Photosensitization of nanocrystalline TiO2 film electrode with cadmium sulphoselenide

Nanocrystalline titanium dioxide (TiO₂) thin films composed of densely packed nanometer-sized grains have been successfully deposited onto an indium-doped-tin oxide (ITO) substrate. Then cadmium sulphoselenide (CdSSe) thin film was deposited onto pre-deposited TiO₂ to form a TiO₂/CdSSe film, at low temperature using a simple and inexpensive chemical method. The X-ray diffraction, selected area electron diffraction, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and water contact angle techniques were used for film characterization. Purely rutile phase of TiO₂ with super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 30-40 (±2) nm was observed. The increase in optical absorption was observed after CdSSe film deposition. Nest like surface morphology of CdSSe on TiO₂ surface results in air trapping in the crevices which prevents water from adhering to the film with increase in water contact angle. Photosensitization of TiO₂ with CdSSe was confirmed with light illumination intensity of 80 mW/cm².     

Photocatalytic and superhydrophilicity properties of N-doped TiO2 nanothin films

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.     

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 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 (I_ph). 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.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.     

Growth of oxide thin films for optical gas sensor applications

Tungsten trioxide and titanium dioxide thin films were synthesised by pulsed laser deposition. We used for irradiations of oxide targets an UV KrF* (λ = 248 nm, τ_FWHM ≅ 20 ns, ν = 2 Hz) excimer laser source, at 2 J/cm² incident fluence value. The experiments were performed in low oxygen pressure. The (0 0 1) SiO₂ substrates were heated during the thin film deposition process at temperature values within the 300-500 °C range. The structure and crystalline status of the obtained oxide thin films were investigated by high resolution transmission electron microscopy. Our analyses show that the films are composed by nanoparticles with average diameters from a few to a few tens of nm. Moreover, the films deposited at substrate temperatures higher than 300 °C are crystalline. The tungsten trioxide films consist of a mixture of triclinic and monoclinic phases, while the titanium dioxide films structure corresponds to the tetragonal anatase phase. The oxide films average transmittance in the visible-infrared spectral range is higher than 80%, which makes them suitable for sensor applications.     

A combined experimental and theoretical analysis of Fe-implanted TiO2 modified by metal plasma ion implantation

Photocatalyst titanium dioxide (TiO₂) thin films were prepared using sol-gel process. To improve the photosensitivity of TiO₂ at visible light, transition metal of Fe was implanted into TiO₂ matrix at 20 keV using the metal plasma ion implantation process. The primary phase of the Fe-implanted TiO₂ films is anatase, but X-ray diffraction revealed a slight shift of diffraction peaks toward higher angles due to the substitutional doping of iron. The additional band gap energy levels were created due to the formation of the impurity levels (Fe-O) verified by X-ray photoelectron spectroscopy, which resulted in a shift of the absorption edge toward a longer wavelength in the absorption spectra. The optical band gap energy of TiO₂ films was reduced from 3.22 to 2.87 eV with an increase of Fe ion dosages from 0 to 1 × 10¹⁶ ions/cm². The band gap was determined by the Tauc plots. The photocatalysis efficiency of Fe-implanted TiO₂ was assessed using the degradation of methylene blue under ultraviolet and visible light irradiation. The calculated density of states for substitutional Fe-implanted TiO₂ was investigated using the first-principle calculations based on the density functional theory. A combined experimental and theoretical Fe-implanted TiO₂ film was formed, consistent with the experimentally observed photocatalysis efficiency of Fe-implanted TiO₂ in the visible region.     

Synthesis and photocatalytic properties of porous TiO2 films prepared by ODA/sol-gel method

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.     

Correlation between microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol-gel dip coating

Titanium dioxide thin films have been prepared from tetrabutyl-orthotitanate solution and methanol as a solvent by sol-gel dip coating technique. TiO₂ thin films prepared using a sol-gel process have been analyzed for different annealing temperatures. Structural properties in terms of crystal structure were investigated by Raman spectroscopy. The surface morphology and composition of the films were investigated by atomic force microscopy (AFM). The optical transmittance and reflectance spectra of TiO₂ thin films deposited on silicon substrate were also determined. Spectroscopic ellipsometry study was used to determine the annealing temperature effect on the optical properties and the optical gap of the TiO₂ thin films. The results show that the TiO₂ thin films crystallize in anatase phase between 400 and 800 °C, and into the anatase-rutile phase at 1000 °C, and further into the rutile phase at 1200 °C. We have found that the films consist of titanium dioxide nano-crystals. The AFM surface morphology results indicate that the particle size increases from 5 to 41 nm by increasing the annealing temperature. The TiO₂ thin films have high transparency in the visible range. For annealing temperatures between 1000 and 1400 °C, the transmittance of the films was reduced significantly in the wavelength range of 300-800 nm due to the change of crystallite phase and composition in the films. We have demonstrated as well the decrease of the optical band gap with the increase of the annealing temperature.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/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 TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

