Preparation and characterization of TiO<Subscript>2</Subscript> sol–gel modified nanocomposite films

In this study, the role of TiO₂ MT-150A loading in the polymeric sol was investigated for the synthesis of immobilized TiO₂ nanocomposite films on glass substrate using the MT-150A nanoparticles-modified sol–gel method. The nanocomposite film properties were examined using different material characterization techniques including X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, UV–Vis spectrophotometer, Scotch tape test and pencil hardness test. The hydrophilicity of films during UV/Vis irradiation and storage in a dark place were evaluated by a contact angle analyzer. The MT-150A loading had a significant effect on the amount of crystallite phases in the films. However, increasing the MT-150A loading in the sol resulted in an increase in rutile phase content. In addition, increasing MT-150A loading in the sol yielded films with higher hydrophilicity but a concentration of 10–30 g/L MT-150A in the sol was found as the maximum for obtaining films with good adherence on the glass substrate.     

Preparation of highly stable TiO<Subscript>2</Subscript> sols and nanocrystalline TiO<Subscript>2</Subscript> films via a low temperature sol–gel route

Highly stable TiO₂ sols were prepared by adjusting the water-to-titanium molar ratio to ~4 in the process of hydrolysis and condensation of titanium isopropoxide in ethanol with HNO₃. Particularly, long-term stable TiO₂ sols were prepared without adding any chemical additives. Anatase TiO₂ nanocrystallites with sizes of 3–5 nm in diameter were uniformly dispersed in the stable sol. Crystallized TiO₂ films were successfully deposited on Si (100) using the stable sol via a dip-coating process with low temperature curing at as low as 100 °C. The synthesized TiO₂ sols and films are promising for use in flexible or dye-sensitized solar cells.     

Preparation and characterization of In<Subscript>2</Subscript>S<Subscript>3</Subscript> semiconductor thin films using the sol–gel method

This study describes the In₂S₃ semiconductor thin film coating on glass substrate by sol–gel method. The In₂S₃ thin film samples were prepared and examined by the X-ray diffraction (XRD), the UV–visible optical absorption and transmission study, and the Scanning Electron Microscope (SEM) image analyses. The XRD analysis results show that the In₂S₃ semiconductor thin films prepared by sol–gel method is formed at T~360–520 °C temperature interval. Band gap energy and optical absorption spectrum analysis of the In₂S₃ thin films reveal that Eg~2.51 eV for the In₂S₃ thin films. According to the EDX result the film was In-rich with the In/S = 1.42 ratio. The thickness of prepared In₂S₃ layer is about 400 nm.     

Preparation and characterization of TiO<Subscript>2</Subscript> hybrid sol for UV-curable high-refractive-index organic–inorganic hybrid thin films

In this study, UV-curable hybrid thin films were successfully prepared from TiO₂ and TiO₂ hybrid sols containing the acrylic monomer DPHA on PMMA substrates. The prepared TiO₂ and TiO₂ hybrid sols showed long-term storage stability and can provide operating control for the preparation of high-refractive-index hybrid thin films. The existence of interaction between the TiO₂ particle and the coupling agent was evidenced by FT-IR and UV–visible spectra. All hybrid thin films showed good adhesion to the PMMA substrate with refractive index falling over the range 1.64–1.77. These results suggested the potential application of present TiO₂ hybrid films in optical devices, such as anti-reflective coatings.     

Characterization of TiO<Subscript>2</Subscript> powders and thin films prepared by non-aqueous sol–gel techniques

Stable TiO₂ sols were prepared using two non-aqueous sol–gel processes with titanium n-butoxide and titanium isopropoxide, respectively. Crystallization and phase transitions of powders and thin films were studied by ex situ and in situ X-ray diffraction. For both methods, TiO₂ began to crystallize around 320 °C in air. Using helium instead of air during heat treatment slowed down the crystallization and substoichiometric powders were formed. TiO₂ thin films were obtained by spin coating. The morphology of the films was evaluated using scanning electron microscopy. The films were homogeneous and transparent in the visible range. The effect of the heating atmosphere and the type of substrate was investigated.     

Preparation of CuAlO<Subscript>2</Subscript> thin films with high transparency and low resistivity using sol–gel method

CuAlO₂ thin films were deposited on quartz substrates by sol–gel process using copper acetate monohydrate and aluminum nitrate nanohydrate as starting materials and isopropyl alcohol as solvent. The influence of annealing temperature on the film structure and the phase evolution of CuAlO₂ films were investigated, so as to obtain CuAlO₂ films with superior performance. The phase compositions of the films were dependent on the annealing temperature. The films annealed at temperatures below 400 °C were amorphous while those annealed above 400 °C were polycrystalline. The phases of CuO and CuAl₂O₄ appeared gradually with the increase of annealing temperature. When the heat treatment temperature was elevated to 900 °C, the uniform and dense films with single phase of CuAlO₂ were obtained, with a resistivity of 15 Ωcm. The transmittance of the 310 nm-thick CuAlO₂ film is 79% at 780 nm and the direct optical band gap is 3.43 eV.     

