Sol–gel derived N-doped ZnO thin films

N-doped ZnO (NZO) thin films have been prepared by a sol–gel method and their electrical and optical properties have been investigated. The prepared NZO films were p-type, and had excellent electrical properties. They had an optical transparency above 85% in the visible range. The UV absorption edge was red-shifted with increasing N-doping concentration. Two emission bands were observed in the photoluminescence (PL) spectra, with one band located in the UV range and the other band consisting of green luminescence. Both UV and green emissions were enhanced with increasing N-doping concentration.     

Sol–gel deposition and characterization of Mn-doped silicate phosphor films

Mn²⁺-doped Zn₂SiO₄ and Mg₂Gd₈(SiO₄)₆O₂ phosphor films were deposited on silicon and quartz glass substrates by sol–gel process (dip-coating). The variations of sol viscosity with time and film thickness with the number of layers were investigated in Zn₂SiO₄: Mn system. The results of XRD and IR showed that the Zn₂SiO₄: Mn films remained amorphous below 700°C and crystallized completely around 1000°C. From AFM studies, it was observed that the grains with 0.5–0.8 μm size packed closely in Zn₂SiO₄: Mn films, which were uniform and crack free. The luminescence properties of Zn₂SiO₄: Mn films were characterized by absorption, excitation and emission spectra as well as luminescence decay. These properties were discussed in detail by a comparison with those of Mn²⁺ (and Pb²⁺)-doped Mg₂Gd₈(SiO₄)₆O₂ phosphor films.     

Sol–gel alumina environmental barrier coatings for SiC grit

SiO₂ surface film is insufficient to protect SiC from the oxidation at widely varying partial pressures of oxygen, in particular in the presence of water vapor (e.g. in gas turbines) and also in other environments, e.g. during brazing for hard “tipping” of turbine blades. This work demonstrates that sol–gel alumina, coated on 0.5 mm coarse SiC grit, may form an acceptable, up to 10 μm thick “environmental barrier coating” EBC for some of these applications. The sol–gel has advantages over other methods (such as CVD) is the simplicity and low cost. We have used NH₄OH pre-treatment to hydroxylate surface of SiC prior to applying alumina coating. Such modified SiC/SiO₂ surface helped to deposit the positively charged alumina sol, and thus allowed to build thick coatings on the SiC grit. There is some indication that these coatings partially convert to mullite through reaction at the interface with the native silica on SiC. Oxidation resistance tests at 1200 °C were performed to show effectiveness of such coated SiC grit.     

UV-induced permanent gratings in sol–gel germanosilicate thin films

Germanosilicate thin films have been elaborated by the sol–gel process and the dip-coating technique. Pulsed or continuous wave UV laser (244 nm) was used to write permanent gratings in these films. In the case of exposure to cw laser, the grating diffraction efficiencies were measured using a focused beam from a He–Ne laser at 633 nm and photo-induced changes in refractive index as high as 4×10⁻³ have been obtained. The thermal behaviour of these gratings has been investigated showing a good stability up to 400°C. Exposure to pulsed fringe pattern led to a glass photo-expansion modulated by a strong corrugation which can be due mainly to photo-ablation at the places of the bright fringes. The waveguide surface at the grating places was investigated through Atomic Force Microscopy (AFM) and microscopic profilometry techniques. Preliminary results on the kinetics of the grating growths are also reported.     

Indium-doped ZnO thin films deposited by the sol–gel technique

Conducting and transparent indium-doped ZnO thin films were deposited on sodocalcic glass substrates by the sol–gel technique. Zinc acetate and indium chloride were used as precursor materials. The electrical resistivity, structure, morphology and optical transmittance of the films were analyzed as a function of the film thickness and the post-deposition annealing treatments in vacuum, oxygen or argon. The obtained films exhibited a (002) preferential growth in all the cases. Surface morphology studies showed that an increase in the films' thickness causes an increase in the grain size. Films with 0.18 μm thickness, prepared under optimal deposition conditions followed by an annealing treatment in vacuum showed electrical resistivity of 1.3 × 10^− 2 Ωcm and optical transmittance higher than 85%. These results make ZnO:In thin films an attractive material for transparent electrodes in thin film solar cells.     

