Preparation of Li2B4O7 thin films by chemical solution decomposition method

Li₂B₄O₇ polycrystalline films on silica glass and Si(111) substrates were prepared by chemical solution decomposition(CSD) method. After spin coating, the wet film was dried at 200 °C, and then annealed at different temperatures to form polycrystalline Li₂B₄O₇ film. These annealed films were characterized by using X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), transmission electron microscope (TEM) and selective area electron diffraction (SAED). All these results show that the main component of the film is Li₂B₄O₇ crystalline phase and the average crystalline size of these films is in the range of 20-50 nm.     

Synthesis of TiO2 nanopellet by TiCl4 as a precursor for degradation of RhodamineB

In the present investigation in order to promote TiO₂ pellet structure and its photocatalytic activity, two new precursors were synthesized in the powder and sol forms, using sol–gel method with precipitation of TiCl₄. Since TiO₂ pellets are normally synthesized by the commercial TiO₂ powder (DegussaP25), in this investigation and in the first step a new synthesized TiO₂ powder was produced and compared with DegussaP25. Subsequently, two types of pellet were made by the new synthesized powder and titania sol. The characterization of the synthesized TiO₂ powder and pellet were performed by XRD, FT-IR, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The result showed that by the new procedure utilized here, without using any additive not only the surface area of the produced TiO₂ powder has been increased, but also the crystalline phase is completely in the anatase form. It was also found that the synthesized pellets by the sol precursor had better morphological structure than the synthesized pellets by theTiO₂ powder (either DegussaP25 or new synthesized powder). Ultimately, in order to evaluate photocatalytic activity of TiO₂ powders and pellet, degradation of RhodamineB was tested.     

TiO2 anatase thin films deposited by spray pyrolysis of an aerosol of titanium diisopropoxide

Titanium dioxide thin films were deposited on crystalline silicon (100) and fused quartz substrates by spray pyrolysis (SP) of an aerosol, generated ultrasonically, of titanium diisopropoxide. The evolution of the crystallization, studied by X-ray diffraction (XRD), atomic force (AFM) and scanning electron microscopy (SEM), reflection and transmission spectroscopies, shows that the deposition process is nearly close to the classical chemical vapor deposition (CVD) technique, producing films with smooth surface and good crystalline properties. At deposition temperatures below 400 °C, the films grow in amorphous phase with a flat surface (roughness∼0.5 nm); while for equal or higher values to this temperature, the films develop a crystalline phase corresponding to the TiO₂ anatase phase and the surface roughness is increased. After annealing at 750 °C, the samples deposited on Si show a transition to the rutile phase oriented in (111) direction, while for those films deposited on fused quartz no phase transition is observed.     

Synthesis of TiO2 sol in a neutral solution using TiCl4 as a precursor and H2O2 as an oxidizing agent

Nanosize TiO₂ thin film on glass substrate was obtained through dip-coating method using TiO₂ sol. Suspended nanosize TiO₂ sols with anatase structure in aqueous solution were synthesized by sol–gel method using TiCl₄ as a precursor. TiCl₄ was reacted with an aqueous solution of NH₄OH to form Ti(OH)₄, and H₂O₂ was then added to form peroxo titanic acid. It was further heated in water and converted to TiO₂. The effects of the preparation parameters, viz., pH value of the Ti(OH)₄ gel, concentration of H₂O₂, and heating temperature and time, on the properties of the TiO₂ sol were investigated. The materials were characterized by X-ray diffraction, Fourier transform-infrared spectroscopy, and transmission electron microscopy. The results showed that the primary TiO₂ particles were rhombus with the major axis ca. 10 nm and minor axis ca. 4 nm, and were in anatase structure. The sol was excellent in dispersibility and was stable in neutral and even slight basic conditions for at least 2 years without causing agglomeration. The best preparation condition was optimized with the pH value of Ti(OH)₄ gel at 8, H₂O₂/TiO₂ mole ratio of 2, and heating at 97 °C for 8 h. The transparent adherent TiO₂ film on glass substrates exhibits strong hydrophilicity after illuminating with ultraviolet light and it can be used as an efficient photocatalyst.     

