Effects of tungsten thickness and annealing temperature on the electrical properties of W-TiO2 thin films

TiO₂ thin films were prepared by RF magnetron sputtering onto glass substrates and tungsten was deposited onto these thin films (deposition time 15-60 s) to form W-TiO₂ bi-layer thin films. The crystal structure, morphology, and transmittance of these TiO₂ and W-TiO₂ bi-layer thin films were investigated. Amorphous, rutile, and anatase TiO₂ phases were observed in the TiO₂ and W-TiO₂ bi-layer thin films. Tungsten thickness and annealing temperature had large effects on the transmittance of the W-TiO₂ thin films. The W-TiO₂ bi-layer thin films with a tungsten deposition time of 60 s were annealed at 200 °C-400 °C. The band gap energies of the TiO₂ and the non-annealed and annealed W-TiO₂ bi-layer thin films were evaluated using (αhν)^1/2 versus energy plots, showing that tungsten thickness and annealing temperature had major effects on the transmittance and band gap energy of W-TiO₂ bi-layer thin films.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.     

Photo-Generated Activities of Nanocrystalline TiO<Subscript>2</Subscript> Thin Films

Transparent nanocrystalline TiO₂ thin films with high photocatalytic activity and photo-induced wettability were successfully deposited on a glass slide. Crystal phase transformations and particle size of TiO₂ were investigated. Structural and morphological properties of the films were investigated. The photocatalytic activity of the TiO₂ films was evaluated. It is found that the photocatalytic activity of TiO₂ thin films is significantly decreased by increasing the annealing temperature, which results in a decrease in BET surface area and an increase in crystal size. In addition, increasing film thickness within a certain range significantly improves the photocatalytic activity without causing crack formation of the TiO₂ films. Photocatalytic oxidation and photo-induced wettability conversion on the films were investigated. It is found that photo-induced hydrophilic conversion is observed even on the samples annealed at high temperature. The best photo-generated activities are obtained by optimization of dip-coating cycles and annealing temperatures.     

Effects of rf-power and working pressure on formation of rutile phase in rf-sputtered TiO2 thin film

Thin TiO₂ films have been deposited on glass substrates by a radio-frequency (rf) magnetron sputtering technique. The films were coated under argon atmosphere at three different rf-powers: 80, 100 and 120 W, and three working pressures: 1.0 × 10⁻², 2.5 × 10⁻³ and 1.0 × 10⁻³ mbar. Film structures were analyzed with XRD. At 100 and 120 W, films coated under low working pressure have developed the rutile phase with the preferred (1 1 0) orientation. However, at 80 W, the films have been observed only in an amorphous phase for all working pressures. This effect could be understood as sputtered TiO₂ molecules were more energetic at high rf-powers and encountered fewer collisions at low pressure before deposited onto the substrates. The films have also been annealed at 773 or 873 K. The post-deposition annealing has significantly improved crystallization of the TiO₂ films. In this contribution, results on optical and wetting properties of these films are also reported.     

Effect of rapid thermal annealing on the structural and electrical properties of TiO2 thin films prepared by plasma enhanced CVD

Titanium oxide thin films were deposited on p-type Si(100), SiO₂/Si, and Pt/Si substrates by plasma enhanced chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄ and oxygen. As-deposited amorphous TiO₂ thin films were treated by rapid thermal annealing (RTA) in oxygen ambient, and the effects of RTA conditions on the structural and electrical properties of TiO₂ films were studied in terms of crystallinity, microstructure, current leakage, and dielectric constant. The dominant crystalline structures after 600 and 800 ‡C annealing were an anatase phase for the TiO₂ film on SiO₂/Si and a rutile phase for the film on a Pt/Si substrate. The dielectric constant of the as-grown and annealed TiO₂ thin films increased depending on the substrate in the order of Si, SiO₂/Si, and Pt/ Si. The SiO₂ thin layer was effective in preventing the formation of titanium silicide at the interface and current leakage of the film. TEM photographs showed an additional growth of SiO_x from oxygen supplied from both SiO₂ and TiO₂ films when the films were annealed at 1000 ‡C in an oxygen ambient. Intensity analysis of Raman peaks also indicated that optimizing the oxygen concentration and the annealing time is critical for growing a TiO₂ film having high dielectric and low current leakage characteristics.     

