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1.
Pure TiO2 and nitrogen doped titanium dioxide (N-TiO2) thin films were prepared by sol-gel method through spin coating on soda lime glass substrates. TiCl4 and urea were used as Ti and N sources in the sol. XRD results showed nitrogen doping has retarded anatase to rutile phase transformation. The doping also leads to a decrease in roughness of the samples from 4 nm (TiO2) to 1 nm (N-TiO2). However, surface analysis by statistical methods reveals that both surfaces have self-affine structure. Optical band gap of thin films was shifted from 3.65 eV (TiO2) to 3.47 eV (N-TiO2). Hydrophilic conversion and photocatalytic degradation properties of thin films were investigated and exhibited that N-TiO2 thin film has more preferable hydrophilicity and photocatalytic properties under UV illumination.  相似文献   

2.
Nitrogen-doped titanium oxide (TiOxNy) films were prepared with ion-assisted electron-beam evaporation. The nitrogen (N) incorporated in the film is influenced by the N2 flux modulated by the N2 flow rate through an ion gun. The TiOxNy films have the absorption edge of TiO2 red-shifted to 500 nm and exhibit visible light-induced photocatalytic properties in the surface hydrophilicity and the degradation of methylene blue. The structures and states of nitrogen in the films are investigated by X-ray diffraction patterns (XRD), and X-ray photoelectron spectroscopy (XPS) and related to their visible light-induced photocatalytic properties. The results indicate that the substitutional N in anatase TiO2 can induce visible light photocatalysis. The substitutional N is readily doped by the energetic nitrogen ions from the ion gun. The best photocatalytic activity is obtained at the largest N loading about 5.6 at.%, corresponding to the most substitutional N in anatase TiO2. The film exhibits the degradation of methylene blue with a rate-constant (k) about 0.065 h−1 and retaining 7° water contact angle on the surface under visible light illumination.  相似文献   

3.
In this study, TiO2−xNx/TiO2 double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO2 film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO2 film thickness, the optical transmittance of TiO2−xNx/TiO2 film was compared with TiO2 thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.  相似文献   

4.
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 TiO2), TA (bottom layer was pure TiO2, surface layer was Ag modified), TT (pure TiO2 thin film) and AA (TiO2 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 (Iph). LSV confirmed the existence of Ag0 state in the TiO2 thin film. SEM and XRD experiments indicated that the sizes of the TiO2 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.  相似文献   

5.
A novel and simple method for preparing F-doped anatase TiO2 (defined as FTO) film with high photocatalytic activity was developed using titanium-n-butoxide and NH4F as TiO2 and fluorine precursors under mild condition, i.e. low temperature (lower than 373 K) and ambient pressure. The prepared samples were characterized by XRD, SEM, X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectrum (DRS), photoluminescence spectrum (PL) and TG-DSC analysis. The photocatalytic activity was evaluated by decomposing X-3B under artificial solar light. The results showed that the crystallinity of TiO2 was improved by F-doping. F ions can prevent the grain growth, and the transformation of anatase to rutile phase was also inhibited. The doped fluorine atoms existed in two chemical forms, and the ones incorporated into TiO2 lattice might take a positive role in photocatalysis. Compared with surface fluorination samples, FTO film exhibited better photocatalytic activity. The high photocatalytic activity of FTO may due to extrinsic absorption through the creation of oxygen vacancies rather than the excitation of the intrinsic absorption band of bulk TiO2. Furthermore, the FTO can be recycled with little photocatalytic activity depression. Without any further treatment besides rinsing, after 6 recycle utilization, the photocatalytic activity of FTO film was still higher than 79%.  相似文献   

6.
The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO2 films sputtered at substrate surface temperature Tsurf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O2 atmosphere in oxide mode of sputtering. The TiO2 films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO2 film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO2 and the total sputtering gas pressure pT are the key deposition parameters influencing the TiO2 film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO2 films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO2 films with high PCA were prepared and (iv) the structure of sputtered TiO2 films is not affected by the substrate surface temperature Tsurf when Tsurf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO2 films and results in a decrease of maximum value of Tsurf necessary for the creation of nanocrystalline nc-TiO2 film. It was demonstrated that crystalline TiO2 films with high PCA can be sputtered at Tsurf ≤ 130 °C. Based on obtained results a phase zone model of TiO2 films was developed.  相似文献   