Synthesis of the nanocrystalline CoFe2O4 ferrite thin films by a novel sol-gel method using glucose as an additional agent

Polycrystalline and nanometer-sized CoFe₂O₄ ferrite thin films are successfully synthesized using glucose as an addition agent. The thermal gravimetric/differential thermal analyzer, X-ray diffractometer, electron diffraction, scanning electron microscope, atomic force microscope and vibrating sample magnetometer are used to characterize the effects of the calcination temperature on the crystalline structure, morphology and magnetic properties of the Co-ferrite thin films. CoFe₂O₄ ferrite thin films have a single phase inverse spinel structure and are crystallized at and above 300 °C which is much lower than the required temperature in the traditional ceramic method (about 500-600 °C). Co-ferrite thin films annealed at relative low temperature of 400 °C show very small particle size with average of 32 nm and excellent magnetic properties for information storage applications.     

Room-temperature ferromagnetism in Cu-doped TiO2 thin films

We report here the observation of significant room-temperature ferromagnetism in a semiconductor doped with nonmagnetic impurities, Cu-doped TiO₂ thin films grown by reactive magnetron sputtering. Films annealed in air were not magnetic while those annealed in vacuum were ferromagnetic with a Curie temperature about 350 K. The magnetic moment per copper atom decreased as the copper concentration increased. These results show that both the oxygen vacancies and the distance between nearest-neighbor copper atoms play a crucial role for the appearance of magnetism.     

Photocatalytic thin films of TiO2 formed by a sol-gel process using titanium tetraisopropoxide as the precursor

Thin TiO₂ films were prepared with the dip-coating technique by using sols deriving from titanium tetraisopropoxide. TiO₂ films were formed on glass substrates previously covered by a SiO₂ layer obtained from a tetraethylortosilicate sol. The films, after a thermal treatment at 673 K, mainly consisted of TiO₂ anatase. The samples were characterised by X-ray diffraction, UV-Vis spectroscopy, scanning electron microscopy and atomic force microscopy. The photoactivity of the various films was tested by using as probe reaction the photo-oxidation of 2-propanol in gas-solid regime. The photoreactivity results indicated that the TiO₂ films were efficient for degrading 2-propanol under UV illumination, propanone being the only compound detected as intermediate product. Films prepared by using Degussa P25 appeared to be more photoactive, but the coating was easily detached by wiping.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Facile synthesis of mesoporous core-shell TiO2 nanostructures from TiCl3

The present study reports the synthesis and formation process of mesoporous core-shell TiO₂ nanostructures by employing a glucose-assisted solvothermal process using water-ethanol mixture as solvent and subsequent calcination process at 550 °C for 4 h. X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption analysis were used to investigate the structural properties of these nanostructures. By optimizing the preparation conditions, especially the contents of water and ethanol in the mixture solvent, mesoporous core-shell TiO₂ nanostructures were obtained. These mesoporous nanostructures have anatase phase and exhibit the superior photocatalytic activity. This synthesis route is facile due to the usage of stable and low-cost Ti precursor such as TiCl₃ and is thus applicable for large-scale production.     

Synthesis and optical properties of TiO2 nanoparticles

Ultrafine TiO₂ particles have been synthesized successfully by a facile gas flame combustion method. The synthesized sample is characterized by X-ray diffraction (XRD), transmission electron micrograph (TEM), Fourier transform infrared (FTIR), and photoluminescence (PL) spectroscopy. The as-prepared TiO₂ nanoparticles appear to be a single anatase crystalline phase and the diameter is about 9 nm. Besides a sharp emission at 398 nm originating from the radiative annihilation of excitions, a weak broad band at about 434 nm from the defect-related emission is also discussed.     

Photoelectrochemical property of ZnFe2O4/TiO2 double-layered films

ZnFe₂O₄/TiO₂ double-layered films on indium-tin oxide (ITO) substrate were prepared by a dip-coating method, and the optical absorption and photocurrent of the as-prepared films were measured. In the double-layered films, the onset of fundamental absorption edge shifts to a longer wavelength, and even shifts to a longer wavelength than that of ZnFe₂O₄-only film as the ZnFe₂O₄ layer thickness increases. Application of the coupled photoanodes double-layered films composed of ZnFe₂O₄ and TiO₂ can obviously increase the photocurrent. It was found that the photocurrent density of ZnFe₂O₄/TiO₂ double-layered films first increased and then decreased with increasing the ZnFe₂O₄ layer thickness. A five-fold increase in the photocurrent density was obtained compared with TiO₂-only films under optimum condition.     

