Tailoring the wettability of nanocrystalline TiO2 films

The water contact angle (WCA) of nanocrystalline TiO₂ films was adjusted by fluoroalkylsilane (FAS) modification and photocatalytic lithography. FAS modification made the surface hydrophobic with the WCA up to ∼156°, while ultraviolet (UV) irradiation changed surface to hydrophilic with the WCA down to ∼0°. Both the hydrophobicity and hydrophilicity were enhanced by surface roughness. The wettability can be tailored by varying the concentration of FAS solution and soaking time, as well as the UV light intensity and irradiation time. Additionally, with the help of photomasks, hydrophobic-hydrophilic micropatterns can be fabricated and manifested via area-selective deposition of polystyrene particles.     

Novel fabrication of net-like and flake-like Fe doped TiO2 thin films

New morphologies of net-like and flake-like TiO₂ thin films with different concentrations of Fe dopant were successfully fabricated by micro-arc oxidation (MAO) process of Ti plates and a subsequent chemical treatment of the as-prepared MAO-TiO₂ thin films. It was found that Fe ions can be easily introduced into the MAO-TiO₂ samples with the increase concentration of K₄(FeCN)₆·3H₂O precursor, and the amount of Fe determined the morphologies of TiO₂ thin films after chemical treatment; net-like morphology was observed with low Fe dopant, while it transformed to a flake-like one when Fe exceeds 1.7 at.%. UV-vis spectroscopy test showed that the absorption edge of the Fe ions doped TiO₂ thin films with new morphologies has an obvious red shift.     

Micro-structuring of TiO2 thin films by laser-assisted diffraction processing

Thin films of TiO₂ are deposited by magnetron sputtering on glass substrate and are irradiated by UV radiation using a KrF excimer laser (248 nm). These thin films are patterned with a razor blade placed on the way of the radiation just in front of the TiO₂ thin film. Just near the edge of the razor blade on the thin film, diffraction lines are observed, resulting in the ablation of the film. These patterns are characterized by optical microscopy, mechanical profilometry. Diffraction up to the 35th order is observed. The results are shown to be compatible with a model in which electronic excitation plays the major role.     

Room temperature ferromagnetism in vacuum-annealed TiO2 thin films

Thin films of pure TiO₂ have been prepared using both spin-coating and sputter-deposition techniques on sapphire and quartz substrates. The structural characteristics of the films have been investigated in detail using Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM). When annealed in vacuum, all films demonstrate room temperature ferromagnetism, while the air-annealed samples show much smaller, often negligible, magnetic moments. The magnetization of the vacuum-annealed sputtered samples depends on film thickness, with the volume magnetization decreasing monotonically with increasing thickness. Furthermore, the magnetization per unit area also decreases slightly with increasing film thickness. These results suggest that ferromagnetism in the vacuum-annealed TiO₂ films is mediated by surface defects or interfacial effects, but does not arise from stoichiometric crystalline TiO₂.     

Electrochromic properties of spray deposited TiO2-doped WO3 thin films

TiO₂-doped WO₃ thin films were deposited onto fluorine-doped tin oxide coated conducting glass substrates using spray pyrolysis technique at 525 °C. The volume percentage of TiO₂ dopant was varied from 13% to 38%. The thin film samples were transparent, uniform and strongly adherent to the substrates. Electrochromical properties of TiO₂-doped WO₃ thin films were studied with the help of cyclic voltammetry (CV), chronoamperometry (CA) and chronocoulometry (CC) techniques. It has been found that TiO₂ doping in WO₃ enhances its electrochromic performance. Colouration efficiency becomes almost double and samples exhibit increasingly high reversibility with TiO₂ doping concentrations, in the studied range.     

Synthesis of MgB2 films by diffusion of magnesium into electrophoretically deposited boron films

The boron films were formed from the optimized stable suspension solution of boron particles using electrophoretic deposition technique. The magnesium film with optimized thickness was deposited onto boron films by vacuum evaporation technique. The heterogeneous structure was given heat treatment in ambient and vacuum atmosphere for diffusion of Mg into the boron films to form MgB₂ phase. XRD studies were carried out on both as deposited and heat treated heterostructure films to investigate their structure and phase. Surface morphological studies of these films were done by SEM.     

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.     

Deposition of graded TiO2 films featured both hydrophobic and photo-induced hydrophilic properties

Graded TiO₂ films were deposited on unheated glass substrates by using a twin dc magnetron sputtering system. The graded TiO₂ films showed a highly polycrystalline structure of anatase with a little rutile phases revealed by X-ray diffraction spectra. The surface energy of the fresh and UV irradiated films were evaluated by water contact angle measurement. The results indicated that the water contact angle of the fresh graded TiO₂ films was found within 100-112°. The films then became a highly hydrophilic surface with the water contact angle of almost zero under 60 min UV irradiation. The XPS spectrum of Ti 2p revealed that the graded TiO₂ films became a stoichiometric titanium oxide layer near the surface, proving that titanium was fully oxidized. It was found that the surface OH group density depended on the substrates employed for given sputtering conditions. In addition, AFM images revealed a considerably rough surface of the graded films with RMS roughness of 12.6-14.5 nm. One can conclude that the unique properties of highly hydrophobicity and photo-induced hydrophilicity can be attributed to fully oxidized chemical composition and higher roughness on the film surface.     