7.
In order to improve the photocatalytic activity, N-doped titanium oxide (TiO2) films were obtained by thermal oxidation of TiN films, which were prepared on Ti substrates by ion beam assisted deposition (IBAD). The dominating rutile TiO2 phase was found in films after thermal oxidation. According to the results of X-ray photoelectron spectroscopy (XPS), the residual N atoms occupied O-atom sites in TiO2 lattice to form TiON bonds. UV-vis spectra revealed the N-doped TiO2 film had a red shift of absorption edge. The maximum red shift was assigned to the sample annealed at 750 °C, with an onset wavelength at 600 nm. The onset wavelength corresponded to the photon energy of 2.05 eV, which was nearly 1.0 eV below the band gap of pure rutile TiO2. The effect of nitrogen was responsible for the enhancement of photoactivity of N-doped TiO2 films in the range of visible light.  相似文献   

8.
Porous surface-fluorinated TiO2 (F-TiO2) films were prepared through PEG modified sol-gel method and surface fluorination. The as-prepared films were characterized with XRD, FTIR, AFM, XPS and UV-vis DRS. The effects of surface fluorination on the photocatalytic activity and hydrophilicity of porous TiO2 film were studied by photocatalytic degradation of rhodamine B (RhB) as well as water contact angle (CA) on porous TiO2 film. The results showed that the surface fluorination increased the adsorption of RhB on the porous TiO2 film and enhanced the photocatalytic degradation of RhB. The concentration and pH of NaF solutions affected much the photocatalytic activity of porous TiO2 film. Porous F-TiO2 film prepared in 40 mM NaF solution at pH 4.0 showed the highest photocatalytic activity. Because of its porous structure, the porous F-TiO2 film had original water CA of 22.7°, which is much smaller than that of normal F-TiO2 film. Under UV light irradiation, the water CA of porous F-TiO2 film decreased to 5.1° in 90 min.  相似文献   

9.
Transparent nano composite PVA–TiO2 and PMMA–TiO2 thin films were prepared by an easy and cost effective dip coating method. Al/PVA–TiO2/Al and Al/PMMA–TiO2/Al sandwich structures were prepared to study the dielectric behavior. The presence of metal–oxide (Ti–O) bond in the prepared films was confirmed by Fourier transform infrared spectroscopy. X-ray diffraction pattern indicated that the prepared films were predominantly amorphous in nature. Scanning electron micrographs showed cluster of TiO2 nanoparticles distributed over the film surface and also there were no cracks and pin holes on the surface. The transmittance of the films was above 80% in the visible region and the optical band gap was estimated to be about 3.77 eV and 3.78 eV respectively for PVA–TiO2 and PMMA–TiO2 films by using Tauc's plot. The determined refractive index (n) values were between 1.6 and 2.3. High value of dielectric constant (?′ = 24.6 and ?′ = 26.8) was obtained for the prepared composite films. The conduction in the composite films was found to be due to electrons. The observed amorphous structure, good optical properties and dielectric behavior of the prepared nano composite thin films indicated that these films could be used in opto-electronic devices and in thin film transistors.  相似文献   

10.
We have used high-energy resolution X-ray photoelectron spectroscopy to measure valence band offsets at the epitaxial anatase TiO2(0 0 1)/n-SrTiO3(0 0 1) heterojunction prepared by molecular beam epitaxy. The valence band offsets range between −0.06 ± 0.05 and +0.16 ± 0.05 eV for anatase thicknesses between 1 and 8 monolayers and three different methods of substrate surface preparation, with no systematic dependence on film thickness. The conduction band offset (CBO) varies over a comparable range by virtue of the fact that anatase and SrTiO3 exhibit the same bandgap (∼3.2 eV). In contrast, density functional theory predicts the VBO to be +0.55 eV. The lack of agreement between theory and experiment suggests that either some unknown factor in the interface structure or composition excluded from the modeling is influencing the band offset, or that density functional theory cannot accurately calculate band offsets in these oxide materials. The small experimental band offsets have important implications for the use of this interface for fundamental investigations of surface photocatalysis. Neither electrons nor holes are likely to become trapped in the substrate and thus be unable to participate in surface photocatalytic processes.  相似文献   

