Effect of the internal stress relaxation during the post-annealing on the photo-induced properties of TiO2 coatings reactively sputtered

Photocatalyst TiO₂ coatings have been reactively sputtered at high pressure on cold glass substrates pre-coated by a SiN_x sodium diffusion barrier. The as-deposited coatings were amorphous and the TiO₂/SiN_x/glass samples were subsequently heated at different temperatures under air. The TiO₂ films crystallise in the anatase structure above temperatures of 250 °C with a [001] preferential orientation. The structural analyses have demonstrated that the crystallites are elongated following the c axis direction, perpendicularly to the surface. No modifications of grain size and texture have been observed over the complete temperature range studied (250-550 °C). However, the lattice parameters evolution shows a decrease of the tensile stress with a rise in annealing temperature. The microstructure is then completely relaxed around 400 °C and finally compressive stress is observed at higher temperature. The study of the photo-induced (photocatalytic and hydrophilic) properties shows an activity maximum at 400 °C. These results suggest that the photo-induced properties would be favoured by a relaxed microstructural state of titanium dioxide.     

Poisoning prevention of TiO2 photocatalyst coatings sputtered on soda-lime glass by intercalation of SiNx diffusion barriers

Amorphous titanium dioxide coatings were deposited at high pressure (about 5 Pa) on cold soda-lime glass by reactive magnetron sputtering. In order to obtain anatase form known for its photocatalytic properties, an annealing at 450 °C was required. The morphology of the photocatalyst coating, examined by scanning and transmission electron microscopy, exhibits a columnar structure with closed intercolumnar porosity. The concentration profile obtained by means of sputtered neutral mass spectrometry revealed the presence of sodium into the TiO₂ coating due to the Na diffusion from the soda-lime glass during the annealing step. This level of contamination reaches 5.5 at.% in the whole film thickness. Since the presence of Na in TiO₂ coatings is harmful to the photocatalytic properties, a silicon nitride (SiN_x) coating, acting as a Na diffusion barrier, was intercalated between the glass substrate and the TiO₂ coating. The concentration profiles showed that the TiO₂ coating deposited on SiN_x/glass substrate is sodium-free. Furthermore, photocatalytic tests revealed that TiO₂/SiN_x/glass system is about threefold more efficient than TiO₂/glass, showing both the poisoning effect of Na and the superior efficiency of SiN_x as a diffusion barrier. To illustrate this, diffusion barriers made of silicon dioxide have also been grown and compared to SiN_x.     

Microstructure characterization and photocatalytic activity of mesoporous TiO2 films with ultrafine anatase nanocrystallites

A series of mesoporous TiO₂ films on borosilicate glass with ultrafine anatase nanocrystallites were successfully synthesized using a non-acidic sol gel preparation route, which involves the use of nonionic surfactant Tween 20 as template through a self assembly pathway. The microstructure of these TiO₂ films was characterized by XRD, SEM, HR-TEM, UV-Vis spectroscopy, and N₂ adsorption-desorption isotherm analysis. Their photocatalytic activities were investigated by using creatinine as a model organic contaminate in water. It was found that all mesoporous TiO₂ films prepared with Tween 20 exhibited a partially ordered mesoporous structure. The photocatalytic activity of the TiO₂ films could be remarkably improved by increasing Tween 20 loading in the sol at the range of 50% (v/v), which yielded large amount of catalyst (anatase) on the glass support and enhanced specific surface area. The optimum Tween 20 loading was 50% (v/v) in the sol, above which good adhesion between TiO₂ films and borosilicate glass could not be maintained. The final TiO₂ film (Tween 20: final sol = 50%,v/v) exhibits high BET surface area (∼ 120 m²/g) and pore volume (0.1554 cm³/g), ultrafine anatase nanocrystallinity (7 nm), uniform and crack free surface morphology, and improved photocatalytic activity.     

Structure and mechanical properties of δ-NbN/SiNx and δ′-NbN/SiNx nano-multilayer films deposited by reactive magnetron sputtering

We deposit cubic δ-NbN/SiN_x and hexagonal δ′-NbN/SiN_x nano-multilayer films using reactive magnetron sputtering in discharge of a mixture of Ar and N₂ gas, and explore the effects of SiN_x layer thickness on the microstructure and mechanical properties for both cubic δ-NbN/SiN_x and hexagonal δ′-NbN/SiN_x multilayer films by virtue of X-ray diffraction, electron diffraction, high-resolution transmission electron microscope, and nanoindentation measurements. We find that the structure for NbN layers is a critical factor in determining the hardness of NbN/SiN_x multilayer films. For cubic δ-NbN/SiN_x nano-multilayer films, as SiN_x layer thickness is smaller than or equal to 0.4 nm, the cubic δ-NbN layers force SiN_x layers to crystallize, accompanied with a remarkable increase in hardness with maximum hardness of 32 GPa. With an increase in thickness, SiN_x layers become amorphous, and correspondingly the hardness decreases. For hexagonal δ′-NbN/SiN_x nano-multilayer films, both the stress and hardness decrease with increasing the SiN_x layer thickness and the nano-multilayer films do not show any enhancement in hardness, compared to δ′-NbN single layer film.     

