The effect of Au and Pt nanoclusters on the structural and hydrogen sensing properties of SnO2 thin films

Au and Pt nanoparticle modified SnO₂ thin films were prepared by the sol-gel method on glass substrates targeting sensing applications. Structural and morphological properties of these films were studied using X-ray Diffraction and Scanning Electron Microscopy. It was proved that the films crystallized in tetragonal rutile SnO₂ crystalline structure. Scanning Electron Microscopy observations showed that the metallic clusters' dimensions and geometry depend on the kind of the metal (Au or Pt) while SnO₂ films surface remains almost the same: nanostructured granular very smooth. Optical properties of the films were studied using UV-visible spectroscopy. The modified SnO₂ films were tested as hydrogen sensors. The response of SnO₂, SnO₂-Au and SnO₂-Pt thin films against hydrogen was investigated at different operating temperatures and for different gas concentrations. The addition of metal nanoparticles was found to decrease the detection limit and the operating temperature (from 180 °C to 85 °C), while increasing the sensing response signal.     

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.     

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.     

Effects of post-deposition annealing on the structure and optical properties of Y2O3 thin films

Y₂O₃ thin film waveguides were prepared by RF magnetron sputtering. The effects of post-deposition annealing on the structure and optical properties have been investigated. The structural evolution of Y₂O₃ films with annealing temperature was investigated by X-ray diffraction (XRD). Spectroscopic ellipsometry was employed to determine the optical properties of Y₂O₃ films annealed at various temperatures. It was found that with increasing annealing temperature, the refractive index (n) of Y₂O₃ films increases. The optical band gap of Y₂O₃ films shifts to higher energy after higher temperature annealing, which is likely due to the reduction of defects and the change of crystalline structure in Y₂O₃ films.     

Cr-doped TiO2 thin films deposited by RF-sputtering

Cr-doped TiO₂ thin films with different band gaps were prepared. Higher Cr doping was beneficial to the formation of the rutile-TiO₂ phase over the anatase-TiO₂ phase. A 4.8% Cr-doped thin film indicated a band gap of 2.95 eV, which was lower than the band gap of the rutile-TiO₂. Cr doping was accompanied by the formation of not only the rutile-TiO₂ phase but also the Cr₂O₃ phase, lead to the degradation of the hydrophilicity. The TiO₂ thin films with the mixed phase were not desirable to improve the hydrophilicity.     

Gas sensing mechanism of TiO2-based thin films

Two classes of thin film gas sensors have been studied: TiO₂ doped with Cr or Nb and TiO₂-SnO₂ mixed systems. Thin films have been prepared by the reactive sputtering from mosaic targets. It is demonstrated that titanium dioxide doped with Nb and Cr should be considered as a bulk sensor. Its performance is governed by the diffusion of point defects, i.e. very slow diffusion of Ti vacancies for TiO₂: 9.5 at% of Nb and fast diffusion of oxygen vacancies in the case of TiO₂: 2.5 at% Cr sensor. The corresponding response times are 55 min for TiO₂: 9.5 at% of Nb and 20 s for TiO₂: 2.5 at% Cr. In turn, sensors based on TiO₂-SnO₂, particularly those of the SnO₂-rich composition, belong to the group of surface sensors.     

Fabrication of TiO2 nanotubes by anodization of Ti thin films for VOC sensing

Ti thin films were anodized in aqueous HF (0.5 wt.%) and in polar organic (0.5 wt.% NH₄F + ethylene glycol) electrolytes to form TiO₂ nanotube arrays. Ti thin films were deposited on microscope glass substrates and then anodized. Anodization was performed at potentials ranging from 5 V to 20 V for the aqueous HF and from 20 V to 60 V for the polar organic electrolytes over the temperatures range from 0 to 20 °C. The TiO₂ nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). It has been observed that anodization of the deposited Ti thin films with aqueous HF solution at 0 °C resulted in nanotube-type structures with diameters in the range of 30-80 nm for an applied voltage of 10 V. In addition, the nanotube-type structure is observed for polar organic electrolyte at room temperature at the anodization voltage higher than 40 V. The volatile organic compound (VOC) sensing properties of TiO₂ nanotubes fabricated using different electrolytes were investigated at 200 °C. The maximum sensor response is obtained for carbon tetrachloride. The sensor response is dependent on porosity of TiO₂. The highest sensor response is observed for TiO₂ nanotubes which are synthesized using aqueous HF electrolyte and have very high porosity.     