11.
A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO2 (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (EF) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO2 (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO2 (1 1 0) interface. Band bending in the TiO2 substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO2 (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.  相似文献   

12.
X-ray photoelectron spectroscopy has been used to study the clean TaB2(0 0 0 1) surface and its reaction with O2. In agreement with previous studies, XPS indicates that the clean surface is boron terminated. The topmost boron layer shows a chemically shifted B 1s peak at 187.1 eV compared to a B 1s peak at 188.6 eV for boron layers below the surface. The 187.1-188.6 eV peak intensity ratio and its variation with angle between the crystal normal and the detector is well described by a simple theoretical model based on an independently calculated electron inelastic mean free path of 15.7 Å for TaB2. The dissociative sticking probability of O2 on the boron-terminated TaB2(0 0 0 1) surface is lower by a factor of 104 than for the metal-terminated HfB2(0 0 0 1) surface.  相似文献   

13.
A high-quality ferromagnetic GaMnN (Mn=2.8 at%) film was deposited onto a GaN buffer/Al2O3(0 0 0 1) at 885 °C using the metal-organic chemical vapor deposition (MOCVD) process. The GaMnN film shows a highly c-axis-oriented hexagonal wurtzite structure, implying that Mn doping into GaN does not influence the crystallinity of the film. No Mn-related secondary phases were found in the GaMnN film by means of a high-flux X-ray diffraction analysis. The composition profiles of Ga, Mn, and N maintain nearly constant levels in depth profiles of the GaMnN film. The binding energy peak of the Mn 2p3/2 orbital was observed at 642.3 eV corresponding to the Mn (III) oxidation state of MnN. The presence of metallic Mn clusters (binding energy: 640.9 eV) in the GaMnN film was excluded. A broad yellow emission around 2.2 eV as well as a relatively weak near-band-edge emission at 3.39 eV was observed in a Mn-doped GaN film, while the undoped GaN film only shows a near-band-edge emission at 3.37 eV. The Mn-doped GaN film showed n-type semiconducting characteristics; the electron carrier concentration was 1.2×1021/cm3 and the resistivity was 3.9×10−3 Ω cm. Ferromagnetic hysteresis loops were observed at 300 K with a magnetic field parallel and perpendicular to the ab plane. The zero-field-cooled and field-cooled curves at temperatures ranging from 10 to 350 K strongly indicate that the GaMnN film is ferromagnetic at least up to 350 K. A coercive field of 250 Oe and effective magnetic moment of 0.0003 μB/Mn were obtained. The n-type semiconducting behavior plays a role in inducing ferromagnetism in the GaMnN film, and the observed ferromagnetism is appropriately explained by a double exchange mechanism.  相似文献   

14.
Porous TiO2 films were deposited on SiO2 pre-coated glass-slides by sol-gel method using octadecylamine (ODA) as template. The amount of ODA in the sol played an important role on the physicochemical properties and photocatalytic performance of the TiO2 films. The films prepared at different conditions were all composed of anatase titanium dioxide crystals, and TiO2 crystalline size got larger with increasing ODA amount. The maximum specific surface area of 41.5 m2/g was obtained for TiO2 powders prepared from titanium sol containing 2.0 g ODA. Methyl orange degradation rate was enhanced along with increasing ODA amount and reached the maximal value at 2.0 g addition of ODA. After 40 min of UV-light irradiation, methyl orange degradation rate reached 30.5% on the porous film, which was about 10% higher than that on the smooth film. Porous TiO2 film showed almost constant activity with slight decrease from 30.5% to 28.5% after 4 times of recycles.  相似文献   