Preparation of CuInS2 thin films by metal-organic decomposition

Metal-organic decomposition (MOD) technique has been developed as a low cost thin film CuInS₂ preparation method for solar cell application. XRD and Raman spectra measurement revealed that deposited films contain CuInS₂. Stoichiometric films with a bandgap of 1.53 eV and an FWHM of 0.45° were obtained from a solution with Cu/In=1.5.     

Crystallisation of TiO2 thin films induced by excimer laser irradiation

Titanium dioxide thin films have been deposited by reactive magnetron sputtering on glass substrate and subsequently irradiated by UV radiation using a KrF excimer laser. In this work, we have study the influence of the laser fluence (F) ranging between 0.05 and 0.40 mJ/cm² on the constitution and microstructure of the deposited films. Irradiated thin films are characterized by profilometry, scanning electron microscopy and X-ray diffraction. As deposited films are amorphous, while irradiated films present an anatase structure. The crystallinity of the films strongly varies as a function of F with maximum for F = 0.125 J/cm². In addition to the modification of their constitution, the irradiated areas present a strongly modified microstructure with appearance of nanoscale features. The physico-chemical mechanisms of these structural modifications are discussed based on the theory of nucleation.     

Methylene blue photoelectrodegradation under UV irradiation on Au/Pd-modified TiO2 films

In this work TiO₂ thin films were modified with gold/palladium (Au/Pd) bimetallic paticles by sputtering method. TiO₂ films were deposited on ITO (SnO₂:In) by Doctor Blade method and post-anneling. The properties of the films were studied through measurements of XRD (X-ray diffraction) and AFM (atomic force microscopy). The degradation of methylene blue was studied by UV-irradiated pure TiO₂ and Au/Pd-modified TiO₂ in aqueous solution. Langmuir-Hinshelwood model was used to obtain kinetic information. Photocatalytic study indicated that Au/Pd-modified TiO₂ photocatalytic activity was better than TiO₂ pure; the best half-life time for Au/Pd-modified TiO₂ in photodegradation was 2.8 times smaller than TiO₂ pure; finally the efficiency in methylene blue photodegradation was improved from 23% to 43% when Au/Pd-modified TiO₂ films were used.     

Chemical synthesis of nanocrystalline SnO2 thin films for supercapacitor application

Nanocrystalline SnO₂ thin films were deposited by simple and inexpensive chemical route. The films were characterized for their structural, morphological, wettability and electrochemical properties using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy techniques (SEM), transmission electron microscopy (TEM), contact angle measurement, and cyclic voltammetry techniques. The XRD study revealed the deposited films were nanocrystalline with tetragonal rutile structure of SnO₂. The FT-IR studies confirmed the formation of SnO₂ with the characteristic vibrational mode of Sn-O. The SEM studies showed formation of loosely connected agglomerates with average size of 5-10 nm as observed from TEM studies. The surface wettability showed the hydrophilic nature of SnO₂ thin film (water contact angle 9°). The SnO₂ showed a maximum specific capacitance of 66 F g⁻¹ in 0.5 Na₂SO₄ electrolyte at 10 mV s⁻¹ scan rate.     

The structure and photocatalytic activity of TiO2 thin films deposited by dc magnetron sputtering

This paper seeks to determine the optimal settings for the deposition parameters, for TiO₂ thin film, prepared on non-alkali glass substrates, by direct current (dc) sputtering, using a ceramic TiO₂ target in an argon gas environment. An orthogonal array, the signal-to-noise ratio and analysis of variance are used to analyze the effect of the deposition parameters. Using the Taguchi method for design of a robust experiment, the interactions between factors are also investigated. The main deposition parameters, such as dc power (W), sputtering pressure (Pa), substrate temperature (°C) and deposition time (min), were optimized, with reference to the structure and photocatalytic characteristics of TiO₂. The results of this study show that substrate temperature and deposition time have the most significant effect on photocatalytic performance. For the optimal combination of deposition parameters, the (1 1 0) and (2 0 0) peaks of the rutile structure and the (2 0 0) peak of the anatase structure were observed, at 2θ ∼ 27.4°, 39.2° and 48°, respectively. The experimental results illustrate that the Taguchi method allowed a suitable solution to the problem, with the minimum number of trials, compared to a full factorial design. The adhesion of the coatings was also measured and evaluated, via a scratch test. Superior wear behavior was observed, for the TiO₂ film, because of the increased strength of the interface of micro-blasted tools.     

Characterization of N,C-codoped TiO2 films prepared by reactive DC magnetron sputtering

Titanium dioxide (TiO₂) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO₂ film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1s peak at 396.8 eV and a C 1s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO₂ film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO₂ catalysts.     

