Mesoporous TiO2 thin films embedded with Au nanoparticles for the enhancement of the photocatalytic properties

Mesoporous TiO₂ thin films were prepared by hydrothermal-oxidation of titanium metal thin films, which were obtained by DC magnetron sputtering technique. Gold nanoparticles, which were prepared by reduction of HAuCl₄, were embedded into the holes of the mesoporous TiO₂ films by capillary method followed by annealing in air up to 400 °C. The size of pore of TiO₂ films is about 100 nm and that of Au nanoparticles is about 10 nm in average. The morphology of the films was analyzed by field emission scanning electron microscope (FE-SEM) and scanning probe microscopes (SPMs). Subsequently, the photocatalytic performances of the obtained nanosystems in the decomposition of methylene blue solution are discussed. The obtained results show that the dispersion of Au nanoparticles on the mesoporous TiO2 matrix will help enhancing the photocatalytic activity with respect to pure TiO₂ under visible light irradiation.     

Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.     

Photoluminescence of Eu-doped TiO2 thin films prepared by low pressure hot target magnetron sputtering

In this work Eu-doped TiO₂ thin films prepared by reactive magnetron co-sputtering of Ti-Eu metallic target have been studied. The results of photoluminescence (PL) and its correlation with microstructure have been described. Structural properties were examined by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). XRD studies have shown that thin films consisted of TiO₂-anatase and AFM images display their high quality and dense nanocrystalline structure. PL spectra, measured at room temperature, show a dominating strong red luminescence corresponding to ⁵D₀-⁷F₂ transition at ∼ 617 nm and ∼ 623 nm. The evolution of photoluminescence and microstructure of the thin films has been examined as they were additionally annealed in an air ambient.     

Effect of porosity on the Seebeck coefficient of mesoporous TiO2 thin films

Mesoporous TiO₂ films were prepared by using titanium tetraisopropoxide as the titania precursor and triblock copolymer as the structure directing agent. The synthesized mesoporous TiO₂ film was confirmed to have the ordered pore structure with rutile phase by small angle and wide angle X-ray diffraction analyses. The mesoporous TiO₂ film has the porosity range from 21.6 to 35.6%, and its Seebeck coefficient was changed according to its porosity, up to −88.6 μV/K. From the obtained Seebeck coefficient, the ordered mesoporous TiO₂ film was found to be a good candidate of thermal sensing layer of thin film thermal sensor.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Surfactant/co-polymer template hydrothermal synthesis of thermally stable, mesoporous TiO2 from TiOSO4

Industrial TiOSO₄ solution was used as inorganic precursor to prepare mesoporous titania via composite template route, using cetyl-trimethylammonium bromide (CTAB) and tri-block copolymer EO₂₀PO₇₀EO₂₀ (P-123) as structure-directing agents (SDA) under high acidic conditions. Mesoporous TiO₂ with high thermal stability was obtained via controlling the hydrolysis and condensation rate of industrial TiOSO₄ solution by adjusting the pH value and post hydrothermal treating. The as-prepared materials were characterized by XRD, nitrogen adsorption-desorption, SEM and HRTEM. The powder calcined at 723 K for 2 h showed higher thermal stability, with BET specific surface area of 218.7 m²/g and an average pore diameter of 3.63 nm.     

Influence of Nd dopant amount on microstructure and photoluminescence of TiO2:Nd thin films

TiO₂ and TiO₂:Nd thin films were deposited using reactive magnetron sputtering process from mosaic Ti–Nd targets with various Nd concentration. The thin films were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectroscopic techniques. Photoluminescence (PL) in the near infrared obtained upon 514.5 nm excitation was also examined. The relationship between the Nd concentration, structural, optical and photoluminescence properties of prepared thin films was investigated and discussed. XRD and TEM measurements showed that an increase in the Nd concentration in the thin films hinders the crystal growth in the deposited coatings. Depending on the Nd amount in the thin films, TiO₂ with the rutile, mixed rutile–amorphous or amorphous phase was obtained. Transmittance measurements revealed that addition of Nd dopant to titania matrix did not deteriorate optical transparency of the coatings, however it influenced on the position of the fundamental absorption edge and therefore on the width of optical band gap energy. All TiO₂:Nd thin films exhibited PL emission that occurred at ca. 0.91, 1.09 and 1.38 μm. Finally, results obtained for deposited coatings showed that titania with the rutile structure and 1.0 at.% of Nd was the most efficient in VIS to NIR photon conversion.     