Synthesis of titania/carbon nanotube heterojunction arrays for photoinactivation of E. coli in visible light irradiation

TiO₂/multi-wall carbon nanotube (MWNT) heterojunction arrays were synthesized and immobilized on Si(0 0 1) substrate as photocatalysts for inactivation of Escherichia coli bacteria. The vertically aligned MWNT arrays were grown on ∼5 nm Ni thin film deposited on the Si by using plasma enhanced chemical vapor deposition at 650 °C. Then, the MWNTs were coated by TiO₂ using dip-coating sol-gel method. Post annealing of the TiO₂/MWNTs at 400 °C resulted in crystallization of the TiO₂ coating and formation of Ti-C and Ti-O-C carbonaceous bonds at the heterojunction. The visible light-induced photoinactivation of the bacteria increased from MWNTs to TiO₂ to TiO₂/MWNTs, in which the bacteria could even slightly breed on the MWNTs. In addition, the TiO₂/MWNTs annealed at 400 °C showed a highly improved antibacterial activity than the TiO₂/MWNTs annealed at 100 °C. The excellent visible light-induced photocatalytic efficiency of the TiO₂/MWNTs/Si film annealed at 400 °C was attributed to formation of the carbonaceous bonds at the heterojunction, in contrast to the 100 °C annealed TiO₂/MWNTs/Si sample which had no such effective bonds.     

Low temperature growth of nanocrystalline Fe2TiO5 perovskite thin films by sol–gel process assisted by microwave irradiation

Nanocrystalline Fe₂TiO₅ thin films have been grown on Si (1 0 0) at room temperature by using simple, cost effective sol–gel process assisted by microwave irradiation for thermal treatment. For comparison purpose the deposited films have been subjected to two kinds of annealing treatments: first set by using conventional annealing and second set by irradiating the deposited films at different microwave powers for 10 min. In both treated films, formation of orthorhombic phase of Fe₂TiO₅ structure has been observed. It is evident that there is a dramatic structural modification when the deposited films are exposed to microwave. There was slight stoichiometric change of Fe₂TiO₅ thin films treated by conventional annealing and microwave annealing. Microwave exposed films have shown 47% of Fe, 6% of Ti and 47% of O in the films of the Fe₂TiO₅, whereas annealed films have shown close to the stoichiometry in Fe₂TiO₅ with 30% of Fe, 14% of Ti and 56% of O. Plausible mechanism for the formation of nanocrystalline orthorhombic phase of Fe₂TiO₅ perovskite structure at low microwave powers has also been discussed. This new innovative microwave heating could open a door for the advanced nanotechnologies to cut down the process cost in post treatment of the nanomaterials.     

Ferroelectric and structural instability of (Pb,Ca)TiO3 thin films prepared in an oxygen atmosphere and deposited on LSCO thin films which act as a buffer layer

Structural, microstructural and ferroelectric properties of Pb_0.90Ca_0.10TiO₃ (PCT10) thin films deposited using La_0.50Sr_0.50CoO₃ (LSCO) thin films which serve only as a buffer layer were compared with properties of the thin films grown using a platinum-coated silicon substrate. LSCO and PCT10 thin films were grown using the chemical solution deposition method and heat-treated in an oxygen atmosphere at 700 °C and 650 °C in a tube oven, respectively. X-ray diffraction (XRD) and Raman spectroscopy results showed that PCT10 thin films deposited directly on a platinum-coated silicon substrate exhibit a strong tetragonal character while thin films with the LSCO buffer layer displayed a smaller tetragonal character. Surface morphology observations by atomic force microscopy (AFM) revealed that PCT10 thin films with a LSCO buffer layer had a smoother surface and smaller grain size compared with thin films grown on a platinum-coated silicon substrate. Additionally, the capacitance versus voltage curves and hysteresis loop measurement indicated that the degree of polarization decreased for PCT10 thin films on a LSCO buffer layer compared with PCT10 thin films deposited directly on a platinum-coated silicon substrate. This phenomenon can be described as the smaller shift off-center of Ti atoms along the c-direction 〈001〉 inside the TiO₆ octahedron unit due to the reduction of lattice parameters. Remnant polarization (P_r) values are about 30 μC/cm² and 12 μC/cm² for PCT10/Pt and PCT10/LSCO thin films, respectively. Results showed that the LSCO buffer layer strongly influenced the structural, microstructural and ferroelectric properties of PCT10 thin films.     