TiO<Subscript>2</Subscript> thin films on soda-lime and borosilicate glass prepared by sol–gel processing: influence of the substrates

TiO₂ films were deposited on soda-lime and borosilicate glass substrates, their optical and microstructural properties were investigated. X-ray diffraction showed significant differences between the sample series. Films deposited on the upper surface of soda-lime glass substrates showed higher indices of refraction than those prepared on the lower surface that had been in contact with the tin bath during float glass production. Results indicate that these differences not only result from different optical properties of the TiO₂ backbone material due to alkali contamination but that also different film porosities can measured by ellipsometric porosimetry.     

Bandgap modification of TiO<Subscript>2</Subscript> sol–gel films by Fe and Ni doping

Nickle and iron doped TiO₂ thin films were prepared on glass substrates by sol–gel dip coating process. Indirect and direct optical energy gaps were calculated with the incorporation of different concentrations of both the ions. Indirect bandgap was found to be a strong function of the dopant concentration, whereas direct energy gap has negligible dependence on the nature of dopant and its concentration. Direct energy gap has always been found to retain a value higher than the indirect energy gap. Variation of observed energy gap properties shows a trend similar to that reported on the basis of numerical calculations or the samples obtained by other techniques. Increase in refractive index and corresponding density of the film sample does not support the change in turn over frequency. The influence of crystalline phase change is also ruled out by XRD investigations. It is concluded that red shift of band edge absorption takes place by incorporation of dopant and sol–gel dip coating technique offers an effective low cost route to the production of these coatings.     

Synthesis and characterization of spinel-type CuAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystalline by modified sol–gel method

Nanocrystalline Copper aluminate (CuAl₂O₄) was prepared by sol–gel technique using aluminum nitrate, copper nitrate, diethylene glycol monoethyl ether and citric acid were used as precursor materials. This method starts from of the precursor complex, and involves formation of homogeneous solid intermediates, reducing atomic diffusion processes during thermal treatment. The formation of pure crystallized CuAl₂O₄ nanocrystals occurred when the precursor was heat-treated at 600 °C in air for 2 h. The stages of the formation of CuAl₂O₄, as well as the characterization of the resulting compounds were done using thermo–gravimetric analysis, X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The products were analyzed by transmission electron microscopy and ultraviolet–visible (UV–Vis) spectroscopy to be round, about 17–26 nm in size and E _g = 2.10 eV.     

Synthesis and photocatalytic activity of mesoporous SiO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>

Mesoporous SiO₂–TiO₂ was synthesized by the sol–gel method using Si(OC₂H₅)₄, Ti(OC₂H₅)₄, and stearyltrimethylammonium chloride. By using acetylacetone as the capping agent of Ti(OC₂H₅)₄, homogeneous SiO₂–TiO₂ composite was obtained. Spherical mesoporous SiO₂–TiO₂ was also synthesized by the sol–gel method using W/O emulsion under microwave irradiation. The specific surface area of these mesoporous SiO₂–TiO₂ materials decreased when the Ti/Si molar ratio was higher than 0.1, which indicated that Ti was homogeneously distributed in mesoporous SiO₂ matrix at Ti/Si ≦ 0.1. The photocatalytic activity of mesoporous SiO₂–TiO₂ materials was investigated by the degradation of methylene-blue in water under UV light irradiation. Mesoporous SiO₂–TiO₂ was effective for the adsorption–decomposition of methylene-blue.     

Correlation between structural and optical properties of TiO<Subscript>2</Subscript>:ZnO thin films prepared by sol–gel method

We have studied structural and optical properties of thin films of TiO₂, doped with 5% ZnO and deposited on glass substrate (by the sol–gel method). Dip-coated thin films have been examined at different annealing temperatures (350–450 °C) and for various layer thicknesses (89–289 nm). Refractive index, porosity and energy band gap were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.97–2.44, the porosity is in the range of 0.07–0.46 and the energy band gap is in the range of 3.32–3.43. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZnO, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 20.23 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 of 8.61–29.48 nm.     

Preparation of Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films by sol–gel technique

In this study we describe the preparation of Ga₂Se₃ semiconductor compound thin films by sol–gel method for different crystal formation temperatures. The films were characterized by X-ray diffraction analyses (XRD), UV–visible spectrometer, and scanning electron microscope (SEM). The XRD spectrum showed that the formation of Ga₂Se₃ crystals were between 743 and 823 K. The thin film crystals that were formed at 773 K corresponded to the β phase and the preferred crystal structure was monoclinic. The value of band gap from optical absorption spectra for the Ga₂Se₃ thin films was estimated to be about E _g ~ 2.56 eV. The thickness of the one-coat Ga₂Se₃ thin films, which was measured by a Spectroscopic Ellipsometer, was about ~200 nm. The average grain sizes of scattered particles were within the limits between 200 and 500 nm.     