Elaboration and characterization of nanocrystalline TiO2 thin films prepared by sol–gel dip-coating

Nanocrystalline TiO₂ thin films were deposited on a ITO coated glass substrate by sol–gel dip coating technique, the layers undergo a heat treatment at temperatures varying from 300 to 450 °C. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, Atomic Force Microscopy (AFM), visible, (Fourier-Transform) infrared and ultraviolet spectroscopy, Fluorescence and spectroscopic ellipsometry. The results indicate that an anatase phase structure TiO₂ thin film with nanocrystallite size of about 15 nm can be obtained at the heat treatment temperature of 350 °C or above, that is to say, at the heat treatment temperature below 300 °C, the thin films grow in amorphous phase; while the heat treatment temperature is increased up to 400 °C or above, the thin film develops a crystalline phase corresponding to the titanium oxide anatase phase. We have accurately determined the layer thickness, refractive index and extinction coefficient of the TiO₂ thin films by the ellipsometric analysis. The optical gap decreases from 3.9 to 3.5 eV when the annealing temperature increases. Photocatalytic activity of the TiO₂ films was studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 350 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

Transparent p-type CuxS thin films

The effect of different mild post-annealing treatments in air, at 270 °C, for 4-6 min, on the optical, electrical, structural and chemical properties of copper sulphide (Cu_xS) thin films deposited at room temperature are investigated. Cu_xS films, 70 nm thick, are deposited on glass substrates by vacuum thermal evaporation from a Cu₂S:S (50:50 wt.%) sulphur rich powder mixture. The as-deposited highly conductive crystalline CuS (covellite) films show high carrier concentration (∼10²² cm⁻³), low electrical resistivity (∼10⁻⁴ Ω cm) and inconclusive p-type conduction. After the mild post-annealing, these films display increasing values of resistivity (∼10⁻³ to ∼10⁻² Ω cm) with annealing time and exhibit conclusive p-type conduction. An increase of copper content in Cu_xS phases towards the semiconductive Cu₂S (chalcocite) compound with annealing time is reported, due to re-evaporation of sulphur from the films. However, the latter stoichiometry was not obtained, which indicates the presence of vacancies in the Cu lattice. In the most resistive films a Cu₂O phase is also observed, diminishing the amount of available copper to combine with sulphur, and therefore the highest values of optical transmittance are reached (65%). The appearance on the surface of amorphous sulphates with annealing time increase is also detected as a consequence of sulphur oxidation and replacement of sulphur with oxygen. All annealed films are copper deficient in regards to the stoichiometric Cu₂S and exhibit stable p-type conductivity.     

Structural characterization of HfN<Subscript>x</Subscript>-based films grown by metal organic chemical vapor deposition

In this paper, HfN_x-based films on SiO₂/Si stack were grown by metal organic chemical vapor deposition (MOCVD), and one of them was ex-situ annealed at elevated temperature. The structural parameters of HfN_x-based films for the as-grown and the post-growth annealing samples were characterized by Rutherford back-scattering spectrometry (RBS), Spectroscopic Ellipsometry (SE) and atomic force microscopy (AFM). The measurements of the post-growth annealing sample by RBS demonstrated that the N: Hf ratio of HfN_x-based films would decrease with depth increase. In addition, The SE results for the structure of HfN_x-based nitride films were in good agreement with those determined by RBS.     

Non-destructive evaluation of strength and residual stress for weldments using continuous indentation technique

TiO₂ photocatalysts are attractive and promising materials due to their excellent properties such as high photocatalytic activity, stability and non-toxicity. Therefore, TiO₂ photocatalyst has applied into various fields such as environmental purifications. The major forms of TiO₂ photocatalysts are fine particles in order to obtain high surface areas. In order to fabricate commercial applications, the coating procedures using binder chemicals must be employed. However, the fine TiO₂ particles slightly scattered at the surface, since most particles are buried in binder chemicals, leading to obtaining poor photocatalytic activity. TiO₂ films can be easily formed on a metallic titanium substrate by anodization. However, the amorphous TiO₂ films with no photocatalytic activities are usually obtained in conventional anodization. We have successfully obtained the high performance photocatalytic TiO₂ films by using combined treatment of pre-nitridation and anodization. The photocatalytic TiO₂ films show the high photocatalytic activities to decompose the various volatile organic compounds such as trichloroethylene, isopropyl alcohol, acetaldehyde, and so on.     