Photocatalytic treatments on dental mirror surfaces using hydrolysis of titanium alkoxide

Anatase titanium dioxide (TiO₂) photocatalytic thin films were directly formed on glass slide and commercial dental mirror substrate surfaces by a hydrolysis of titanium alkoxide, and the hydrophilicity, the degree of oxidizing power and the transparency of the anatase TiO₂-coated substrate surfaces. The contact angles of water and the decomposition rates of methylene blue on the anatase TiO₂ photocatalytic thin films improved with the increasing duration of a tetraethyl orthotitanate (TEOT) hydrolysis, but they hardly changed for the longer duration. The reflectance of anatase TiO₂ photocatalytic thin films coated on glass slide substrate surfaces was higher as the duration of a TEOT hydrolysis increased. Similar tendencies concerning hydrophilicity and transparency were recognized in cases of commercial dental mirror substrate surfaces. A hydrolysis of titanium alkoxide obtained superhydrophilic and antibacterial treatments with excellent transparency on commercial dental mirror substrate surfaces.     

Photocatalytic functional coatings of TiO2 thin films on polymer substrate by plasma enhanced atomic layer deposition

We prepared photocatalytic TiO₂ thin films which exhibited relatively high growth rate and low impurity on polymer substrate by plasma enhanced atomic layer deposition (PE-ALD) from Ti(NMe₂)₄ [tetrakis (dimethylamido) Ti, TDMAT] and O₂ plasma to show the self-cleaning effect. The TiO₂ thin films with anatase phase and bandgap energy about 3.3 eV were deposited at growth temperature of 250 °C and the photocatalytic effects were compared with commercial Activ glass. From contact angles measurement of water droplet and photo-induced degradation test of organic liquid, TiO₂ thin films with anatase phases showed superhydrophilic phenomena and decomposed organic liquid after UV irradiation. The anatase TiO₂ thin film on polymer substrate showed highest photocatalytic efficiency after 5 h UV irradiation. We attribute the highest photocatalytic efficiency of TiO₂ thin film with anatase structure to the formation of suitable crystalline phase and large surface area.     

Photocatalytic Decomposition of Formic Acid Under Visible Light Irradiation Over V-ion-implanted TiO2 Thin Film Photocatalysts Prepared on Quartz Substrate by Ionized Cluster Beam (ICB) Deposition Method

Unique visible-light-responsive TiO₂ photocatalysts (λ>450 nm) were successfully developed by implantation of V ions into the TiO₂ thin films prepared on a quartz substrate by an ionized cluster beam (ICB) deposition method. After V ions implantation into TiO₂ thin film, the photocatalytic activity of the thin films for the decomposition of formic acid into CO₂ and H₂O was found to proceed efficiently under visible light irradiation longer than 450 nm. The TiO₂ thin film photocatalysts were characterized by XRD, UV-vis, XPS, FE-SEM and AFM.     

Single step electrosynthesis of Cu2ZnSnS4 (CZTS) thin films for solar cell application

The Cu₂ZnSnS₄ (CZTS) thin films have been electrodeposited onto the Mo coated and ITO glass substrates, in potentiostatic mode at room temperature. The deposition mechanism of the CZTS thin film has been studied using electrochemical techniques like cyclic voltammetery. For the synthesis of these CZTS films, tri-sodium citrate and tartaric acid were used as complexing agents in precursor solution. The structural, morphological, compositional, and optical properties of the CZTS thin films have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and optical absorption techniques respectively. These properties are found to be strongly dependent on the post-annealing treatment. The polycrystalline CZTS thin films with kieserite crystal structure have been obtained after annealing as-deposited thin films at 550 in Ar atmosphere for 1 h. The electrosynthesized CZTS film exhibits a quite smooth, uniform and dense topography. EDAX study reveals that the deposited thin films are nearly stoichiometric. The direct band gap energy for the CZTS thin films is found to be about 1.50 eV. The photoelectrochemical (PEC) characterization showed that the annealed CZTS thin films are photoactive.     