Particulate sol–gel synthesis and optical and electrical properties of CeO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> nanocomposite

CeO₂/TiO₂ nanocomposite was synthesized by particulate sol–gel method. The X-ray diffractogram shows the presence of cubic CeO₂ and anatase TiO₂ in the composite. The high resolution scanning electron micrographs reveal the nanoparticulate nature of the prepared composite. The composite absorbs UV light and exhibits near-band gap emission corresponding to TiO₂ and deep level emission due to crystal defects. The Nyquist plot displays two semicircular arcs indicating the material heterogeneity. The physicochemical characteristics of the synthesized nanocomposite are in favour of its application as an ingredient of sunscreen formulations; under UV light the photocatalytic activity of CeO₂/TiO₂ composite, tested through the degradation of rhodamine B, is very much less than that by pristine anatase TiO₂. Reduced adsorption of moisture by the nanocomposite is a possible reason for the observed very low photocatalytic activity.     

Synthesis and characterization of CeO<Subscript>2</Subscript>–graphene composite

The synthesis and characterization of graphite oxide (GO), graphene (GS), and the composites: GS–CeO₂ and GO–CeO₂ are reported. This synthesis was carried out by mixing aqueous solutions of CeCl₃·7H₂O and GO, which yields the oxidized composite GO–CeO₂. GO–CeO₂ was hydrothermally reduced with ethylene glycol, at 120 °C, yielding the reduced composite GS–CeO₂. GO, GS ,and the composites with CeO₂ were characterized by CHN, TG/DTG, BET, XRD, SEM microscopy, FTIR, and Raman spectroscopy. The estimation of crystallite size of CeO₂ anchored on GO and on GS by Raman, XRD, and SEM agreed very well showing diameters about 5 nm. The role of particles of CeO₂ coating carbon sheets of GO and GS was discussed.     

Photoelectrochemical performance of bilayered Fe–TiO<Subscript>2</Subscript>/Zn–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films for solar generation of hydrogen

A visible-light sensitive bilayered photoanode of Fe–TiO₂/Zn–Fe₂O₃ has been developed by spray pyrolytically depositing Zn–Fe₂O₃ layers onto predeposited Fe–TiO₂ thin film on ITO substrate. Fe–TiO₂/Zn–Fe₂O₃ photoelectrodes were characterized by XRD, Raman, AFM, UV-vis absorption spectroscopy. Photoelectrochemical properties of bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode were studied by Mott–Schottky curves and I–V characteristics. Bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode was observed to possess much higher separation efficiency of photogenerated charge carriers and could generate nine times better photocurrent density than pure Fe–TiO₂. Solar to hydrogen conversion efficiency exhibited by this electrode was 0.77%.     

Novel sol–gel synthesis of transparent and electrically bistable LiNbO<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> nanocomposites thin films

The morphological and electrical characterization of transparent nanostructured LiNbO₃–SiO₂ thin films synthesized by a novel sol–gel route is reported. Films annealed at different temperatures exhibit different size of the nanocrystals, as demonstrated by Atomic Force Microscopy and Glancing Incidence X-ray diffraction. The dc electrical measurements performed on planar devices reveal electrical bistability. A clear relationship between the electrical bistability and the size of LiNbO₃ nanocrystals embedded in the matrix is observed.     

Preparation of LiCoPO<Subscript>4</Subscript> powders and films via sol–gel

Lithium intercalation materials are of special interest as cathodes in rechargeable batteries. An uncomplicated sol–gel process has been used for the synthesis of Li–Co phosphates powders and, for the first time, of LiCoPO₄ films. The powders were prepared from aqueous solutions, containing Li, Co and phosphate precursors to which acid citric and ethylene glycol was added, during the drying process at 75 °C. The X-ray diffraction patterns of the prepared powders confirmed the presence of LiCoPO₄ with an olivine-like structure as main phase. The morphological investigations of the powder showed a platelet-like structure with an average grain size of 0.75 μm. The films of LiCoPO₄ were deposited onto ITO glass substrates with the combination of the dip-coating process under the same conditions. Finally, the films were annealed in inert atmosphere at 300 °C. The morphological investigations reveal a smooth and homogeneous surface of the prepared Li–Co phosphate films. The preliminary electrical investigation on the prepared LiCoPO₄ films showed lithium ions electrochemical activity in the range 3.0–4.5 V.