Synthesis of Fe-doped nanosized SnO2 powders by chemical co-precipitation method

Fe-doped nanosized SnO₂ powders were prepared by chemical co-precipitation technique using SnCl₄ and FeCl₃ as starting materials and water as a carrier. Experimental results show that the grain size of Fe-doped SnO₂ crystallites is smaller than 5 nm, and the particle size is smaller than 15 nm. When the calcination temperature is below 650 °C, the SnO₂ crystal has tetragonal lattice structure. At higher temperature the particles become a two-phase mixture of tetragonal SnO₂ and hexagonal Fe₂O₃ crystallites. Fe doping can obviously prevent the growth of nanosized SnO₂ crystallites, and a higher Fe-doping concentration is more effective to prevent the growth of nanosized SnO₂ particles when the calcination temperature is below 550 °C.     

Multinuclear NMR study of phosphosilicate gels derived from POCl3 and Si(OC2H5)4

Solid state ¹H, ²⁹Si and ³¹P MAS NMR have been used to investigate the microstructure of phosphosilicate gels prepared by a modified sol-gel method involving hydrolysis of silicon precursors in a solely aqueous environment at 50 °C. Gels with molar compositions 5, 10, 20 and 30 mol% P₂O₅ in P₂O₅-SiO₂ were studied. After drying to 400 °C the gels have very similar structures formed by a siloxane framework containing silanol groups and trapped molecules of orthophosphoric acid together with a very small amount, of pyrophosphoric acid. Unlike the gel samples previously synthesized by the hydrolysis of the silicon precursor in alcoholic solution at room temperature, the co-polymerization of phosphorus and silicon is much reduced. Although co-polymerization increases with phosphorus content, it still represents less than 50% of the phosphorus in the 30 mol% P₂O₅ gel. Furthermore there is no evidence for six-coordinated silicon in the glassy matrix.     

Aggregation effects in non-linear absorption of CuPc-SiO2 sono-xerogels

It is known that aggregation effects in metallophthalocyanine/SiO₂ composites play an important role in the optical properties of these materials. With the aim to avoid phthalocyanine dimer and oligomer formation induced in aqueous solution, alternative processing methods for trapping the organic in the matrices have been tested. The combination of ultrasonic energy used to promote the reactions and the methanol used as solvent, makes it possible to obtain monolithic xerogels under extremely acid conditions, preserving their homogeneity and transparency. Textural parameters and pore size distribution of the composites and the optical absorption features have been evaluated. Finally, the effects of molecular self-association degree on the non-linear absorption of the samples have been analyzed. All the samples studied exhibit reverse saturable absorption behavior but the figure of merit is strongly determined by the aggregation state of the active phase in the composite.     

Effect of Y2O3 addition on the phase transition and growth of YSZ nanocrystallites prepared by a sol-gel process

The effect of Y₂O₃ addition on the phase transition and growth of yttria-stabilized zirconia (YSZ) nanocrystallites prepared by a sol-gel process with various mixtures of ZrOCl₂ · 8H₂O and Y(NO₃)₃ · 6H₂O ethanol-water solutions at low temperatures has been studied. DTA/TGA, XRD, SEM, TEM and ED have been utilized to characterize the YSZ nanocrystallites. The crystallization temperature of 3YSZ, in which Y₂O₃/(Y₂O₃ + ZrO₂) = 0.03, gel powders estimated by DTA/TG is about 427 °C. When 3YSZ and 5YSZ gels are calcined at 500-700 °C, their crystal structures as composed of coexisting tetragonal and monoclinic ZrO₂, and tetragonal phase decreases with calcination temperature increasing from 500 to 700 °C. Pure cubic ZrO₂ is obtained when added Y₂O₃ is greater than 8 mol%. A nanocrystallite size distribution between 10 and 20 nm is obtained in TEM observations.     