Enhanced photocatalytic activity of Au-buffered TiO2 thin films prepared by radio frequency magnetron sputtering

Au-buffered TiO₂ thin films have been prepared by radio frequency magnetron sputtering method. The structural and morphological properties of the thin films were characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic activity of the samples was evaluated by the photodecomposition of methylene blue. The Au-buffer thin layer placed between the TiO₂ thin films significantly enhanced photocatalytic activity by 50%. Annealing the Au-buffered TiO₂ thin film at 600 °C decreased the film roughness, but it increased the surface area and anatase crystalline size, enhancing the photocatalytic activity.     

Preparation of Ti/SnO2-Sb2O4 photoanode by electrodeposition and dip coating for PEC oxidations

Thin films of antimony-doped SnO₂ on titanium substrate with a doping range of 1.5-8 mol% were prepared by an electrodeposition and dip coating method. The prepared Ti/SnO₂-Sb₂O₄ thin films were tested as a photoanode in the photoelectrocatalytic(PEC) experiments to degrade phenol in aqueous solution in order to evaluate their PEC performance. The photocatalytic (PC), electrocatalytic (EC) and PEC activity of Ti/SnO₂-Sb₂O₄ thin films was compared in the degradation processes. And the effect of annealing temperature on their PEC activity was also investigated. The experimental results confirmed that the Sb-doped Ti/SnO₂ thin films enhanced the phenol degradation and the Ti/SnO₂-Sb₂O₄ film containing 6 mol% of Sb calcinated at 450 °C achieved the best performance for phenol degradation. The degradation experiments also demonstrated that the Ti/SnO₂-Sb₂O₄ film achieved faster degradation of phenol in the PEC process than in the PC and EC processes. Compared with Ti/TiO₂ and Ti/SnO₂ photoanodes, the Ti/SnO₂-Sb₂O₄ photoanode showed higher activity.     

Effect of thermal treatment on the electrical properties of the sol–gel-derived (Zr,Sn)TiO4 thin films

The effect of heating temperatures on the electrical properties of sol–gel-derived (Zr,Sn)TiO₄ thin films deposited on a p-type (1 0 0) Si substrate was studied. The leakage currents of films with two different heating temperatures chosen to burn-out the solvent as a function of applied voltage were measured at different temperatures. The activation energies obtained from the Arrhenius plot of the leakage current density versus measured temperature for (Zr,Sn)TiO₄ films were then extracted. Additionally, microstructures of films with two different heating temperatures chosen to burn-out the solvent were analyzed by a conductive atomic force microscope (AFM) and an X-ray diffraction (XRD). Finally, the conductive mechanisms of leakage current and leakage current correlated to microstructures were also discussed.     

Simple fabrication of rod-like N-doped TiO2/Ag with enhanced visible-light photocatalytic activity

Rod-like N-doped TiO₂/Ag composites were successfully synthesized by a modified sol–gel method, without adding any surfactants. The entire preparation differs from the traditional sol–gel synthesis of TiO₂ that the reaction can get controlled by adjusting the flow speed of water vapor and NH₃. Characterization results show that as-prepared samples were uniform nanorods with an average length of ca. 3 µm and a cross section diameter of ca. 150 nm. The rod-like structure was formed during the annealing process. A possible mechanism was proposed to illustrate the formation of rod-like Ag–N–TiO₂. The degradation of methylene blue performed under visible light with the prepared nanorods as the photocatalyst demonstrated the photocatalytic activities of TiO₂ can be improved by the synergistic effect of N doping and Ag modification. In addition, as-prepared TiO₂-based photocatalyst exhibits a significantly enhanced photo-chemical stability after 5 catalytic cycles mainly due to the rod-like morphology. This indicated that they have some potential value in practical application.     

