Preparation of self-supporting hierarchical nanostructured anatase/rutile composite TiO2 film

Via the combination of an electrospinning method with a hydrothermal reaction, a large-scale cedar-like hierarchical nanostructured TiO2 film with an anatase/rutile composite phase was fabricated.

First-principles study of the electronic structures and magnetic properties of 3d transition metal-doped anatase TiO2

We study the electronic structures and magnetic properties of the anatase TiO2 doped with 3d transition metals (V, Cr, Mn, Fe, Co, Ni), using first-principles total energy calculations based on density functional theory (DFT). Using a molecular-orbital bonding model, the electronic structures of the doped anatase TiO2 are well understood. A band coupling model based on d-d level repulsions between the dopant ions is proposed to understand the chemical trend of the magnetic ordering. Ferromagnetism is found to be stabilized in the V-, Cr-, and Co-doped samples if there are no other carrier native defects or dopants. The ferromagnetism in the Cr- and Co-doped samples may be weakened by the donor defects. In the Mn-, and Fe-doped samples, the ferromagnetism can be enhanced by the acceptor and donor defects, respectively.

Possible origin of ferromagnetism in undoped anatase TiO2

Using first-principles electronic structure calculations we find that the titanium vacancy and divacancy may be responsible for the unexpected ferromagnetism in undoped anatase TiO2. An isolated titanium vacancy produces a magnetic moment of 3.5 mu(B), and an isolated titanium divacancy produces a magnetic moment of 2.0 mu(B). The origin of the collective magnetic moments is the holes introduced by the titanium vacancy or divacancy in the narrow nonbonding oxygen 2p(pi) band. At the center of the divacancy, an O-2 dimer forms during the relaxation, which lowers the total energy of the system and leads to the decrease in the total magnetic moment due to a hole compensation mechanism. For both the two native defects, the ferromagnetic state is more stable than the antiferromagnetic state.

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO2 thin films were fabricated. The Ag/TiO2 composite films were prepared by incorporating Ag in the pores of TiO2 films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N-2 adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy.

Study of crystal formation in titanate glass irradiated by 800 nm femtosecond laser pulse

The structure of the titanate glass is destroyed during irradiation by the femtosecond laser pulses, and (TiO6)(8-) and (TiO4)(4-) anion units are exsolved from the network of the titanate glass. These anion units are rearranged to form some crystals such as anatase and Ba2TiO4 crystals. By Raman spectroscopy, it is found that these crystals have a strong dependence on the intensity of the femtosecond laser pulses. The relation between the generation of these crystals and space distribution of the femtosecond laser power intensity is qualitatively explained. (c) 2005 Elsevier B.V. All rights reserved.

Effect of microstructure of TiO2 thin films on optical band gap energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to 3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.

Investigation on microstructure and optical properties of titanium dioxide coatings annealed at various temperature

TiO2 coatings were prepared on fused silica with conventional electron beam evaporation deposition. After TiO2 thin films were annealed at different temperatures for 4 h, several properties were investigated by X-ray diffraction (XRD), spectrometer.. photoelectron spectroscopy (XPS) and AFM. It was found that with the annealing temperature increasing, the transmittance of TiO2 coatings decreased, and the cutoff wavelength shifted to long wavelength in near ultraviolet band. Especially, when coatings were annealed at high temperature, the optical loss is very serious, which can be attributed to the scattering and the absorption of TiO2 coatings. XRD patterns revealed that only anatase phase was observed in TiO2 coatings regardless of the different annealing temperatures. XPS results indicated that the fine chemical shift of TiO2 2p(1/2) should be attributed to existence of oxygen vacancies around Ti+4 ion. The investigation on surface morphology by AFM showed that the RMS of titania thin films gradually increases from less than 0.40 nm to 5.03 nm and it should be ascribed to the growth of titanium dioxide grain size with the increase of annealing temperature. (C) 2005 Elsevier B.V. All rights reserved.

薄膜材料对TiO2基薄膜激光损伤阈值的影响

abstract {The optical property, structure, surface properties (roughness and defect density) and laser-induced damage threshold (LIDT) of TiO₂ films deposited by electronic beam (EB) evaporation of TiO₂ (rutile), TiO₂ (anatase) and TiO₂ + Ta₂O₅ composite materials are comparatively studied. All films show the polycrystalline anatase TiO₂ structure. The loose sintering state and phase transformation during evaporating TiO₂ anatase slice lead to the high surface defect density, roughness and extinction coefficient, and low LIDT of films. The TiO₂ + Ta₂O₅ composite films have the lowest extinction coefficient and the highest LIDT among all samples investigated. Guidance of selecting materials for high LIDT laser mirrors is given.}