Sol-gel preparation and optical properties of SiO2-Ta2O5 glass

Tantalum-doped silica glass was fabricated by the sol-gel process in order to obtain a glass with a high refractive index for optical use. A crack-free, clear glass rod was successfully prepared from a low-density gel and used as the core material for fabricating optical fibers. Transmission loss in the fabricated fibers was high, in the range of 10³-10⁴ dB/km, which may be caused by coloration due to the multivalency of tantalum; however, the loss was reduced by nearly one order of magnitude by heat treatment at 800 °C, that is, to 75 dB/km at a wavelength of 0.8 μm.     

The coordination state and valence state of selected transition metal ions in SiO2-B2O3 xerogels

A series of SiO₂-B₂O₃ xerogels with changing SiO₂/B₂O₃ mol% and doped with selected transition metal ions was prepared. These mixed oxide materials contained copper, nickel, cobalt, manganese, chromium and vanadium ions coordinated to oxygen donor atoms in water and OH groups. Extensive studies of the transition metal complexes in the xerogels by such spectral techniques as diffuse reflectance (UV-vis), electron paramagnetic resonance and fluorescence spectroscopies show that there exist Cu(II) in the coordination environment of D_4h symmetry, Ni(II) in octahedral coordination sphere, Co(II) in both tetrahedral and octahedral environments, Mn(II) preferably in the O_h coordination and Mn(III) in pseudo-octahedral sphere; then octahedrally coordinated Cr(III) ions occur in coupled pairs or clusters and V(IV) as VO²⁺ ions exist in distorted (C_4v) octahedral surrounding.     

Luminescence of CaS and MnS nanocrystallites co-activated sol-gel derived silica xerogel

CaS and MnS nanocrystallites co-activated sol-gel derived silica xerogel has been prepared by sol-gel processing. Their photoluminescence characteristics have been evaluated and compared with those of the undoped silica xerogel. Two emission bands have been observed from the doped sample, one at 440 nm while the other at 580 nm. CaS and MnS nanocrystallites embedded in sol-gel derived silica xerogel show sharp emission band. The novel luminescence phenomenon is attributed to the luminescent centers of CaS and MnS in the silica xerogel.     

Preparation and characterization of ZrO2-SiO2 binary films for planar optical waveguides

ZrO₂-SiO₂ binary films for active optical waveguides were prepared by the sol-gel method with zirconium oxychloride and tetraethoxysilane as precursors. The main factors that influence the film thickness and refractive index have been found. The relationship between the film refractive index composition and heat treatment temperature has been determined. The continuous tuning of the thickness and refractive index of the thin films has also been achieved, which will open up new possibilities in the development of active optical waveguides.     

Sol-gel processing of TeO2-TiO2-PbO thin films

TeO₂-TiO₂-PbO thin films were prepared by sol-gel processing from tellurium(IV) isopropoxide precursor and their transmittance spectrum was measured, from which the refractive index was calculated. The hydrolysis of tellurium(IV) isopropoxide and the decomposition process of its hydrolysis product were investigated. The discrepancy between the observed hydrolysis behavior of tellurium(IV) isopropoxide and the partial charge model on the reactivity of metal alkoxides toward hydrolysis, being calculated with the Pauling electronegativity, is explained by a combination of the inductive and steric effects of isopropoxide groups and the electronic configuration of the tellurium atom with lone pair electrons.     

Self organized nano crystallinity of magnetite precipitated from a 4.9Na2O · 33.3CaO · 17.1Fe2O3 · 44.7B2O3 glass

Glasses with the mol% composition 4.9Na₂O · 33.3CaO · 17.1Fe₂O₃ · 44.7B₂O₃ were melted, rapidly quenched using a twin roller technique, and subsequently tempered in the range from 550 to 620 °C. This led to the crystallization of magnetite with mean crystallite sizes in the 10-20 nm range. Using higher temperatures resulted in a larger quantity of formed crystallites and slightly larger mean crystallite sizes. Larger tempering times did not lead to substantial crystal growth. The time law of Ostwald ripening was not followed. This is explained by an increase in viscosity of the residual glassy phase during nucleation and crystal growth. Here, the smaller iron concentration near the crystals leads to higher viscosities and to the formation of a diffusional barrier around the crystals, which reduces further crystal growth. The crystallization stops, if T_g of the residual glassy phase is equal to the tempering temperature. Magnetite nano crystals with sizes in the 10-20 nm range offer a wide range of applications, such as the preparation of ferrofluids or of materials for medical diagnostics and therapy.     