Interfaces analysis of the HfO2/SiO2/Si structure

The physical and chemical properties of the HfO₂/SiO₂/Si stack have been analyzed using cross-section HR TEM, XPS, IR-spectroscopy and ellipsometry. HfO₂ films were deposited by the MO CVD method using as precursors the tetrakis 2,2,6,6 tetramethyl-3,5 heptanedionate hafnium—Hf(dpm)₄ and dicyclopentadienil-hafnium-bis-diethylamide—Сp₂Hf(N(C₂H₅)₂)₂.The amorphous interface layer (IL) between HfO₂ and silicon native oxide has been observed by the HRTEM method. The interface layer comprises hafnium silicate with a smooth varying of chemical composition through the IL thickness. The interface layer formation occurs both during HfO₂ synthesis, and at the annealing of the HfO₂/SiO₂/Si stack. It was concluded from the XPS, and the IR-spectroscopy that the hafnium silicate formation occurs via a solid-state reaction at the HfO₂/SiO₂ interface, and its chemical structure depends on the thickness of the SiO₂ underlayer.     

Morphology and natural wettability properties of sol-gel derived TiO2-SiO2 composite thin films

Previous studies suggest that granular interfaces induce a natural and persistent super-hydrophilicity in TiO₂-SiO₂ composite thin films deposited by sol-gel route. This effect enables to consider self-cleaning applications that do not require a permanent UV exposure, whereas such a permanent exposure is necessary for pure TiO₂ films. In this study, TiO₂-SiO₂ composite thin films have been deposited from a TiO₂ anatase crystalline suspension and different SiO₂ polymeric sols. Wettability studies show that a suitable control of the TiO₂-SiO₂ mixed sol formulations noticeably enhances persistence of the natural super-hydrophilicity in composite films. It is shown that, beside granular interface effects, modifications in the composite film morphologies can noticeably influence wettability properties.     

Favorable recycling photocatalyst TiO2/CFA: Effects of loading percent of TiO2 on the structural property and photocatalytic activity

A series of photocatalysts TiO₂/CFA were prepared using coal fly ash (CFA), waste discharged from coal-fired power plant, as substrate, and then these photocatalysts were characterized by scanning electron microscope, X-ray diffraction analysis, nitrogen adsorption test and ultraviolet-visible absorption analysis. The effects of loading percent of TiO₂ on the photocatalytic activity and re-use property of TiO₂/CFA were evaluated by the photocatalytic decoloration and mineralization of methyl orange solution. The results show that the pore volume and the specific surface area of the TiO₂/CFA both increased with the increase in the loading percent of TiO₂, which improved the photocatalytic activity of TiO₂/CFA. However, when the loading percent of TiO₂ was too high (up to 54.51%), superfluous TiO₂ was easy to break away from CFA in the course of water treatment, which was disadvantaged to the recycling property of TiO₂/CFA. In this study, the optimal loading percent of TiO₂ was 49.97%, and the efficiencies of photocatalytic decoloration and mineralization could be maintained above 99% and 90%, respectively, when the photocatalyst was used repeatedly, without any decline, even at the sixth cycle.     

Synthesis and bactericidal ability of Ag/TiO2 composite films deposited on titanium plate

In this study, we develop a bactericidal coating material for micro-implant, TiO₂ films with Ag deposited on were prepared on titanium plates by sol-gel process. Their anti-microbial properties were analyzed as a function of the annealed temperature using Escherichia coli as a benchmark microorganism. Ag nanoparticles deposited on TiO₂ film were of metallic nature and could grow to larger ones when the annealed temperature increased. The results indicated that the smaller size of Ag nanoparticles, the better bactericidal ability. On the other hand, the positive antibacterial effect of TiO₂ enhanced the bactericidal effect of Ag.     

The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes

CdS/TiO₂ nanocomposites were prepared via a simple wet chemical method, and characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their ability to degrade Acid Rhodamine B was investigated under visible light irradiation. The results indicate that CdS/TiO₂ nanocomposite with a mass ratio of 4:1(TiO₂:CdS) showed high photocatalytic activity and the CdS loaded on TiO₂ nanotube surface exhibited a hexagonal phase. The dispersion of CdS on TiO₂ nanotube surface had an important effect on the degradation efficiency of pollutant, which provides a strategy for practical industry application.     

Co-doped In2O3 thin films: Room temperature ferromagnets

Laser-ablated Co-doped In₂O₃ thin films were fabricated under various growth conditions on R-cut Al₂O₃ and MgO substrates. All Co:In₂O₃ films are well-crystallized, single phase, and room temperature ferromagnetic. Co atoms were well substituted for In atoms, and their distribution is greatly uniform over the whole thickness of the films. Films grown at 550 °C showed the largest magnetic moment of about 0.5 μ_B/Co, while films grown at higher temperatures have magnetic moments of one order smaller. The observed ferromagnetism above room temperature in Co:In₂O₃ thin films has confirmed that doping few percent of magnetic elements such as Co into In₂O₃ could result in a promising magnetic material.