Enhanced photocatalytic degradation properties of nitrogen-doped titania nanombe arrays

Nitrogen-doped TiO₂ nanotubes array were synthesized to improve the photocatalytic efficiency by annealing the anodized titania nanotubes with ammonia at 500 °C. Detailed structural analysis revealed that the nitrogen-doped titania nanotubes are of highly ordered structure, and exhibit a decreased phase transformation temperature compared with those that are not doped, as evidenced by the decrease in full width at half maximum (FWHM) of the (110) peak of rutile phase and the occurrence of the typical Raman peaks of rutile phase at 196, 235, 442, 610 cm^?1. According to the photocatalytic degradation of methyl orange under visible light irradiation, the nitrogen-doped TiO₂ nanotubes exhibit enhanced photocatalytic efficiency compared with their non-doped nanotubes, which might be a result of either the nitrogen doping induced band gap narrowing or the synergistic effect produced by both nitrogen and fluorine dopants.     

Electrochemical behaviors of TiO2−x films synthesized by plasma-based ion implantation and deposition in fibrinogen containing PBS solution

TiO_2−x films were synthesized on carbon by plasma-based ion implantation and deposition (PBII-D). Electrochemical behaviors of the prepared films were investigated in phosphate buffer solution (PBS) and fibrinogen containing PBS solution (PBS(Fn)), to probe charge transfer phenomena between TiO_2−x film and fibrinogen. Electrochemical impedance spectroscopy (EIS) as well as simulated values of equivalent circuit units including reaction resistance and electric double layer has been obtained, indicating different charge transfer rate occurred across the interfaces. The shape of Mott-Schottky spectroscopy around the rest-open potential indicates that TiO_2−x films are typical n-type semiconductor. Donor density results calculated by Mott-Schottky theory show that TiO_2−x films exhibit higher donor density in PBS(Fn) than in PBS, indicating charge transfer from fibrinogen to TiO_2−x films, and the space charge layers bend lower.     

The photocatalytic activity of sprayed Zn1 − xMgxO thin films

ZnO has received much attention in the degradation and complete mineralization of environmental pollutants. For the purpose of increasing the photocatalytic efficiency of ZnO, Mg was doped into ZnO thin films.Zn_1 − xMg_xO thin films were prepared by spray pyrolysis method on glass substrates. The deposition temperature was 500 °C. Mg concentration was varied in the range of 0.0 to 0.3 in intervals of 0.05. The pure ZnO films were polycrystalline with preferred orientation (100). Zn_1 − xMg_xO becomes amorphous with increasing Mg concentration. The optical band gap of Zn_1 − xMg_xO changes from 3.26 to 3.59 eV with increasing Mg content. Also, the photocatalytic activity increased with Mg, and the film with x = 0.3 showed the best result.     

Purifying behavior of photocatalytic TiO2 anodized in nitrate ion containing solution

Mesoporous titanium dioxide films were fabricated on titanium plates by micro-arc oxidation method. To increase the photocatalytic activity of the films, NH₄NO₃ was added to the H₂SO₄ solution, and anodizing was carried out at high voltages using a DC power supply. The crystal structure, chemical composition, surface morphology and the optical property of the films were investigated by XPS, XRD, UV-VIS spectroscopy and SEM. The photocatalytic activity of the films was evaluated by the decomposition of aniline blue, and the activity of the films for the degradation turned out to be improved by the additives to the electrolyte solution. The enhanced photocatalytic activity might result from the increased porosity and nitrate ion incorporation into the anodic films by micro arcing, and thereby the TiO₂ layer might exhibit an improved absorption property for the visible light.     

Effect of Nb doping on the phase transition and optical properties of sol-gel TiO2 thin films

Various content Nb-doped TiO₂ thin films were prepared by sol-gel process. XRD analysis shows that the existence of crystalline TiO₂ in anatase and rutile form depends on the Nb content in the examined samples. It is observed that Nb promotes the anatase to rutile phase transition but has a depression effect on the anatase grain growth. It is found that incorporation of about 4 at.% of Nb completely transforms anatase TiO₂ to the rutile form at a calcination temperature as high as 900 °C. The mechanism is proposed. Optical analyses show that the films have an average of 60% transmission in visible region. The energy gap values using Tauc's formula have also been estimated. The band gap of rutile Ti_1−xNb_xO₂ solid solutions increases with increasing x.     