Facile synthesis of mesoporous Ag-loaded TiO2 thin film and its photocatalytic properties

Ag nanoparticles highly dispersed into TiO₂ thin films are synthesized via a remarkably simple one-pot route in the presence of a P123 triblock copolymer as template directing and reducing agents, where the reduction of Ag⁺ to Ag⁰ by in situ heat-induced reduction through the oxidation of template at 400 °C and the controlled polymerization of TiO₂ take place simultaneously. The obtained mesoporous Ag/TiO₂ films deposited on soda-lime glass were optically transparent and crack-free. SEM and Kr adsorption clearly prove that Ag/TiO₂ films at different Ag contents are mesoporous with large surface area and regularly ordered mesopores and the thickness of the obtained films is ∼280 ± 20 nm. The pristine TiO₂ film exhibits a specific surface area of 63 cm²/cm² and specific pore volume of 0.013 mm³/cm² that it is decreased to 42 cm²/cm² and 0.010 mm³/cm² respectively as a result of Ag-loaded mesoporous TiO₂. The newly prepared photocatalysts Ag/TiO₂ films were evaluated for their photocatalytic degradation of 2-chlorophenol as a model reaction. It was found that the meso-ordered Ag/TiO₂ films are more photoactive 8 times than nonporous commercial photocatalysts Pilkington Glass Activ™. The recycling tests indicated that Ag/TiO₂ films was quite stable during that liquid-solid heterogeneous photocatalysis since no significant decrease in activity was observed even after being used repetitively for 10 times, showing a good potential in practical application. In general, the cubic mesoporous Ag/TiO₂ nanocomposites are stable and can be recycled without loss of their photochemical activity.     

Simultaneous improvement of photocatalytic and superhydrophilicity properties of nano TiO2 thin films

Anatase TiO₂ nano thin films were prepared on glass substrates by sol–gel dip coating method using Tween-80 as a surfactant, TiCl₄ as the Ti precursor, and ethanol as a solvent. Atomic force microscopy, X-ray diffraction, and UV–Vis. photospectrometery experiments were performed to analyze the surface, structural and optical characteristics of the films. The effects of chemical aging time on the morphology, photocatalytic and superhydrophilicity behaviors of the films were studied. We show there is an optimum aging time at 2 h which photocatalytic and superhydrophilicity properties are at their maximum values simultaneously. This is useful in the self-cleaning industry.     

Effect of annealing on the properties of nanostructured CuO thin films for enhanced ethanol sensitivity

Copper oxide (CuO) thin films were grown on glass substrates by low cost spray pyrolysis technique for three different molar concentrations (0.05 M, 0.10 M and 0.15 M), at a substrate temperature of 350 °C, and subsequently annealed at 400 °C for 2 h. The effects of precursor concentration and annealing on the structural, electrical and morphological properties of the crystallized films were investigated. X-ray diffractograms of the films showed the formation of single phase CuO with tenorite structure. The electrical properties of the films like carrier concentration, Hall co-efficient (R_H), mobility and conductivity were studied from Hall effect measurements. The positive values of R_H confirmed the p-type conductivity of the films. Resistivity decreased drastically by two orders of magnitude for the annealed films. The microstructures characterized by a scanning electron microscope for 0.15 M concentration of the precursor revealed that the morphology of the films was substantially affected by annealing. The film surface revealed uniformly distributed cluster of peanut shaped grains after annealing. The response of the as deposited and annealed CuO sensor to low concentration of ethanol (10 ppm) was compared. The annealed CuO film showed higher sensor response than the as-deposited CuO film did. The result suggested that annealing causes significant effect on the sensing performance of CuO to ethanol.     

One-step electrochemical preparation of the ternary (BixSb1−x)2Te3 thin films on Au(1 1 1): Composition-dependent growth and characterization studies

This study reports on the synthesis of ternary semiconductor (Bi_xSb_1−x)₂Te₃ thin films on Au(1 1 1) using a practical electrochemical method, based on the simultaneous underpotential deposition (UPD) of Bi, Sb and Te from the same solution containing Bi³⁺, SbO⁺, and HTeO₂⁺ at a constant potential. The thin films are characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS) and reflection absorption-FTIR (RA-FTIR) to determine structural, morphological, compositional and optic properties. The ternary thin films of (Bi_xSb_1−x)₂Te₃ with various compositions (0.0 ≤ x ≤ 1.0) are highly crystalline and have a kinetically preferred orientation at (0 1 5) for hexagonal crystal structure. AFM images show uniform morphology with hexagonal-shaped crystals deposited over the entire gold substrate. The structure and composition analyses reveal that the thin films are pure phase with corresponding atomic ratios. The optical studies show that the band gap of (Bi_xSb_1−x)₂Te₃ thin films could be tuned from 0.17 eV to 0.29 eV as a function of composition.