Structural, thermal and optical characterization of TiO2:ZrO2 thin films prepared by sol-gel method

We have studied the structural and optical properties of thin films of TiO₂, doped with 5% ZrO₂ and deposited on glass substrate (by the sol-gel method). The dip-coated thin films have been examined at different annealing temperatures (350 to 450 °C) and for various layer thicknesses (63-286 nm). Refractive index and porosity were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.62-2.29 and the porosity is in the range of 0.21-0.70. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZrO₂, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 14.8 nm grains). However, the undoped TiO₂ exhibits an amorphous phase. After heat treatments of thin films, titanium oxide starts to crystallize at the annealing temperature 350 °C. The obtained structures are anatase and brookite. The calculated grain size, depending on the annealing temperature and the layer thickness, is in the range (8.58-20.56 nm).     

An investigation of super-hydrophilic properties of TiO2/SnO2 nano composite thin films

A sol-gel dip coating technique was used to fabricate TiO₂/SnO₂ nano composite thin films on soda-lime glass. The solutions of SnO₂ and TiO₂ were mixed with different molar ratios of SnO₂:TiO₂ as 0, 3, 4, 6, 8, 9, 10.5, 13, 15, 19.5, 25 and 28 mol.% then the films were prepared by dip coating of the glasses. The effects of SnO₂ concentration, number of coating cycles and annealing temperature on the hydrophilicity of films were studied using contact angle measurement. The films were characterized by means of scanning electron microscopy, X-ray diffraction and atomic force microscopy measurements. The nano composite thin films fabricated with 8 mol.% of SnO₂, four dip coating cycles and annealing temperature of 500 °C showed super-hydrophilicity.     

Study of optical and structural properties of Cu2ZnSnS4 thin films

Cu₂ZnSnS₄ is a promising semiconductor to be used as absorber in thin film solar cells. In this work, we investigated optical and structural properties of Cu₂ZnSnS₄ thin films grown by sulphurization of metallic precursors deposited on soda lime glass substrates. The crystalline phases were studied by X-ray diffraction measurements showing the presence of only the Cu₂ZnSnS₄ phase. The studied films were copper poor and zinc rich as shown by inductively coupled plasma mass spectroscopy. Scanning electron microscopy revealed a good crystallinity and compactness. An absorption coefficient varying between 3 and 4 × 10⁴cm^− 1 was measured in the energy range between 1.75 and 3.5 eV. The band gap energy was estimated in 1.51 eV. Photoluminescence spectroscopy showed an asymmetric broad band emission. The dependence of this emission on the excitation power and temperature was investigated and compared to the predictions of the donor-acceptor-type transitions and radiative recombinations in the model of potential fluctuations. Experimental evidence was found to ascribe the observed emission to radiative transitions involving tail states created by potential fluctuations.     

Thermal treatment effect on the optical properties of ZrO2 thin films deposited by thermionic vacuum arc

This paper shows the ex situ thermal treatment effects of the ZrO₂ thin films obtained by TVA (thermionic vacuum arc) technique on the optical properties (e.g., transmittance, refractive index and band-gap energy) of ZrO₂ thin films. The crystal structure, surface and optical properties were investigated for ZrO₂ thin films deposited on glass substrates by thermionic vacuum arc (TVA) method. The thermal treatment effect on the optical properties of the thin films was determined. The XRD analysis showed that the deposited ZrO₂ thin films have baddeleyite (monoclinic) and zirconium (hexagonal) structures. The thicknesses and refractive index were determined by interferometric measurements. The thin films were thermal treated at different temperatures (350 °C, 450 °C and 550 °C), and the analysis showed that the optical properties of ZrO₂ deposited thin films were improved by thermal treatment at 450 °C.     