Nanocrystalline TiO2 thin films for NH3 monitoring: microstructural and physical characterization

Nanocrystalline titanium oxide thin films have been deposited by spin coating technique and then have been analyzed to test their application in NH₃ gas-sensing technology. In particular, spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of titanium oxide thin films. The structure and the morphology of such material have been investigated by X ray diffraction, Scanning microscopy, high resolution electron microscopy and selected area electron diffraction. The X-ray diffraction measurements confirmed that the films grown by this technique have good crystalline tetragonal mixed anatase and rutile phase structure. The HRTEM image of TiO₂ thin film showed grains of about 50–60 nm in size with aggregation of 10–15 nm crystallites. Selected area electron diffraction pattern shows that the TiO₂ films exhibited tetragonal structure. The surface morphology (SEM) of the TiO₂ film showed that the nanoparticles are fine with an average grain size of about 50–60 nm. The optical band gap of TiO₂ film is 3.26 eV. Gas sensing properties showed that TiO₂ films were sensitive as well as fast in responding to NH₃. A high sensitivity for ammonia indicates that the TiO₂ films are selective for this gas.     

Co-emission of UV, violet and green photoluminescence of ZnO/TiO2 thin film

ZnO/TiO₂ thin films were fabricated on quartz glass substrates by E-beam evaporation. The structural and optical properties were investigated by X-ray diffraction (XRD), Raman spectra, optical transmittance and photoluminescence. XRD analysis indicates that the TiO₂ buffer layer can increase the preferential orientation along the (002) plane of the ZnO film. PL measurements suggest that co-emission of strong UV peak at 378 nm, violet peak at 423 nm and weak green luminescence at 544 nm is observed in the ZnO/TiO₂ thin film. The violet luminescence emission at 423 nm is attributed to the interface trap in the ZnO film grain boundaries.     

Fabrication and characterization of nano TiO2 thin films at low temperature

Anatase TiO₂ thin films were successfully prepared on glass slide substrates via a sol–gel method from refluxed sol (RS) containing anatase TiO₂ crystals at low temperature of 100 °C. The influences of various refluxing time on crystallinity, morphology and size of the RS sol and dried TiO₂ films particles were discussed. These samples were characterized by infrared absorption spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission-scanning electron microscopy (FE-SEM) and UV–vis absorption spectroscopy (UV–vis). The photocatalytic activities of the TiO₂ thin films were assessed by the degradation of methyl orange in aqueous solution. The results indicated that titania films thus obtained were transparent and their maximal light transmittance exceeded 80% under visible light region. The TiO₂ thin films prepared from RS-6 sol showed the highest photocatalytic activity, when the calcination temperature is higher than 300 °C. The degradation of methyl orange of RS-6 thin films reached 99% after irradiated for 120 min, the results suggested that the TiO₂ thin films prepared from RS sol exhibited high photoactivities.     

Preparation of macroporous and mesoporous TiO2 film with various solvents

To investigate the effects of solvents on the microstructure, porous TiO₂ films have been prepared by sol-gel method using hydroxypropyl cellulose as the additive. Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethanol, and the mixed solution of half ethylene glycol monomethyl ether and half ethanol were chosen as the solvents. Infrared spectra, scanning electron microscope micrographs, and X-ray diffraction patterns have been studied to characterize the microstructure of the sol and film samples. The results showed that mesoporous TiO₂ films with the pore size around 20 nm, 10 nm and 6 nm were obtained when propylene glycol monomethyl ether, the mixed solution of half ethylene glycol monomethyl ether and half ethanol, and ethanol were used as solvent, respectively. It was found that COC group in the solvent was beneficial to enlarge the pore size, because the oxygen bridge in the COC groups could be pulled out and act with titanoxane polymers. When ethylene glycol monomethyl ether was used as the solvent, macroporous TiO₂ film with pore size around 200 nm was obtained. This can be ascribed to the high enough concentration of effective COC groups of the solvent.     

