Fabrication and characterization of nano TiO2 thin films at low temperature

Anatase TiO₂ thin films were successfully prepared on glass slide substrates via a sol–gel method from refluxed sol (RS) containing anatase TiO₂ crystals at low temperature of 100 °C. The influences of various refluxing time on crystallinity, morphology and size of the RS sol and dried TiO₂ films particles were discussed. These samples were characterized by infrared absorption spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission-scanning electron microscopy (FE-SEM) and UV–vis absorption spectroscopy (UV–vis). The photocatalytic activities of the TiO₂ thin films were assessed by the degradation of methyl orange in aqueous solution. The results indicated that titania films thus obtained were transparent and their maximal light transmittance exceeded 80% under visible light region. The TiO₂ thin films prepared from RS-6 sol showed the highest photocatalytic activity, when the calcination temperature is higher than 300 °C. The degradation of methyl orange of RS-6 thin films reached 99% after irradiated for 120 min, the results suggested that the TiO₂ thin films prepared from RS sol exhibited high photoactivities.     

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO₂ thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OⁱPr)₄} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me₂N)₂Ti(OⁱPr)₂} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO₂ polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO₂ thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO₂ thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO₂ film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO₂ film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO₂ film synthesized with BTDIP precursor to apply dye-sensitized solar cell.     

Synthesis of titanium oxide layers on glass substrates with aqueous refluxed sols (RS) and photocatalytic activities

Nanocrystalline anatase films were prepared on glass substrates by the dip-coating method from aqueous refluxed sols and calcined at 100, 300 and 500 °C. FT-IR, TEM, SEM, XRD, UV–VIS and XPS analysis were used to characterize the microstructure, phase evolution and chemical composition of the refluxed sols (RS) sols and TiO₂ films. The photocatalytic activities of the TiO₂ films were evaluated by photocatalytic degradation of aqueous methyl orange solutions. It was found that the RS sols were flavescent, alkalescent and contained anatase crystals. The TiO₂ thin films contained not only Ti and O elements, but also a small amount of N and Na elements. The TiO₂ films were transparent and its maximal light transmittance exceeded 80% under visible light region. Calcined at 300 °C, the TiO₂ thin film showed the highest photocatalytic activity, when the calcination temperature is higher than 300 °C, the decrease in photocatalytic activity is due to sintering and growth of TiO₂ crystallites resulting in the decrease of surface area. The results suggested that RS sols are promising novel precursors for synthesizing TiO₂ films, and refluxing technique is quite efficient in preparing titania nanocrystalline films.     

Structure and luminescence properties of TiO2:Er3+ nanocrystals annealed at different temperatures

Erbium doped TiO₂ nanocrystals with the structures of anatase, pyrochlore Er₂Ti₂O₇, and rutile, characterized by X-ray diffraction, have been obtained at different annealing temperatures from 300 °C to 900 °C. The nanocrystalline size for anatase TiO₂ is reduced with increasing doped erbium concentration. Following ultraviolet 325 nm irradiation, the intensity of the green emission is the most intense for the TiO₂:Er³⁺ nanocrystals with a structure of pyrochlore Er₂Ti₂O₇, which evolves from the structure of anatase annealed at 800 °C. Moreover, following ultraviolet 325 nm and infrared 980 nm irradiation, the visible emission spectra for the nanocrystals annealed at 900 °C change drastically. Correspondingly, the structure of anatase disappears, while that of rutile becomes dominant, which indicates that phase transformation occurs.     

Influence of calcination temperature on structural and optical properties of TiO2-SiO2 thin films prepared by sol-gel dip coating

We prepared TiO₂-SiO₂ thin films with various TiO₂/SiO₂ ratios by sol-gel dip coating method and explored the dependence of their structural and optical properties on calcination temperature. The absorption peaks relevant to Si—O, Si—O—Ti and Ti—O bonds appeared in the FTIR spectra. With increasing TiO₂ content, the intensity of Si—O bond peaks decreases and that of Ti—O bond peaks increases. The XRD results show that the temperature of transformation from amorphous to anatase phase is lowered as TiO₂ content increases. The crystallite size of anatase phase in composite thin films increases with increasing TiO₂ content and calcination temperature. At 1000°C, the mixed phase of anatase and rutile appears in the pure TiO₂ thin films. The rutile films are denser than the anatase films. The increase in refractive index of composite thin films with calcination temperature is related to the decreased thickness and increased density as a result of evaporation of water and organic matters below 400°C. On the other hand, it is related to the change in the crystal phase and crystallite size of the films over 400°C.     