Ultra-thin film growth of titanium dioxide on W(1 0 0)

We have employed low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy to follow the epitaxial growth of thin films of TiO₂ on W(1 0 0). The films were grown both by metal vapour deposition of titanium onto the substrate in UHV with subsequent annealing in a low partial pressure of oxygen, and by metal vapour deposition in a low partial pressure of oxygen. LEED patterns showed the characteristic patterns of (1 1 0) oriented rutile. A systematic spot splitting was observed and attributed to a stepped surface. The calculated step height was found to be in good agreement with that expected for rutile TiO₂(1 1 0), 3.3 Å. Titanium core level shifts were used to identify oxidation states as a function of film thickness allowing the interpretation in terms of a slightly sub-stoichiometric interface layer in contact with the substrate. In combination with the LEED patterns, the film structure is therefore determined to be (1 1 0) oriented rutile with a comparable level of stoichiometry to UHV prepared bulk crystals. The ordered step structure indicates considerable structural complexity of the surface.     

Synthesis and photoelectric characterization of delafossite conducting oxides CuAlO2 laminar crystal thin films via sol-gel method

Thin films of delafossite of CuAlO₂ laminar crystals on metal substrates (Ni plates) were prepared by sol-gel processing and subsequent thermal treatment in vacuum. The influence of annealing treatment on surface morphologies and structure of the samples is discussed. Field-emission scanning electron microscope (FESEM) shows the laminar surface architecture of the as-prepared CuAlO₂ thin films. The electrical property of sample was investigated by current-voltage analysis, which indicates that a rectifying junction between CuAlO₂ film and metal substrate is formed and forward current exceeds reverse current by a factor of up to three. Otherwise, the photoelectrochemical characteristics recorded under 250 mW/cm² illumination show that the as-prepared thin film electrode which was annealed at 1150 °C for 4 h in vacuum possesses the highest photocurrent density, which is 0.7 mA/cm² at 0 V vs Ag/AgCl.     

Pure and Nb-doped TiO1.5 films grown by pulsed-laser deposition for transparent p-n homojunctions

Pure and Nb-doped titanium oxide thin films were grown on sapphire substrates by pulsed-laser deposition in vacuum (10⁻⁷ mbar). The PLD growth leads to titanium oxide thin films displaying a high oxygen deficiency (TiO_1.5) compared with the stoichiometric TiO₂ compound. The structural and electrical properties (phase, crystalline orientation, nature and concentration of charge carriers, etc.) of these titanium oxide films were studied by XRD measurements and Hall effect experiments, respectively. The undoped TiO_1.5 phase displayed a p-type semiconductivity. Doping this titanium oxide phase with Nb⁵⁺ leads to an n-type behaviour as is generally observed for titanium oxide films with oxygen deficiency (TiO_x with 1.7 < x < 2). Multilayer homojunctions were obtained by the stacking of TiO_1.5 (p-type) and Nb-TiO_1.5 (n-type) thin films deposited onto sapphire substrates. Each layer is 75 nm thick and the resulting heterostructure shows a good transparency in the visible range. Finally, the I-V curves obtained for such systems exhibit a rectifying response and demonstrate that it is possible to fabricate p-n homojunctions based only on transparent conductive oxide thin films and on a single chemical compound (TiO_x).     

Transparent titania nanotubes of micrometer length prepared by anodization of titanium thin film deposited on ITO

Transparent TiO₂ nanotube arrays of micrometer lengths were prepared by anodization of titanium thin film RF sputtered on indium tin oxide (ITO) which was coated on glass substrate. The sputtering process took place at elevated temperature of 500 °C. The structures of the films were studied using scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the optical properties of the films were investigated using UV-visible spectroscopy. Two types of electrolytes were used in this work: an aqueous mixture of acetic acid and HF solution and a mixture of NH₄F and water dissolved in ethylene glycol. The concentration of NH₄F, voltage and the thickness of the sputtered titanium film were varied to study their effect on the formation of TiO₂ nanotube arrays. It is demonstrated in this work that the nanoporous layer is formed on top of the ordered array of TiO₂ nanotubes. Furthermore, the optical transmittance of TiO₂ nanotubes annealed at 450 °C is much lower than the non annealed TiO₂ nanotubes in the visible wavelength region.     

RHEED study of titanium dioxide with pulsed laser deposition

Reflection high-energy electron diffraction (RHEED) operated at high pressure has been used to monitor the growth of thin films of titanium dioxide (TiO₂) on (1 0 0) magnesium oxide (MgO) substrates by pulsed laser deposition (PLD). The deposition is performed with a synthetic rutile TiO₂ target at low fluence. The topography and structure of the deposited layers are characterized using in situ high pressure RHEED and atomic force microscope (AFM). Based on these observations the growth mode of the films is discussed. The results will be compared to earlier results obtained for the growth of TiN films on (1 0 0) MgO.     