Synthesis and tuning of ordering and crystallinity of mesoporous titanium dioxide film

Synthesis of well-organized and highly crystalline mesoporous titania (TiO₂) film is demonstrated using triblock copolymer (Pluronic P123) as a structure directing template, through the evaporation induced self-assembly (EISA) process. The issue of thermal and structural stability of a mesoporous TiO₂ film was addressed via optimization of annealing temperature and time. An anatase phase, high crystallinity TiO₂ film with ordered pores was obtained at 430 °C after annealing for 15 min. The synthesized film was crack free with TiO₂ nanoparticle size of 10–15 nm, quasi-hexagonal pore diameter in the range of 8–10 nm and film thickness of ~ 150 nm.     

Oxygen plasma induced hydrophilicity of TiO2 thin films

Anatase nano-TiO₂ thin films were fabricated by reactive magnetron sputtering metal Ti target followed by thermal annealing in air at 450 °C for 2 hrs. The crystalline structure of the sample films were characterized by X-ray diffraction (XRD) and the hydrophilicity was characterized with the diameters of 1 μl water drop. The films were irradiated by oxygen plasmas and the effects of the radio frequency (rf) power, the gas pressure and the irradiation time of the oxygen plasmas on the hydrophilicity of the TiO₂ thin films were investigated. Hydrophilicity can be induced by oxygen plasmas and further more the hydrophilicity shows high stability whenever under the natural light or in dark.     

Thermal stability and electrical properties of Ag–Ti films and Ti/Ag/Ti films prepared by sputtering

Ag–Ti (100 nm) alloy film, and Ti/Ag (100 nm) double-layer and Ti/Ag (100 nm)/Ti triple-layer films were prepared by rf sputtering to investigate the effect of Ti on suppression of agglomeration of the Ag thin film caused by thermal treatment. Scanning electron microscopy revealed that the Ag–Ti and Ti/Ag/Ti films had high thermal stability. X-ray photoelectron spectroscopy analysis showed that the surfaces of both kinds of films were covered with a TiO₂ layer after annealing, which was considered to be the key factor for improvement of the thermal stability of the films. In addition, scratch tests indicated improvement of the adhesive strength of the Ti/Ag/Ti film to the SiO₂ substrate due to the underlying Ti film layer, which effectively promoted suppression of Ag agglomeration. However, the resistivity of the Ag–Ti films increased abruptly with increasing Ti content due to the impurity scattering effect, and minimum usage of the alloying element was required to achieve low resistivity. In contrast, the Ti/Ag/Ti film exhibited both low resistivity and high thermal stability.     

Photoinduced properties of nanocrystalline TiO<Subscript>2</Subscript> sol-gel derived thin films

In this paper, nanostructure TiO₂ thin films were deposited on glass substrates by sol-gel dip coating technique. X-ray diffraction and Fourier transform infrared spectroscopy were used to determine film behaviour. The super-hydrophilicity was assessed by contact angle measurement. Photocatalytic properties of these films were evaluated by degradation of methylene blue under UV irradiation. The XRD pattern of TiO₂ powder samples confirmed the presence of polycrystalline anatase phase with a crystal size of 17 nm. The results indicated that UV light irradiation had significant effect on super-hydrophilic and photocatalytic properties of TiO₂ thin films.     