15.
Lei Zhao 《Applied Surface Science》2008,254(15):4620-4625
Nitrogen-doped titanium dioxide (TiO2−xNx) thin films have been prepared by pulse laser deposition on quartz glass substrates by ablated titanium dioxide (rutile) target in nitrogen atmosphere. The x value (nitrogen concentration) is 0.567 as determined by X-ray photoelectron spectroscopy measurements. UV-vis spectroscopy measurements revealed two characteristic deep levels located at 1.0 and 2.5 eV below the conduction band. The 1.0 eV level is attributable to the O vacancy state and the 2.5 eV level is introduced by N doping, which contributes to narrowing the band-gap by mixing with the O2p valence band. The enhanced degradation efficiency in a broad visible-light range was observed from the degradation of methylene blue and methylene orange by the TiO2−xNx film.  相似文献   

16.
Indium tin oxide (ITO) and titanium dioxide (TiO2) single layer and double layer ITO/TiO2 films were prepared using reactive pulsed laser ablation deposition (RPLAD) with an ArF excimer laser for applications in dye-sensitized solar cells (DSSCs). The films were deposited on SiO2 substrates either at room temperatures (RT) or heated to 200-400 °C. Under optimized conditions, transmission of ITO films in the visible (vis) range was above 89% for films produced at RT and 93% for the ones deposited at higher temperatures. Increasing the substrate temperature from RT to 400 °C enhances the transmission of TiO2 films in the vis-NIR from about 70% to 92%. High transmission (≈90%) was observed for the double layer ITO/TiO2 with a transmission cut-off above 900 nm. From the transmission data, the energies gaps (Eg), as well as the refractive indexes (n) for the films were estimated. n ≈ 2.03 and 2.04, respectively for ITO films and TiO2 film deposited at 400 °C in the visible region. Post-annealing of the TiO2 films for 3 h at 300 and 500 °C was performed to enhance n. The refractive index of the TiO2 films increases with the post-annealing temperature. The direct band gap is 3.6, 3.74 and 3.82 eV for ITO films deposited at RT, 200, and 400 °C, respectively. The TiO2 films present a direct band gap of 3.51 and 3.37 eV for as deposited TiO2 films and when annealed at 400 °C, respectively. There is a shift of about 0.1 eV between ITO and ITO/TiO2 films deposited at 200 °C. The shift decreases by half when the TiO2 film was deposited at 400 °C. Post-annealing was also performed on double layer ITO/TiO2.  相似文献   

17.
TiO2 μ-donuts have been fabricated on glass and silicon substrates using polymer masks in combination with a sol-gel technique. Cylindrical poly(methyl methacrylate) (PMMA) nanopillars have been created using a composite polymer of polystyrene (PS) and PMMA followed by careful removal of the PS. Atomic force microscopy (AFM) analyses show that the height and diameter of the PMMA cylinders used as the mask are 440 ± 5 nm and 2.1 ± 0.2 μm, respectively. The cylindrical PMMA nanopillars have been coated with the sol of the TiO2 precursor by a spin coating technique and annealed in air at elevated temperature to remove the PMMA mask. Removal of the PMMA mask has resulted in the formation of well ordered μ-donuts of TiO2 on silicon surfaces. The interior and exterior heights of the TiO2 μ-donuts are found to be 373 ± 152 nm and 457 ± 136 nm, respectively; and the interior and exterior diameters of the TiO2 μ-donuts are found to be 1.33 ± 0.63 μm and 2.82 ± 0.50 μm, respectively. X-ray photoelectron spectroscopy (XPS) spectra of the TiO2 μ-donuts as well as the smooth TiO2 thin film showed signals from Ti and O confirming the presence of TiO2 with Ti 2p3/2 and O 1s peaks at 458.8 eV and 530.4 eV, respectively. The O 1s peak of the TiO2 μ-donuts shows another peak at binding energy 532.0 eV due to SiO2, as during annealing, the PMMA evaporates and the Si substrate is exposed. The X-ray diffractometer (XRD) pattern of the smooth TiO2 thin film indicates that the anatase phase is present, with the characteristic peaks observed at 2θ values of 25.4°, 37.4°, and 48° corresponding to (1 0 1), (0 0 4), and (2 0 0) planes, respectively. UV-vis absorption spectra of TiO2 μ-donuts on glass showed an unusual absorption of light in the visible region at ∼524 nm in addition to the usual UV absorption at ∼337 nm.  相似文献   