Effects of organic content and H2O/TEOS molar ratio on the porosity and pore size distribution of hybrid naphthaleneaminepropylsilica xerogel

The hybrid naphthaleneaminepropylsilica material was obtained by a sol-gel route, varying the organic loading and the water/TEOS molar ratio. Infrared spectroscopy was used to identify the organic and inorganic phases. The morphology of the hybrid material was studied by using scanning electron microscopy and N₂ adsorption-desorption isotherms. It was observed that the increase in the organic content produces a decrease in the size and volume of the pores as well as in the surface area of the xerogel. The best porosity was obtained for water/TEOS molar ratio between 4 and 6.     

Inclusion of carbon nanotubes in a TiO2 sol-gel matrix

We report here the successful inclusion of carbon nanotubes (CNs) into a TiO₂ matrix prepared by a sol-gel method. The presence of CNs in the sol-gel matrix and the structure of the film were analyzed principally by transmission electron microscopy. Complementary information about the behavior of embedded carbon nanotubes versus heat treatment and ion irradiation were obtained by X-ray photoelectron spectroscopy. The elaboration of an inorganic matrix containing embedded carbon nanotubes leads to a new nanocomposite. The possible applications of this nanocomposite are discussed.     

Local structure of LuBO3 prepared via sol-gel process and its transformation with temperature: B-NMR and L-edge XAS studies

The present work deals with the temperature effect on the stability range of LuBO₃ prepared by sol-gel synthesis. Structural modifications from vaterite to calcite form versus the thermal treatments have been measured by X-ray diffraction and infrared spectroscopy. Several samples derived from the xerogel annealed at 400, 800 and 1200 °C were studied by ¹¹B solid state NMR and at the lutetium L_I-L_III edges by X-ray absorption spectroscopy to determine the local atomic arrangement around the rare earth and the boron ions. The predominance of BO₄ groups and the eightfold coordination of lutetium atoms in the LuBO₃ xerogel in samples treated up to 800 °C indicate an evolution of the xerogel to vaterite form after thermal treatment instead of the expected calcite form as established for samples prepared by solid state reaction.     

Cobalt ortho- and para-substituted tetraphenylporphyrins inserted in SiO2 gels

The sol-gel method, generally, allows the trapping of important organic and biological systems in inorganic networks. Free and metallic porphyrins feature a wide range of important electrical, optical, and catalytic properties. To fix them in gels it is necessary to substitute an appropriate reactive group in the periphery of the macrocycle, which thus becomes more soluble in water or alcohols. The substituents more frequently employed have been -SO₃⁻, -Na⁺, -COOH and pyridinium salts. We have tried to increase the number, type, and spatial position of such substituents, to evaluate their influence in the quality and properties of the final materials. In this work we report the results obtained with the Co(II) complexes of the meso-5,10,15,20-tetraphenylporphyrin macrocycle, in which the amino, -NH₂(basic) or hydroxyl, -OH (acid) groups have been placed in the ortho- and para-positions of the phenyl groups. The insertion of cobalt porphyrins was made possible by the addition of small quantities of pyridine, methanol or dimethylformamide (DMF). Maxima in the transparency and strength of the materials were obtained with the para-amino substituted porphyrin, when methanol and pyridine were employed as the solvent media. Our results reveals that methanol has no influence on the morphology of the silica network, but DMF changes it drastically. The procedure here described has been successfully extended to trap other free and metallic porphyrinic systems.     