Holographic gratings in DR1-doped sol–gel silica and ORMOSILs thin films

Holographic diffraction gratings have been obtained in Disperse Red 1 (DR1)-doped silica and ORganically MOdified SILanes thin films (ORMOSILs), produced by tetraethylorthosilicate (TEOS) and 3-(triethoxysilyl)propyl isocyanate (ICPTEOS) as precursors for the sol–gel process. For the DR1 + TEOS film, the grating is associated to an irreversible bleaching of the dye and may be detected by a Raman micro-spectroscopy mapping. For films based on ICPTEOS, a transient phase diffraction grating is created by the photoinduced birefringence. Two characteristic relaxation times of the birefringence grating have been measured.     

Densification of sol–gel TiO2 very thin films studied by SPR measurements

Very thin TiO₂ films have been prepared by sol–gel and deposited on a silver layer for Surface Plasmon Resonance (SPR) measurements. Densification of the samples has been studied by determining from SPR measurements the optical index (ranging from 1.68 to 1.92) and thickness (ranging from 6 to 2 nm) at each step of the annealing procedure. The structure of the layer (amorphous and/or crystalline) has been checked at the final stage of the thermal treatment by High Resolution Transmission Electron Microscopy (HRTEM).     

Inhomogeneous distribution of organic molecules adsorbed in sol–gel glasses

The effects of the porous matrix upon the radiative characteristics of quinine sulphate doped sol–gel glasses are investigated. The broadenings of the absorption and fluorescence spectra are explained by the attachment of the molecules on distorted sites or in a non-planar fashion, creating an inhomogeneous distribution of adsorbed molecules. For this reason, each emitting center relaxes with its own characteristics. This inhomogeneous distribution is also supported by the non-exponential and the wavelength dependence of the fluorescence decay.     

Sol–gel synthesis, comparative characterisation, and reliability analyses of undoped and Al-doped zinc oxide thin films

Thin films of sol–gel derived undoped and Al-doped zinc oxide material systems were fabricated for potential use in transparent conducting oxide modules. A comparative characterisation of the functional properties of the films was performed. Undoped zinc oxide thin films were obtained with desired properties. Al doping reduced the average crystallite size, and led to a denser and less porous morphology, and also caused an increase in transparency in the UV region. An improvement in electrical conductivity was achieved upon Al doping. Temperature cycling and accelerated delamination test results demonstrated the high physical reliability of the thin films of the material system obtained in this study.     

Structural and optical properties of vanadium pentoxide sol–gel films

The V₂O₅ films were obtained using sol–gel procedure. The composition and mesostructure of the layers were investigated with the UV and Raman spectroscopy, as well as with electron microscopy. We showed that the changes in the properties of thin layers accompanying the variation of film thickness are connected with the changes in the microstructure of the film rather than with changes in its composition. The thin V₂O₅ layers obtained in the present study are composed of disordered clusters; their mean size is 4–13 nm.     

Sol–gel preparation of boron-containing cordierite Mg2(Al4−xBx)Si5O18 and its crystallization

Five cordierite-based powders were investigated regarding their thermal and crystallization behaviors. The powders were obtained from amorphous gels having nominal compositions of 2Mg : xAl : (4 − x)B : 5Si where x = 4 down to 0. Thermal gravimetry analysis of the dry gels showed some absorbed water and decomposition of organic ligands in addition to network condensation. Gradual substitution of B for Al in the dried gel powders showed a new band in their infrared spectra corresponding to triangular BO₃, whereas the bands corresponding to Al vanished. This also showed a noticeable effect on the crystallization trends, type and stability of cordierite. Cordierite crystallized in samples of B/Al ratio up to 1 while protoenstatite predominated in samples of higher B/Al ratios. In addition, some silica minerals, with little amorphous phase, were formed. Incorporation of boron and increase in temperature enhanced the transformation of γ cordierite to its form.     