Synthesis and characterisations of Au-nanoparticle-doped TiO2 and CdO thin films

In the present study, pure and gold nanoparticle (Au NP)-doped titanium dioxide (TiO₂) and cadmium oxide (CdO) thin film were prepared by the sol–gel method, and the effect of Au NP doping on the optical, structural and morphological properties of these thin films was investigated. The prepared thin films were characterised by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet–visible–near infrared (UV–Vis–NIR) spectra. While the optical band increases from 3.62 to 3.73 for TiO₂ thin films, it decreases from 2.20 to 1.55 for CdO thin films with increasing Au doping concentration. Analysis of XRD indicates that the intensities of peaks of the crystalline phase have increased with the increasing Au NP concentrations in all thin films. SEM images demonstrate that the surface morphologies of the samples were affected by the incorporation of Au NPs. Consequently, the most significant results of the present study are that the Au NPs can be used to modify the optical, structural and morphological properties of TiO₂ and CdO thin films.     

Photoemission investigations on nanostructured TiO2 grown by cluster assembling

Nanostructured titanium dioxide (ns-TiO₂) films were grown by supersonic cluster beam deposition method. Transmission electron microscopy demonstrated that films are mainly composed by TiO₂ nanocrystals embedded in an amorphous TiO₂ phase while their electronic structure was studied by photoemission spectroscopy. The cluster assembled ns-TiO₂ films are expected to exhibit several structural and chemical defects owing to the large surface to volume ratio of the deposited clusters. Ultraviolet photoemission spectra (hv = 50 eV) from the valence band unveil the presence of a restrained amount of surface Ti 3d defect states in the band gap, whereas Ti 2p core level X-ray photoelectron (hv = 630 eV) spectra do not manifestly disclose these defects.     

Preparation of alkaline solid polymer electrolyte based on PVA-TiO2-KOH-H2O and its performance in Zn-Ni battery

A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO₂) ceramic fillers, KOH, and H₂O was prepared by a solution casting method. The properties of PVA-TiO₂-KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO₂ filler was added. The SEM result showed that TiO₂ particles dispersed into the PVA matrix although some TiO₂ aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm⁻¹. The Zn-Ni secondary battery with the alkaline polymer electrolyte PVA-TiO₂-KOH had excellent electrochemical property at the low charge-discharge rate.     

Effect of additives and precursor chemical structure on crystalline shape and optical properties of TiO2

This paper proposes a new simple approach for synthetic of shape-defined anatase nanocuboids TiO₂ by using combination of titanium tetra isopropoxide (TTIP) and orthotitanic acid (H₄TiO₄) as titanium precursor. In first step by adding precursor to ethanol solution mixed with HCl the primary sol has been prepared, therefore two other different films by adding Methylcellulose (MC) as a carbon containing material and adding TiO₂ nanopowder as nanofiller have been prepared and properties of thin film as a function of parameters of annealing temperature and additives, have been discussed. The films were deposited on glass substrates and characterized by using UV–vis spectroscopy and scanning electron microscopy (SEM). SEM results show that optical properties of TiO₂ thin films were changed by baking in 300, 400 and 500 °C as annealing temperature. Moreover, they indicate that the additives have strong effect on anatase structure and therefore influence the optical properties.     

Photocatalytic thin films containing TiO2:N nanopowders obtained by the layer-by-layer self-assembling method

In this work, TiO₂-N powders were synthesized by high-energy ball milling, using commercial titanium dioxide (TiO₂) in the anatase phase and urea to introduce nitrogen into TiO₂ in order to enhance their photocatalytic properties in the visible spectral region. Several samples were prepared by milling a mixture of TiO₂-urea during 2, 4, 8, 12 and 24 h and characterized by spectroscopic and analytical techniques. X-ray diffraction (XRD) results showed the coexistence of anatase and high-pressure srilankite TiO₂ crystalline phases in the samples. Scanning electron microscopy (SEM) revealed that the grain size of the powder samples decreases to 200 nm at 24 h milling time. UV-Vis diffuse reflectance spectroscopic data showed a clear red-shift in the onset of light absorption from 387 to 469 nm as consequence of nitrogen doping in the samples. The photocatalytic activity of the TiO₂-N samples was evaluated by methylene blue degradation under visible light irradiation. It was found that TiO₂-N samples had higher photocatalytic activity than undoped TiO₂ samples, which could be assigned to the effect of introducing N atoms and XPS results confirm it. Using polyethylenimine (PEI), transparent thin films of TiO₂-N nanoparticles were prepared by layer-by-layer self assembly method. UV-visible spectrophotometry was employed in a quantitative manner to monitor the adsorbed mass of TiO₂ and PEI after each dip cycle. The adsorption of both TiO₂ and PEI showed a saturation dip time of 15 min.