A heterostructured SnO2–TiO2 thin film prepared by Langmuir–Blodgett technique

SnO₂–TiO₂ heterostructure films were prepared through Langmuir–Blodgett (LB) route. LB films of octadecyl amine (ODA)–titanyl oxalate multilayer deposited on Si (100) and decomposed at 600 °C showed rutile and anatase phases of ultrathin TiO₂ film. Subsequently, multilayer LB film of ODA–stannate deposited on the pre deposited TiO₂ film after decomposition at 600 °C resulted in thin SnO₂ films on the TiO₂ thin film. The phase analysis of the SnO₂–TiO₂ film showed cassiterite phase of SnO₂ as well as the rutile/anatase mixture of TiO₂ indicating a SnO₂–TiO₂ heterostructured film. Surface morphology of the pure TiO₂ film and SnO₂–TiO₂ film were analyzed by using AFM. Electrical characterization by AC impedance analysis suggested SnO₂–TiO₂ heterostructure formation. DC current voltage measurement showed increase in photocurrent indicating visible light absorption and efficient charge separation under the sunlight type radiation.     

Effect of substrate type, dopant and thermal treatment on physicochemical properties of TiO2–SnO2 sol–gel films

Thin nanocrystalline TiO₂–SnO₂ films (0–50 mol% SnO₂) were prepared on quartz and stainless steel substrates by sol–gel coating method. The obtained films were investigated by XRD, Raman spectroscopy and XPS. The size of the nanocrystallites was determined by XRD–LB measurements. We ascertained that the increase of treatment temperature and concentration of SnO₂ in the films favour the crystallization of rutile phase. The substrate type influences more substantially the phase composition of the TiO₂–SnO₂ films. It was established that a penetration of elements took place from the substrate into the films. TiO₂ films deposited on quartz substrate include a Si which stabilizes anatase phase up to 600 °C. The films which are deposited on stainless steel substrate and treated at 700 °C show the presence of significant quantity of rutile phase. This phenomenon could be explained by the combined effect of Sn dopant as well as Fe and Cr, which also are penetrated in the films from the steel substrate. The titania films doped up to 10 mol% SnO₂ on stainless steel possess only 12–17 nm anatase crystallites, whereas the TiO₂–(10–50 mol%) SnO₂ films contain very fine grain rutile phase (4 nm).     

Structural and electrical characterization of TiO2 films grown by spray pyrolysis

The sol-gel spray pyrolysis method was used to grow TiO₂ thin films onto silicon wafers at substrate temperatures between 315 and 500 °C using pulsed spray solution feed followed by annealing in the temperature interval from 500 to 800 °C in air. According to FTIR, XRD, and Raman, the anatase/rutile phase transformation temperature was found to depend on the film deposition temperature. Film thickness and refractive index were determined by Ellipsometry, giving the refractive indexes of 2.1-2.3 and 2.2-2.6 for anatase and rutile, respectively. According to AFM, film roughness increases with annealing temperature from 700 to 800 °C from 0.60 to 1.10 nm and from 0.35 to 0.70 nm for the films deposited at 375 and 435 °C, respectively. The effective dielectric constant values were in the range of 36 to 46 for anatase and 53 to 70 for rutile at 10 kHz. The conductivity activation energy for TiO₂ films with anatase and rutile structure was found to be 100 and 60 meV, respectively.     