High-temperature anomalies of dielectric constant in TiO2 thin films

Anatase and rutile TiO₂ thin films were prepared by chemical vapor deposition with precursors Ti(OPrⁱ)₄ and Ti(dpm)₂(OPrⁱ)₂ (dpm = 2,2,6,6-tetramethylheptane-3,5-dione and Prⁱ = isopropyl), respectively. The dielectric properties of TiO₂ thin films have been studied in 20-1100 K temperature range in air, in controlled Ar/O₂ atmospheres, and in vacuum with silicon-based metal-insulator-semiconductor Au/TiO₂/Si capacitors. High-temperature (T_c ∼ 980 K) anomalous behavior of dielectric constant was observed in both anatase and rutile TiO₂ thin films.     

Chemical changes induced on a TiO2 surface by electron bombardment

We study the TiO₂ (Ti⁴⁺) chemical reduction induced by electron bombardment using Auger electron spectroscopy and factor analysis. We show that the electron irradiation of a TiO₂ sample is characterized by the appearance of a lower Ti oxidation state, Ti₂O₃ (Ti³⁺), followed by a further deposition of carbon, which is present inevitably in the environment even under ultra-high vacuum conditions. The appearance of C over the surface is found to be a complex mechanism which affects the reduction process through passivation of the electron-induced oxygen desorption and formation of titanium carbide. For very high irradiation doses, we also found that the chemical changes on the surface are stopped due to the deposition of carbon in a graphitic form.     

The d.c. magnetron sputtering behavior of TiO2−x targets with added Fe2O3 or Nd2O3

Targets of 6 mm thickness were prepared from TiO₂ powder with different amounts of Fe₂O₃ and Nd₂O₃ added. The targets were sintered in a vacuum furnace to obtain sub-stoichiometric rutile TiO_2−x. For both added metal oxides, it was found that they were present as titanates forming a second phase. The sputtering behavior of these mixed-oxide targets was investigated. First, the dependence of the discharge voltage and the deposition speed on the argon pressure was measured. Second, the effect of the oxygen addition on the same two parameters was investigated. Both were compared with the dependencies measured for a pure TiO_2−x target. All experiments were performed in constant power mode. The results show that Fe₂O₃ and Nd₂O₃ exhibit different effects on the sputtering behavior of TiO_2−x targets.     

Electrochromic investigation of sol-gel-derived thin films of TiO2-V2O5

Thin films of TiO₂ and TiO₂-V₂O₅ were obtained by dip-coating sol-gel technique. Sols were prepared from titanium ethoxide and inorganic V₂O₅ sol received by dissolution of vanadium pentoxide in hydrogen peroxide. Sol-gel TiO₂ and TiO₂-V₂O₅ films are deposited on conductive glass substrates. TiO₂ and TiO₂-V₂O₅ systems were characterized by FTIR and Raman spectroscopy. Optical transmittance measurements were carried out. Electrochromic characterization was recorded by cyclic voltammetry using three-electrode arrangement. All samples demonstrated electrochromic effect.     

Third-order optical nonlinearities in anatase and rutile TiO2 thin films

Titanium dioxide (TiO₂) films have been fabricated on fused quartz and Si(001) substrates by pulsed laser deposition technique and the single-phase anatase and rutile films were obtained under the optimal conditions. The surface images and optical transmission spectra were investigated by scanning electron microscopy and double beam spectrophotometer, respectively. The values of optical band-gap and linear refractive index of the anatase and rutile films were determined. The optical nonlinearities of the films were measured by Z-scan method using a femtosecond laser (50 fs) at the wavelength of 800 nm. Through the open-aperture and closed-aperture Z-scan measurements, the real and imaginary parts of the third-order nonlinear optical susceptibility were calculated and the results show that the anatase phase TiO₂ films exhibit larger nonlinear refractive effects compared with rutile phase. The figure of merit, T, defined by T = βλ/n₂, was calculated to be 0.8 for anatase films, meeting the requirement of T < 1 and showing potential applications in all-optical switching devices.     