Visible-light absorption and photocatalytic activity of Cr-doped TiO2 nanocrystal films

Chromium doped titanium dioxide (TiO₂) nanocrystal films with various doping concentration have been successfully prepared by a sol–gel dip-coating process. These films have been characterized by XRD, XPS, AFM, and UV–vis absorption spectroscopy. It is found that Cr doping can effectively reduce the transition temperature of anatase to rutile phase as well as the grain size. The absorption edges of TiO₂ thin films shift towards longer wavelengths (i.e. red shifted) from 375 nm to about 800 nm with increasing Cr concentration, which greatly enhances TiO₂ nano-materials on the absorption of solar spectrum. The appearance of UV–vis absorption features in the visible region can be ascribed to the newly formed energy levels such as Cr 2p level and oxygen vacancy state between the valence and the conduction bands in the TiO₂ band structure. The enhancement of the photocatalytic properties is observed for Cr-doped TiO₂ thin film.     

Microanalysis of Pd and V-doped TiO2 thin films prepared by sputtering

Thin films of TiO₂ doped with vanadium and palladium, prepared by the magnetron sputtering method, were studied by means of X-ray diffraction (XRD), Scanning Electron Microscopy with Energy Disperse Spectrometer (SEM-EDS) and Atomic Force Microscopy (AFM). Investigations have brought important information about microstructure due to dopant incorporation in the TiO₂ host lattice. Directly after deposition thin films were XRD-amorphous and SEM investigations did not reveal details on the microstructure. Analysis of the topography of prepared thin films required application of Atomic Force Microscope. The AFM images show that as-deposited sample was dense with grain sizes varied in the range of 5.5 nm-10 nm, that indicated high quality nanocrystalline behavior. Additional annealing results in the formation of three phases in the thin film, e.g. (Ti,V)O₂ — solid solution, PdO and metallic inclusions of Pd. SEM-EDS system allowed analysis of the elemental composition, especially the V one, which lines have not been evidenced in the XRD diffraction pattern. EDS maps show homogenous distribution of elements Ti, O, V, Pd in prepared thin films.     

Synthesis and characterization of photosensitive TiO<Subscript>2</Subscript> nanorods by controlled precipitation route

Nanocrystalline TiO₂ thin films have been successfully synthesized by controlled precipitation route. These films are further annealed at 623 K for 2 h. The change in structural, morphological, optical, and wettability properties are studied by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), scanning electron microscopy (SEM), optical absorption, and contact angle measurement. From the XRD pattern it is clear that the as-grown TiO₂ films are amorphous in nature which becomes polycrystalline after annealing. The FTIR study reveals the formation of TiO₂ compound. Scanning electron micrographs shows that the as-grown TiO₂ film consists of agglomerated nanograins well covered to the substrate surface which gets converted into vertical nanorods after annealing. As-deposited and annealed TiO₂ films showed hydrophilic behavior as water contact angles were 24° and 32°, respectively. The optical absorption study reveals the small red shift due to annealing and attributed to grain size. The annealed TiO₂ film showed conversion efficiency of 0.037% in photoelectrochemical cell with 1 M NaOH electrolyte.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Synthesis of novel photocatalytic InVO4-TiO2 thin films with visible light photoactivity

Novel InVO₄-TiO₂ thin films were synthesized by introducing nano InVO₂ into the TiO₂ thin films via a sol-gel method. The photocatalytic efficiency of InVO₄-TiO₂ thin films was investigated by photodegrading of methyl orange in aqueous solution under visible light irradiation. A wide range of characterization techniques, such as X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), UV-vis absorption spectroscopy (UV-vis), were applied to characterize the obtained thin films. The results indicated that the InVO₄-TiO₂ thin films consist of uniform anatase TiO₂ crystals of 70-80 nm with highly dispersed orthorhombic InVO₄ nanocrystals. The decoloration of methyl orange results illustrated that the InVO₄-TiO₂ thin films with 0.5 wt.% InVO₄ showed the best photoactivities under visible light irradiation, the decoloration rate reached 32.5% after irradiated for 15 h. The InVO₄-TiO₂ thin films exhibited photoactivity under visible light after doped InVO₄ in the TiO₂ films.