Development of photo-patternable organo-mineral hybrid films from the sol–gel condensation of alkoxysilanes

We describe the synthesis and refractive index characterisation of four organo-siloxanes materials, applicable to the fabrication of photo-patternable channel waveguides. By combining aliphatic, aromatic and vinylic alkoxysilane precursors, organically modified silicates materials have been synthesised using the sol–gel process. Control of the refractive index was achieved through the variation of aliphatic and aromatic alkoxide content within the materials. It is clearly demonstrated that the presence of aromatic groups significantly increases the refractive index to 1.562. Conversely, the addition of vinylic groups decreases the value to 1.490. These findings are attributed to the atypical polarisability exhibited by aromatic and aliphatic precursors, which strongly affect the overall molar refraction.     

Sol–gel thin film deposition and characterization of a new optically active compound: Er2Ti2O7

This paper reports on the first sol–gel thin film preparation of a new optically active compound: Er₂Ti₂O₇ (ETO). Optical, microstructural and spectroscopic properties of ETO films annealed in a temperature range 300–1000°C are studied. This work shows that the porosity and microstructure of ETO films depend closely on the heat-treatment temperature. Photoluminescence (PL) has been observed for films heat-treated at 600°C or more. The PL decay appears strongly influenced by quenching effects. For thin films treated at 600°C, quenching is essentially due to the presence of hydroxyl groups. After heat-treatment at 800°C or more, quenching can be explained by the high concentration of erbium atoms and by their distribution in the ETO lattice.     

Spectroscopic study of Eu(fod)3 complex adsorbed on an amorphous silicon inorganic–organic hybrid

By using tetraethylorthosilicate (TEOS) and N-[3(trimethoxysilyl) propyl]-ethylenediamine as precursors, an inorganic–organic hybrid is synthesized, which is employed as a substrate to adsorption and hence spectroscopic study of the Eu(fod)₃ complex. Eu(fod)₃ and the silicon hybrid were mixed in stoichiometric amounts to produce samples with 1%, 5% and 10% (m/m) of adsorbed complex, with the matrices being pressed at 380 mPa for 0.5, 30 and 60 min. It is verified that the intensity of the ⁵D₀→⁷F₂ emission band decreases as the percentage of complex is increased, which is interpreted as consequence of the modification of the coordination sphere of the complex.     

Deposition and photoluminescence of sol–gel derived Tb:Zn2SiO4 films on SiO2/Si

Tb³⁺ doped Zn₂SiO₄ films have been deposited on SiO₂ buffered Si wafers by sol–gel method. The structures of these films have been investigated with X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The results revealed that these films were composed of nanometer-size grains with a Willemite structure and had smooth surfaces. Photoluminescence measurements of the films showed a strong emission from ⁵D₄ to ⁷F₅ at 544 nm. The blue emission from ⁵D₃–⁷F_j was depressed because of cross-relaxation effect. The decay kinetics of the ⁵D₄–⁷F₅ green emission was studied and a best fitting was obtained by a double exponential function. The lifetime of the excited ⁵D₄ state is estimated to be 5.2 ms.     

Synthesis of nanocrystalline photocatalytic TiO2 thin films and particles using sol–gel method modified with nonionic surfactants

A simple sol–gel route has been developed for the preparation of nanocrystalline photocatalytic TiO₂ thin films and particles at 500 °C. The synthesis involved a novel chemistry method employing nonionic surfactant molecules as a pore directing agent along with acetic acid-based sol–gel route without direct addition of water molecules. This study investigated the effect of surfactant type and concentration on the homogeneity, morphology, light absorption, dye adsorption and degradation, and hydrophilicity of TiO₂ films as well as on the structural properties of the corresponding TiO₂ particles. The method resulted in the synthesis of mesoporous TiO₂ material with enhanced structural and catalytic properties including high surface area, large pore volume, pore size controllability, small crystallite size, enhanced crystallinity, and active anatase crystal phase. The prepared TiO₂ thin films were super-hydrophilic and possessed thermally stable spherical bicontinuous mesopore structure with highly interconnected network. Highly porous TiO₂ films prepared with polyethylene glycol sorbitan monooleate surfactant exhibited four times higher photocatalytic activity for the decoloration of methylene blue dye than the nonporous control TiO₂ films prepared without the surfactant. This sol–gel method modified with surfactant templates is useful in the preparation of nanostructured anatase TiO₂ thin films with high photocatalytic activity and desired pore structure.     