Optical properties of TiO2 thin films after Ag ion implantation

Metal plasma ion implantation has being successfully developed for improving the electronic and optical properties of semiconductor materials. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. The TiO₂ thin film was optimized to obtain a high-purity crystalline anatase phase by calcinations at 550 °C. The TiO₂ coating was uniform without aggregation, which provided good photo conversion efficiency. Ag ion implantation into the as-calcined TiO₂ thin films was conducted with 1 × 10¹⁵ ~ 1 × 10¹⁶ ions/cm² at 40 keV. The peak position and intensity of the photoluminescence and UV-Vis absorption spectra are quite sensitive to Ag doping. The optical characterization showed a shift in optical absorption wavelength towards infrared ray side, which was correlated with the structure variation of the Ag⁺ implanted TiO₂. Due to the strong capability of forming compounds between the energetic silver ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

Photocatalytic activity of pulsed laser deposited TiO2 thin films in N2, O2 and CH4

We report on pulsed laser deposition of TiO₂ films on glass substrates in oxygen, methane, nitrogen and mixture of oxygen and nitrogen atmosphere. The nitrogen incorporation into TiO₂ lattice was successfully achieved, as demonstrated by optical absorption and XPS measurements. The absorption edge of the N-doped TiO₂ films was red-shifted up to ∼ 480 nm from 360 nm in case of undoped ones.The photocatalytic activity of TiO₂ films was investigated during toxic Cr(VI) ions photoreduction to Cr(III) state in aqueous media under irradiation with visible and UV light. Under visible light irradiation, TiO₂ films deposited in nitrogen atmosphere showed the highest photocatalytic activity, whereas by UV light exposure the best results were obtained for the TiO₂ structures deposited in pure methane and oxygen atmosphere.     

Natural and persistent superhydrophilicity of SiO2/TiO2 and TiO2/SiO2 bi-layer films

Sol-gel SiO₂/TiO₂ and TiO₂/SiO₂ bi-layer films have been deposited from a polymeric SiO₂ solution and either a polymeric TiO₂ mother solution (MS) or a derived TiO₂ crystalline suspension (CS). The chemical and structural properties of MS and CS bi-layer films heat-treated at 500 °C have been investigated by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscospy. Water contact angle measurements show that MS SiO₂/TiO₂ and CS TiO₂/SiO₂ bi-layer films exhibit a natural superhydrophilicity, but cannot maintain a zero contact angle for a long time over film aging. In contrast, CS SiO₂/TiO₂ bi-layer films exhibit a natural, persistent, and regenerable superhydrophilicity without the need of UV light. Superhydrophilic properties of bi-layer films are discussed with respect to the nature of the TiO₂ single-layer component and arrangement of the bi-layer structure, i.e. TiO₂ underlayer or overlayer.     

Effect of sputtering pressure and post-annealing on hydrophilicity of TiO2 thin films deposited by reactive magnetron sputtering

A series of TiO₂ thin films was deposited onto glass substrates without intentional heating or biasing by magnetron sputtering of a titanium target using Ar/O₂ reactive mixtures over a broad range of total sputtering pressures from 0.12 Pa to 2.24 Pa. Each of the film types was deposited by the threshold poisoned mode at a specific given oxygen flow rate monitored in-situ by optical emission spectroscopy. Both the sputtering pressure and thermal annealing are the key factors for the TiO₂ films to yield fast-response superhydrophilicity with a water contact angle of 5°. The mechanism of superhydrophilicity for the TiO₂ films deposited by high-pressure sputtering will be discussed based on empirical studies of X-ray diffractometry, high-resolution scanning microscopy and atomic force spectroscopy.     