18.
The effect of thickness of TiO2 coating on synergistic photocatalytic activity of TiO2 (anatase)/α-Fe2O3/glass thin films as photocatalysts for degradation of Escherichia coli bacteria in a low-concentration H2O2 solution and under visible light irradiation was investigated. Nanograined α-Fe2O3 films with optical band-gap of 2.06 eV were fabricated by post-annealing of thermal evaporated iron oxide thin films at 400 °C in air. Increase in thickness of the Fe2O3 thin film (here, up to 200 nm) resulted in a slight reduction of the optical band-gap energy and an increase in the photoinactivation of the bacteria. Sol-gel TiO2 coatings were deposited on the α-Fe2O3 (200 nm)/glass films, and then, they were annealed at 400 °C in air for crystallization of the TiO2 and formation of TiO2/Fe2O3 heterojunction. For the TiO2 coatings with thicknesses ≤50 nm, the antibacterial activity of the TiO2/α-Fe2O3 (200 nm) was found to be better than the activity of the bare α-Fe2O3 film. The optimum thickness of the TiO2 coating was found to be 10 nm, resulting in about 70 and 250% improvement in visible light photo-induced antibacterial activity of the TiO2/α-Fe2O3 thin film as compared to the corresponding activity of the bare α-Fe2O3 and TiO2 thin films, respectively. The improvement in the photoinactivation of bacteria on surface of TiO2/α-Fe2O3 was assigned to formation of Ti-O-Fe bond at the interface.  相似文献   

19.
Increasing environmental pollution caused by the volatile organic compounds due to their toxicity makes their removal imperative. So it is crucial to develop processes which can degrade these compounds effectively. The paper demonstrates that the photocatalytic activity of TiO2 toward the decomposition of gaseous benzene in a batch reactor can be greatly enhanced by loading TiO2 onto the surface of CexZr1−xO2 (x ≥ 0.25) using sol-gel technology. This research investigated the relationship between x amount and the photocatalytic activity of TiO2. The prepared photocatalysts were characterized by BET, XRD, UV-vis diffuse reflectance and XPS analyses. The specific surface area of photocatalyst decreases as x decreases. XRD results reveal the no peaks of titania were detected. Among the five catalysts prepared, only the binding energy values of Ti2p3/2 of TiO2/Ce0.5Zr0.5O2 shift toward lower value. The order of photocatalytic activity is TiO2/Ce0.5Zr0.5O2 > TiO2/Ce0.75Zr0.25O2 > TiO2/CeO2 ≈ TiO2/Ce0.25Zr0.75O2 > TiO2/ZrO2 ≈ TiO2. The mechanism role of Ceria-Zirconia mixed oxides in photocatalytic reaction was speculated.  相似文献   

20.
The CeO2/TiO2 and TiO2/CeO2 interface composite films were prepared on glass substrates by the sol-gel process via dip-coating and calcining technique. The scanning electron microscopy (SEM) revealed that the TiO2 layer has a compact and uniformity glasslike surface with 200 nm in thickness, and the CeO2 layer has a coarse surface with 240 nm in thickness. The X-ray diffractometer (XRD) analysis showed that the TiO2 layer is made up of anatase phase, and the CeO2 layer is structured by cubic fluorite phase. Through a series of photo-degradation experiments, the relationship of the photocatalytic activity with the constituents of the films was studied. In virtue of the efficient interfacial charge separation via the process of electron transfer from TiO2 to CeO2, the photocatalytic activity of the CeO2/TiO2 composite film is high. Contrarily, the photocatalytic activity of the TiO2/CeO2 composite film is low, due to its inert surface made up of CeO2 with broad bandwidth. Apart from the effect of the film structure, the effect of film thickness on photocatalytic activity was also discussed.  相似文献   

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