Characterization and photocatalytic activity of boron-doped TiO<Subscript>2</Subscript> thin films prepared by liquid phase deposition technique

Boron doped TiO₂ thin films have been successfully deposited on glass substrate and silicon wafer at 30°C from an aqueous solution of ammonium hexa-fluoro titanate and boron trifluoride by liquid phase deposition technique. The boric acid was used as an F ⁻ scavenger. The resultant films were characterized by XRD, EDAX, UV and microstructures by SEM. The result shows the deposited film to be amorphous which becomes crystalline between 400 and 500°C. The EDAX and XRD data confirm the existence of boron atom in TiO₂ matrix and a small peak corresponding to rutile phase was also found. Boron doped TiO₂ thin films can be used as photocatalyst for the photodegradation of chlorobenzene which is a great environmental hazard. It was found that chlorobenzene undergoes degradation efficiently in presence of boron doped TiO₂ thin films by exposing its aqueous solution to visible light. The photocatalytic activity increases with increase in the concentration of boron.     

Phase transformation in semi-transparent TiO2 films irradiated with CO2 laser

Anatase (TiO₂) thin films were obtained by immersion of glass plates into a titanium sol-gel precursor followed by calcination at 450 °C for 3 h. The Raman results for the CO₂ laser irradiated TiO₂ films show that laser radiation is able to promote favorable changes of anatase phase in anatase/rutile mixtures. Nevertheless, the transformation process level depends on laser characteristics and scan speed of the radiation treatment.     

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.     

Nonlinear optical response of titanium oxide nanostructured thin films

Titanium (IV) oxide thin films prepared by low temperature (95 °C) hydrothermal growth were observed to undergo important structural modifications upon variation of the deposition period, modifications strongly affecting the nonlinear optical (NLO) response of the films. Depending on the growth time, the films were observed to contain anatase or rutile TiO₂. It was found that only anatase TiO₂ exhibits significant nonlinear optical response.     

Synthesis and variable temperature electrical conductivity studies of highly ordered TiO<Subscript>2</Subscript> nanotubes

Rafts of aligned, high aspect ratio TiO₂ nanotubes were fabricated by an electrochemical anodization method and their axial electrical conductivities were determined over the temperature range 225–400 °C. Length, outer diameter, and wall thickness of the nanotubes were approximately 60–80 μm, 160 nm, and 30 nm, respectively. Transmission electron microscopy studies confirmed that the TiO₂ nanotubes were initially amorphous, and became polycrystalline anatase after heat treatment at temperatures as low as 250 °C in air. The activation energy for conductivity over the temperature range 250–350 °C was found to be 0.87 eV. The conductivity values are comparable to those of nanocrystalline and nanoporous anatase thin films reported in literature.     

The effect of the H2 flow rate on the structure and optical properties of TiO2 films deposited by inductively coupled plasma assisted chemical vapor deposition

The optical and photocatalytic properties of TiO₂ are closely related to crystalline structures, such as rutile and anatase. In this paper, TiO₂ films were produced by inductively coupled plasma (ICP) assisted chemical vapor deposition (CVD) without extra heating of the substrate, and the effect of H₂ addition on the structure and optical properties of the films was investigated. After increasing the partial pressure of H₂, the structure of the TiO₂ films changed from anatase to rutile, which usually appears at high temperatures (> 600 °C). The light transmittance decreased with increasing the H₂ flow rate due to the increased surface roughness. The photocatalytic activity of the anatase TiO₂ film was better than that of the rutile TiO₂ film.     

Influence of nitric acid-assisted hydrothermal conditions on the characteristics of TiO2 catalysts and their activity in the oxidative steam reforming of methanol

Titania (TiO₂) nanoparticles (NPs) with different morphologies (spherical, rod-shaped, and mixed) were prepared by hydrothermal treatment of different nitric acid (HNO₃)/titanium (IV) isopropoxide (TTIP) molar ratios (0.25, 0.5, 1.0, and 1.7) at different hydrothermal temperatures (90, 150, 200, and 250 °C), hydrothermal times (6, 12, and 24 h), and calcination temperatures (500, 625, and 750 °C). The crystalline structure, morphology, and surface texture of the obtained TiO₂ NPs were characterized by X-ray diffraction, nitrogen adsorption–desorption isotherm, field emission-scanning electron microscopy, and high resolution-transmission electron microscopy analyses. Under a larger HNO₃: TTIP molar ratio, higher hydrothermal temperature, and higher hydrothermal time, the spherical mixed anatase–rutile phase TiO₂ NPs were converted to a nanorod (NR)-shaped rutile phase (TiO₂-R). The TiO₂-R NRs gave the highest methanol conversion level (65%) and hydrogen yield (45%) in the oxidative steam reforming of methanol at 400 °C.     