Effect of annealing and O2 pressure on structural and optical properties of pulsed laser deposited TiO2 thin films

In this paper, effect of annealing and O₂ pressure on the structural and optical properties of pulsed laser deposited thin films of TiO₂ is reported. XRD, FTIR spectra and SEM images confirm that at high annealing temperatures, the rutile phase and crystalline quality of thin films increases. Higher pressure of O₂ during deposition improves the rutile phase and favors the rod like growth of TiO₂ thin film. The red shift in photoluminescence (PL) spectra of TiO₂ thin films with annealing temperature is reported. Contact angle measurement data for the thin films reveals the hydrophobic nature of the films. The very low reflectivity (～10%) reported in this paper may be promising for anti-reflection coating applications of pulsed laser deposited TiO₂ thin films.     

Controlling the particle size of nanobrookite TiO2 thin films

In this study, pure nanobrookite TiO₂ thin films were successfully deposited on glass substrates with the spin-coating method using titanium butoxide and acetic acid. The particle size of TiO₂ films was controlled by the water:AcAc volume ratio. This study shows that it is possible to obtain single oriented pure brookite films. The structural and optical properties of the nanobrookite TiO₂ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), ultraviolet-visible spectroscopy (UV-vis), scanning electron microscopy (SEM), spectrophotometer (NKD), and Fourier transform infrared spectrometer (FTIR).     

Photosensitive nanostructured TiO2 grown at room temperature by novel “bottom-up” approached CBD method

The current paper incorporates with a “bottom-up” approached chemical bath deposition method to grow titanium dioxide (TiO₂) nanostructure at room temperature on glass and stainless steel substrates. The room temperature deposited TiO₂ films are heat treated at 673 K for 1 h in air and the corresponding change in structural, morphological and optical properties are studied by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and UV-VIS-NIR spectrophotometer. The heat-treated films are utilized as a photocathode in photoelectrochemical (PEC) cell in 1 M NaOH electrolyte. The experimental results show that, the CBD method allows formation of photosensitive, anatase TiO₂ thin film, which can be potentially tuned in many functional applications with feasibility.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

Effect of annealing temperature on the structure and optical properties of sputtered TiO2 films

TiO₂ thin films were deposited by DC reactive magnetron sputtering. Some TiO₂ thin films samples were annealed for 5 min at different temperatures from 300 to 900 °C. The structure and optical properties of the films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and ultraviolet-visible (UV-vis) spectrophotometry, respectively. The influence of the annealing temperature on the structure and optical properties of the films was investigated. The results show that the as-deposited TiO₂ thin films are mixtures of anatase and rutile phases, and possess the column-like crystallite texture. With the annealing temperature increasing, the refractive index and extinction coefficient increase. When the annealing temperature is lower than 900 °C, the anatase phase is the dominant crystalline phase; the weight fraction of the rutile phase does not increase significantly during annealing process. As the annealing temperature rises to 900 °C, the rutile phase with the large extinction coefficient becomes the dominant crystalline phase, and the columnar structure disappears. The films annealed at 300 °C have the best optical properties for the antireflection coatings, whose refractive index and extinction coefficient are 2.42 and 8 × 10⁻⁴ (at 550 nm), respectively.     

Influence of heat treatment on the particle size of nanobrookite TiO2 thin films produced by sol-gel method

Pure nanobrookite titania (TiO₂) thin films were deposited on glass substrates by the spin-coating method using titanium butoxide and acetic acid. The particle sizes of TiO₂ films were controlled by heat treatment temperatures. The activation energy for particle growth was calculated as 23.1 kJ/mol. The structural and optical properties of the nanobrookite TiO₂ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), ultraviolet-visible absorption spectroscopy (UV-vis), and Fourier transform infrared spectroscopy (FTIR).     

Morphology and photocatalytic activity of highly oriented mixed phase titanium dioxide thin films

Thin TiO₂ films on quartz substrates were prepared by spin coating of undoped and metal-ion-doped Sol-Gel precursors. These films were characterised by Scanning Electron Microscopy, Laser Raman Microspectroscopy, X-ray Diffraction and UV-Vis Transmission. The photocatalytic performances of the films were assessed by the photo-degradation of methylene-blue in aqueous solution under UV irradiation. Films exhibited a high degree of orientation and a thermal stabilization of the anatase phase as a result of substrate effects. In the absence of dopants, the rutile phase formed as parallel bands in the anatase which broadened as the transformation progressed. TiO₂ films doped or co-doped with transition metals exhibited the formation of rutile in segregated clusters at temperatures under ~ 800 °C as a result of increased levels of oxygen vacancies. Photocatalytic activity of the films synthesised in this work was low as likely a result of poor TiO₂ surface contact with dye molecules in the solution. The presence of transition metal dopants appears detrimental to photocatalytic activity while the performance of mixed phase films was not observed to differ significantly from single phase material.