Thermo-optic properties of TiO2, Ta2O5 and Al2O3 thin films for integrated optics on silicon

The direct measurement of the thermo-optic coefficients of aluminium oxide, tantalum pentoxide and titanium dioxide thin films is presented. Using ellipsometry on monolithically integrated permutations of the layers of silicon, silicon dioxide and the material under test, allows the direct measurement of the overall thermo-optic coefficient accounting for thermally induced changes in the dielectric permittivity and density of the materials as well as the elasto-optic effect due to the non-matching thermal expansion coefficients of the different materials.     

Photocatalytic properties of Au/TiO2 thin films prepared by RF magnetron co-sputtering

Au/TiO₂ thin films with various Au doping contents were deposited on quartz substrates by radio frequency (RF) magnetron co-sputtering. The as-deposited Au/TiO₂ films were characterized by energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), XRD, and UV-vis techniques. Au doping and UV treatment enhanced the photocatalytic efficiency of TiO₂ thin films. The optimal RF power of the Au target and UV treatment time were 5 W and 1 h, respectively. The enhanced photoactivity of Au(5 W)/TiO₂ thin films with UV treatment is found to result from the increased hydroxyl concentration.     

On the optical, structural, and morphological properties of ZrO2 and TiO2 dip-coated thin films supported on glass substrates

This article reports the optical and morphological properties of dip-coated TiO₂ and ZrO₂ thin films on soda-lime glass substrates by metal-organic decomposition (MOD) of titanium^IV and zirconium^IV acetylacetonates respectively. Thermogravimetric and differential thermal analysis (DTA–TG) were performed on the precursor powders, indicating pure TiO₂ anatase and tetragonal ZrO₂ phase formation. Phase crystallization processes took place in the range of 300–500 °C for anatase and of 410–500 °C for ZrO₂. Fourier Transform Infrared Spectroscopy (FT-IR) was used to confirm precursor bidentate ligand formation with keno-enolic equilibrium character. Deposited films were heated at different temperatures, and their structural, optical and morphological properties were studied by grazing-incidence X-ray Diffraction (GIXRD) and X-Ray Photoelectron Spectroscopy (XPS), Ultraviolet Visible Spectroscopy (UV-Vis), and Atomic Force Microscopy (AFM) respectively. Film thinning and crystalline phase formation were enhanced with increasing temperature upon chelate decomposition. The optimum annealing temperature for both pure anatase TiO₂ and tetragonal ZrO₂ thin films was found to be 500 °C since solid volume fraction increased with temperature and film refractive index values approached those of pure anatase and tetragonal zirconia. Conditions for clean stoichiometric film formation with an average roughness value of 2 nm are discussed in terms of material binding energies indicated by XPS analyses, refractive index and solid volume fraction obtained indirectly by UV-Vis spectra, and crystalline peak identification provided by GIXRD.     

Effects of internal stress on photocatalytic properties of TiO2 films

Effects of internal stress on photocatalytic properties have been investigated on titanium dioxide films deposited by reactive magnetron sputtering. Atomic peening effects by bombardments of high-energy particles in sputtering processes should generate not only compressive stress, but also oxygen defects in the films. Therefore, the films with higher compressive stress performed almost no photocatalytic activity. Furthermore, compressive or tensile stress was applied on the films deposited on curved micro sheet glasses by flattening the substrates after the deposition by external force. It was found that the photodecomposition activity of the films applied the slight compressive stress improved clearly, whereas the one of the films applied the tensile stress degraded.     

Phase transformation in semi-transparent TiO2 films irradiated with CO2 laser

Anatase (TiO₂) thin films were obtained by immersion of glass plates into a titanium sol-gel precursor followed by calcination at 450 °C for 3 h. The Raman results for the CO₂ laser irradiated TiO₂ films show that laser radiation is able to promote favorable changes of anatase phase in anatase/rutile mixtures. Nevertheless, the transformation process level depends on laser characteristics and scan speed of the radiation treatment.