Effects of oxygen flow ratios and annealing temperatures on Raman and photoluminescence of titanium oxide thin films deposited by reactive magnetron sputtering

Titanium oxide (TiO_x) thin films were deposited on the Si(100) substrates by direct-current reactive magnetron sputtering at 3-15 % oxygen flow ratios (FO₂% = FO₂/(FO₂ + FAr) × 100%), and then annealed by rapid thermal annealing (RTA) at 350-750 °C for 2 min in air. The phase, bonding and luminescence behaviors of the as-deposited and annealed TiO_x thin films were analyzed by X-ray diffraction (XRD), Raman spectroscopy and photoluminescence (PL) spectroscopy, respectively. The as-deposited TiO_x films were amorphous from XRD and showed weak Raman intensity. In contrast, the distinct crystalline peaks of anatase and rutile phases were detected after RTA at 550-750 °C from both XRD and Raman spectra. A mixture of anatase and rutile phases was obtained by RTA at 3 FO₂% and its amount increased with annealing temperature. Only the anatase phase was detected in the 6-15 FO₂% specimens after RTA. The PL spectra of all post-annealed TiO_x films showed a broad peak in visible light region. The PL peak of TiO_x film at 3 FO₂% at 750 °C annealing can be fitted into two Gaussian peaks at ~ 486 nm (2.55 eV) and ~ 588 nm (2.11 eV) which were attributed to deep-level emissions of oxygen vacancies in the rutile and anatase phases, respectively. The peak around 550 nm was observed at 6-15 FO₂% which is attributed to electron-hole pair recombination from oxygen vacancy state in anatase phase to valence band. The variation of intensity of PL peaks is concerned with the formation of the rutile and anatase phases at different FO₂% and annealing temperatures.     

Structural and dielectric properties of Li2O-doped TiO2

The dielectric properties of the system Li–Ti–O have been exploited in the frequency range 20 Hz–1 MHz in order to obtain permittivity data of materials having high-κ′ and low loss. Doping of titanium dioxide with lithium oxide acts as a strong promoter of the anatase to rutile phase transition and it may reduce the phase transition temperature (915 °C) by more than 100 °C, possibly due to induced oxygen concentration disorders in the ternary Li–Ti–O system. For TiO₂:Li₂O molar ratios of 98.92:1.08 and calcination temperature of 950 °C the resulting material exhibits high-κ′ and low-loss permittivity properties with lack of interfacial polarization effects. Its dielectric response is superior compared to pure (undoped) rutile as obtained by calcination at much higher temperatures (1180 °C).     

Preparation, characterization and photocatalytic activity of in situ Fe-doped TiO2 thin films

Fe-doped TiO₂ thin films were prepared in situ on stainless steel substrates by liquid phase deposition, followed by calcination at various temperatures. It was found that some Fe³⁺ ions were in situ doped into the TiO₂ thin films. At 400 °C, the film became photoactive due to the formation of anatase phase. At 500 °C, the film showed the highest photocatalytic activity due to an optimal Fe³⁺ ion concentration in the film. At 900 °C, the photocatalytic activity of the films decreased significantly due to the further increase of Fe³⁺ ion concentration, the formation of rutile phase and the sintering and growth of TiO₂ crystallites.     

Hydrophilic properties of nano-TiO2 thin films deposited by RF magnetron sputtering

Microstructure and hydrophilicity of nano-titanium dioxide (TiO₂) thin films, deposited by radio frequency magnetron sputtering, annealed at different temperatures, were studied by field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle methods. It is found that the crystal phase transforms from amorphous to rutile structure with increase of annealing temperature from room temperature to 800 °C. It is also indicated that the organic contaminants on the surface of the films can be removed and the oxygen vacancies can be reduced by the annealing treatment. Annealed at the temperature below 300 °C, amorphous TiO₂ thin films show rather poor hydrophilicity, and annealed at the temperature range from 400 to 650 °C, the super hydrophilicity anatase of TiO₂ thin films can be observed. However, when the annealing temperature reaches 800 °C, the hydrophilicity of the films declines mainly derived from the appearance of rutile.