Ablation and compaction of amorphous SiO2 irradiated with ArF excimer laser

The structure of amorphous SiO₂ exposed to ArF excimer laser irradiation was examined. Threshold fluence for causing ablation with a single pulse depended on sample preparation: more specifically, 1 J/cm² for thermally grown SiO₂ films on silicon and 2.5 J/cm² for bulk SiO₂. It was found that the bond angle of Si-O-Si was reduced by irradiation near the interface of thermally grown SiO₂ films. In contrast, evolution of the bond angle by irradiation was absent in both the bulk SiO₂ and SiO₂ film-near the top surface, even though the concentration of puckered four-membered rings deduced from Raman spectra dramatically increased. It is assumed that planar three-membered rings were generated in the SiO₂ thin layer near the interface, and puckered four-membered rings were generated in the bulk SiO₂. The concentration of both the Si³⁺ and Si²⁺ structure was increased at a fluence of 800 mJ/cm² with an increasing number of pulses, although generation of both was absent at higher fluence for a single pulse. The author proposes that the structure of SiO₂ is created by flash heating and quenching by pulse laser irradiation. Structural similarities were found between the irradiated SiO₂ and SiO₂ at high temperatures.     

Nanocrystalline TiO2 films studied by optical, XRD and FTIR spectroscopy

We report the deposition of thin titanium dioxide films on Si(1 0 0) and silica glass at low temperatures between 200 and 350 °C by a technique of ultraviolet-assisted injection liquid source chemical vapor deposition (UVILS-CVD) with 222 nm radiation. The composition and optical properties of the films deposited have been studied using a variety of standard characterisation methods. A strong absorption peak around 438 cm⁻¹, corresponding to Ti-O stretching vibration, was observed by Fourier transform infrared spectroscopy for different deposition temperatures. Nanostructured films on Si wafers were observed by atomic force microscopy while X-ray diffraction results showed that crystalline TiO₂ layers could be formed at deposition temperatures as low as 210 °C. The deposition kinetics and influence of the substrate temperature on the film are discussed. The activation energy for this photo-CVD process at temperatures between 200 and 350 °C was found to be 0.435 eV. This is much lower than the value (E_a=5.64 eV) obtained by conventional thermal CVD. The thicknesses of the films grown, from several nanometers to micrometers can be accurately controlled by changing the number of drops introduced by the injection liquid source. Under optimum deposition conditions, refractive index values as high as 2.5 and optical transmittance of between 85% and 90% in the visible region of the spectrum can be obtained.     

Study of the phase transition and the thermal nitridation of nanocrystalline sol-gel titania films

Nanocrystalline titania films were prepared by a complexing agent-assisted sol-gel method and converted to titanium nitride by a thermal nitridation process. The effect of acetylacetone (AcAc), diethanolamine (DEA) and acid catalysts (HCl and HNO₃) on the structure and morphology of the heat-treated titania films and on their nitridation products was examined by FTIR spectroscopy, X-ray diffraction (XRD) and atomic force microscopy (AFM). The carbothermal reduction of titania during the nitridation process with the formation of carboxynitrides has been considered. The results showed that the oxide to nitride transition strongly depends on the complexing agent used to prepare the titania films. The XRD results indicated the dependence of the lattice parameter of the nitridation product on the complexing agent or acid catalyst: AcAc and DEA lead to TiN_x with a lattice parameter α close to the theoretical value, while with HCl the lattice parameter was found sensibly lower showing the presence of an oxynitride. These results are accounted for by the effect of complexing agents and acid catalysts on the size of both TiO₂ and TiN grains and the different reactivity of the anatase and rutile phases. The possibility of tailoring the composition and morphology of TiN films by using complexing agents is envisaged.     

Preparation and characterization of transparent Eu doped Y2O3 aerogel monoliths, for application in luminescence

This paper focuses on a new sol-gel preparation method of Eu doped Y₂O₃ aerogels, for application in luminescence and their characterization. The preparation method is based on a sol-gel technique using metal salts, by controlling the hydrolysis of these precursors with an epoxide. The monoliths prepared in this manner are transparent in the visible radiation domain. They have a mesoporous texture, a specific surface area of ≈350 to 400 m² g⁻¹ and they are X-ray amorphous. The gel network could be clearly observed by Transmission Electron Microscopy and showed the presence of localized poorly crystalline nanodomains, with some Eu segregation. A first evaluation of the luminescence which they develop during crystallization, has been carried out as a function of the heat treatment schedule.