Effects of deposition rates on laser damage threshold of TiO2/SiO2 high reflectors

TiO2 single layers and TiO2/SiO2 high reflectors (HR) are prepared by electron beam evaporation at different TiO2 deposition rates. It is found that the changes of properties of TiO2 films with the increase of rate, such as the increase of refractive index and extinction coefficient and the decrease of physical thickness, lead to the spectrum shift and reflectivity bandwidth broadening of HR together with the increase of absorption and decrease of laser-induced damage threshold. The damages are found of different morphologies: a shallow pit to a seriously delaminated and deep crater, and the different amorphous-to-anatase-to-rutile phase transition processes detected by Raman study. The frequency shift of Raman vibration mode correlates with the strain in. film. Energy dispersive X-ray analysis reveals that impurities and non-stoichiometric defects are two absorption initiations resulting to the laser-induced transformation. (C) 2008 Elsevier B. V. All rights reserved.

Design of Narrow-Gap TiO2: A Passivated Codoping Approach for Enhanced Photoelectrochemical Activity

To improve the photoelectrochemical activity of TiO2 for hydrogen production through water splitting, the band edges of TiO2 should be tailored to match with visible light absorption and the hydrogen or oxygen production levels. By analyzing the band structure of TiO2 and the chemical potentials of the dopants, we propose that the band edges of TiO2 can be modified by passivated codopants such as (Mo+C) to shift the valence band edge up significantly, while leaving the conduction band edge almost unchanged, thus satisfying the stringent requirements. The design principle for the band-edge modification should be applicable to other wide-band-gap semiconductors.

Spectroscopic ellipsometry study of In2O3 thin films

In2O3 films grown by helicon magnetron sputtering with different thicknesses were characterized by spectroscopic ellipsometry in the energy range from 1.5 to 5.0 eV. Aside from one amorphous sample prepared at room substrate temperature, polycrystalline In2O3 films with cubic crystal structure were confirmed for other four samples prepared at the substrate temperature of 450 A degrees C. Excellent SE fittings were realized by applying 1 and/or 2 terms F&B amorphous formulations, building double layered film configuration models, and further taking account of void into the surface layer based on Bruggeman effective medium approximation for thinner films. Spectral dependent refractive indices and extinction coefficients were obtained for five samples. The curve shapes were well interpreted according to the applied dispersion formulas. Almost similar optical band gap values from 3.76 to 3.84 eV were obtained for five samples by Tauc plot calculation using extinction coefficients under the assumption of direct allowed optical transition mode.

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

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 anoclization 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 anoclization voltage. The peaks at 25.3 degrees and 48.0 degrees of X-ray diffraction pattern illuminate that the TiO2 nanotube arrays annealed at 500 degrees C are mainly in anatase phase. The filed emission (FE) properties of the samples were investigated. A turn-on electric field 7.8 V/mu m, a field enhancement factors approximately 870 and a highest FE current density 3.4 mA/cm(2) were obtained. The emission current (2.3 mA/cm(2) at 18.8 V/mu m) was quite stable within 480 min. The results show that the FE properties of TiO2/Ti have much relation to the structure parameters.

Synthesis of Titania in Ethanol/Acetic Acid Mixture Solvents: Phase and Morphology Variations

The phase and morphology variations of titania prepared in ethanol/acetic acid mixture solvents have been systematically investigated. X-ray diffraction results and microscopy observations reveal that pure anatase aggregates consisted of small nanoparticles, pure rutile microspheres comprised of nanofibers, and their mixtures could be obtained by varying ratios of ethanol to acetic acid under solvothermal conditions. The contents of anatase and rutile in the mixed phases also vary with the ratios of ethanol to acetic acid. Field emission scanning electron microscopy and high resolution transmission electron microscopy results show that the two phases are separated from each other in final products and form aggregates with morphologies resembling to their pure phase products obtained under favorable conditions. The as-produced rutile nanofibers, either in pure phase or in mixed phases, tend to grow into hollow microspheres.

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles

A simple method to prepare titania nanomaterials of core-shell structure, hollow nanospheres and mesoporous nanoparticles has been developed. The core-shell nanostructures with NH4Cl as core and TiO2 center dot xH(2)O-NH4Cl as shell were prepared in nonaqueous system by the deposition on the surface of the aggregated NH4Cl crystals, which could be transformed into mesoporous anatase nanoparticles or hollow nanospheres by calcination at 500A degrees C or extraction with methanol, respectively. The hierarchical mesoporous nanostructures benefited the photocatalytic activities of the resultant titania nanomaterials, demonstrated by the UV light photodegradation of Methyl Orange.