIAXRD and Raman results show as-deposited N-doped TiO₂ thin films to be nearly amorphous and that the rutile and anatase phases coexisted when the N-doped TiO₂ thin films were annealed at 623 and 823 K for 1 h, respectively. SEM microstructure shows uniformly close packed and nearly round particles with a size of about 10 nm which are on the slide glass surface for TiO₂ thin films annealed at 623 K for 1 h. AFM image shows the lowest surface roughness for the N-doped TiO₂ thin films annealed at 623 K for 1 h. The N-doped TiO₂ thin films annealed at 623 K for 1 h exhibit the best photocatalytic activity, with a rate constant (k_a) of about 0.0034 h⁻¹.