Ferroelectric properties of BiFeO3 films grown by sol–gel process

Several methods have been used to prepare ferroelectromagnetic BiFeO₃ films. In this paper, we adopted a sol–gel process to fabricate BiFeO₃ films on indium tin oxide (ITO)/glass substrates. X-ray diffraction pattern indicated that the samples are randomly oriented. Cross section scanning microscopy showed that the thicknesses of both films were about 1.2 μm and no apparent diffusion between the BiFeO₃ films and ITO/glass substrates. Remnant polarization of 2.0 and 1.75 μC/cm² were identified by the measuring of electric hysteresis loops for the films annealed at 500 and 600 °C respectively at an applied field of 108 kV/cm. Dielectric property and loss factor were investigated as a function of frequency. In addition, magnetism was detected at 77 K.     

Stability of second-order nonlinear optical properties in sol–gel matrix bearing silylated chalcone and disperse red 1

We report the syntheses of two triethoxysilanes for thin film fabrication. One silane (SGDR1) contains disperse red 1 (DR1) which is a second-order nonlinear optical (NLO) active chromophore. The other silane (SGCHC) bears a chalcone derivative. In order to improve the poor temporal stability of second-order NLO effects in the resulting poled sol–gel film, photo-crosslink was induced between the double bonds in chalcone units after mixing SGDR1 and SGCHC. Under UV exposure, the photocrosslink was studied with UV–visible absorption and IR vibrational spectroscopy. The decaying behavior of the molecular order parameter (A₂) after corona poling was investigated using polarized absorption spectroscopy (PAS). Second-order non-linear optical properties of the sample were studied using second-harmonic generation (SHG) and linear electro-optic (E/O) signal measurement. Poled and UV-cured film of SGDR1/SGCHC exhibited much better stability than thermally poled sample with respect to the molecular order parameter and linear electro-optic effect.     

Preparation and optical properties of sol–gel derived Er-doped Al2O3–Ta2O5 films

Thin films of the system xAl₂O₃–(100 − x)Ta₂O₅–1Er₂O₃ were prepared by a sol–gel method and a dip-coating technique. The influences of the composition and the crystallization of the films on Er³⁺ optical properties were investigated. Results of X-ray diffraction indicated that the crystallization temperature of Ta₂O₅ increased from 800 to 1000 °C with increased values of x. In crystallized films, the intensities of the visible fluorescence and upconversion fluorescence tend to decrease with an increase in x values, due to the high phonon energy of Al₂O₃; the strongest fluorescence is observed in a crystallized film for x = 4 heat treated at 1000 °C. In amorphous films obtained by heat treatment at relatively low temperatures the Er³⁺ fluorescence could not be observed because strong fluorescence from organic residues remaining in the films thoroughly covered the Er³⁺ fluorescence. On the other hand, the Er³⁺ upconversion fluorescence in the amorphous films was observed to be stronger than that in the crystallized films. The strongest upconversion fluorescence is observed in an amorphous film for x = 75 heat treated at 800 °C.     

Photoluminescence properties of an oligo-phenylkene vinylene derivative doped in polymer/silica hybrid sol–gel matrix

An oligo-phenykene vinylene derivative 4,4′-(1,4-phenylene dithenylene)-bis-(N-methyl pyridinium iodide) (OPVD) was introduced into poly(hydroxyethyl methacrylate) (PHEMA)-impregnated silica composite film by the sol–gel process. The X-ray diffraction and UV–VIS reveal that this method can restrict the crystallization of OPVD and OPVD molecules tend to form J-aggregates in the composite film. The results of photoluminescence of OPVD in the composite film indicate that as compared with OPVD itself, the emission peak of OPVD in the composite film undergoes a blue shift about 80 nm, fluorescence intensity enhances and the photostability is much better, which make such composite film of more practical significance.