TiO2 thin films for dyes photodegradation

The aim of the present study is to investigate the influence of the TiO₂ specific surface (powder, film) on the photocatalytic degradation of methyl orange. Porous TiO₂ films were deposited on transparent conducting oxide substrates by spray pyrolysis deposition. The films were characterized by X-ray diffraction (XRD), Scanning Electronic Microscopy, and the UV-Vis spectroscopy. The XRD spectra of nanoporous TiO₂ films revealed an anatase, crystalline structure that is known as the most suitable structure in photocatalysis. The average thickness of the films was 260 nm and the measured band gap is 3.44 eV. The influence of the operational parameters (dye concentration, contact time) on the degradation rate of the dye on TiO₂ was examined. There were calculated the kinetic parameters and the process efficiency. Using thin films of TiO₂ is technologically recommended but raises problems due to lowering the amount of catalyst available for the dye degradation.     

Low-temperature deposition of crystallized TiO2 thin films

Crystallized TiO₂ thin films were deposited on a non-heated substrate by two methods: oxygen-ion-assisted reactive evaporation (ORE) and high-rate reactive sputtering (HRS) using two sputtering sources. When the films were deposited on an unheated glass substrate, amorphous films were initially grown on the substrate in case of both deposition methods, although an increase in oxygen-ion energy above 600 eV led to a growth of a crystallized layer on the amorphous films in the case of ORE. When the films were deposited by HRS on a crystallized TiO₂ seed layer, homo-epitaxial growth was observed, and crystallized TiO₂ films with an excellent hydrophilic property were obtained on unheated substrate. In contrast, when the films were deposited by ORE, amorphous films were initially grown on the crystallized TiO₂ seed layer in a similar manner to the deposition of films on a glass substrate, and homo-epitaxial growth was not observed. These results suggest that the large kinetic energy of titanium atoms arriving at the substrate during HRS is a key factor in promoting epitaxial growth of the TiO₂ film at low temperature.     

The mechanism of TiO2 deposition by direct current magnetron reactive sputtering

Thin films are generally thought of as being the product of a reaction between the surface and atoms and/or molecules in the gas phase. However, a relatively new theory, the theory of charged clusters (TCC), suggests that charged clusters nucleate in the gas phase and become the growth unit for a thin film. The aim of this study was to determine whether or not TiO₂ thin film deposition by DC reactive sputtering occurs via this mechanism. TiO₂ was deposited on unheated transmission electron microscopy grids to observe TiO₂ clusters, as well as glass and silicon substrates to observe the resulting thin films. The results showed that TiO₂ clusters were indeed produced in the chamber of a direct current reactive sputtering system. Furthermore, these clusters were observed as close as 50 mm away from the target. Clusters 3 nm and <2 nm in diameter were found 250 mm and 50 mm away from the target, respectively The cluster size was found to have a direct effect on the film deposited. Smaller clusters produced a facetted crystalline anatase film whereas larger clusters produced an amorphous film.     

Hydrophilicity of anatase TiO2/Cr-doped TiO2 thin films with different band gaps

Based on the concept that the electron-hole separation effect caused by a different band-gap structure would improve its hydrophilicity, anatase-TiO₂/Cr-doped TiO₂ thin films were synthesized by DC magnetron sputtering. The optical band gaps of TiO₂ thin films decreased from 3.23 to 2.95 eV with increasing Cr-doping content. Multilayer TiO₂ thin films with different band gaps exhibited a superhydrophilicity under UV illumination. In particular, in anatase TiO₂ (3.23 eV)/4.8% Cr-doped TiO₂ (2.95 eV), the hydrophilicity, which indicated a contact angle of less than 20°, lasted for 48 h in the dark after UV illumination was discontinued. This outstanding result has rarely been reported for TiO₂ thin films, which confirmed that the prominent superhydrophilicity of anatase TiO₂/Cr-doped TiO₂/glass could be attributed to the retardation of electron-hole recombination caused by the band-gap difference.