Self-Structuring of Lamellar Bridged Silsesquioxanes with Long Side Spacers

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

Influence of pH on the incorporation and growth of Pb2CrO5 crystallites in silica matrix

Pb2CrO5 nanoparticles were embedded in an amorphous SiO2 matrix by the sol-gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb2CrO5/SiO2 compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka-Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb2CrO5/SiO2 compounds were shown and discussed. In general, an acid pH initially dissolves Pb2CrO5 nanoparticles and following heat treatment at 600 A degrees C crystallized into PbCrO4 composition with grain size around 6 nm in SiO2 matrix. No Pb2CrO5 solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.

Ligand Exchange Inducing Efficient Incorporation of CisPt Derivatives into Ureasil-PPO Hybrid and Their Interactions with the Multifunctional Hybrid Network

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Controlled Cisplatin Delivery from Ureasil-PEO1900 Hybrid Matrix

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Lanthanide-Containing Light-Emitting Organic-Inorganic Hybrids: A Bet on the Future

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Optical emission and electron capture of rare-earth trivalent ions located at distinct sites in SnO(2) thin films

We present photoluminescence and decay of photo excited conductivity data for sol-gel SnO(2) thin films doped with rare earth ions Eu(3+) and Er(3+), a material with nanoscopic crystallites. Photoluminescence spectra are obtained under excitation with several monochromatic light sources, such as Kr(+) and Ar(+) lasers, Xe lamp plus a selective monochromator with UV grating, and the fourth harmonic of a Nd: YAG laser (4.65eV), which assures band-to-band transition and energy transfer to the ion located at matrix sites, substitutional to Sn(4+). The luminescence structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at grain boundary layer, where it is placed in asymmetric sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference between capture energy and grain boundary barrier is not so evident, even though the luminescence spectra are rather distinct.

Formation of SnO2 gels from dispersed sols in aqueous colloidal solutions

Transparent SnO2 gels were obtained from SnCl4 aqueous solution. The sol formation from tin oxihydroxy peptization in different concentrations and by electrolyte addition in solution was measured. It was verified that the residual presence of chloride ions compromises the colloidal system stability. The sol-gel transition was investigated as a function of the quantity of solid particles in the aqueous environment and of aging time at 60°C by infrared spectroscopy and rheological measurements. The transition from plastic to pseudoplastic flow observed with the increase in loading suggests that a continuous and three-dimensional network formation is closely related to hydrogen bridges and/or hydrogen clusters, culminating in the gel formation. © 1990.

SnO2:Eu nanocrystallites in SnO2 monolithic xerogels

By simple room temperature broad band time-resolved spectroscopy it was possible to discriminate different Eu3+ spectra in SnO2 monolithic gels obtained by a sol-gel synthetic route. Nanocrystalline domains of the cassiterite-like SnO2:Eu could be easily identified in the transparent medium. From X-ray diffraction profiles a mean particle radius of 2.2 nm was estimated. © 1992.

Study of SnO2 gels by Eu3+ fluorescence spectroscopy

Eu3+ fluorescence spectroscopy was used as a probe to study the changes in local arrangements of tin oxyhydroxide precipitate → sol → gel → glass conversion. Electronic transition intensities and 5D0 excited state lifetime variations were followed during the entire process. Adsorption of Eu3+ ions on the colloid and changes of chemical interactions occurring in each step are described. © 1992 Elsevier Science Publishers B.V. All rights reserved.

Spectroscopic characterization of SnO2 gels - Code: CP11

Excitation and dynamic emission spectra of Eu3+ ions were simultaneously used with FTIR and Raman spectroscopy to study the structural evolution during SnO2 sol → gel → xerogel conversion. Results make evident an increase of the surroundings symmetry for the Eu3+ ions dissolved in SnO2 matrix and a decrease of the amount of hydroxo groups (Sn-OH) during drying. These phenomena were associated to the pursuit of the condensation reaction after gelation. © 1994 Kluwer Academic Publishers.

Short Range Order Evolution in the Preparation of SnO2 Based Materials

The evolution of Eu3+ doped SnO2 xerogels to the cassiterite structure observed during sintering was studied by means of Eu3+ spectroscopy, XRD and EXAFS at the Sn K-edge. Eu3+ ions adsorbed at the surface of colloidal particles present a broad distribution of sites, typical of oxide glasses. With sintering at 300°C, this distribution is still broadened. Crystallization is clearly observed by the three techniques with increasing sintering temperature. It is found that the addition of Eu3+ limits the crystallite growth.

Electrical and optical characteristics of SnO2 thin films prepared by dip coating from aqueous colloidal suspensions

Starting from aqueous colloidal suspensions, undoped and Nb5+ doped SnO2 thin films have been prepared by using the dip-coating sol gel process. X-ray diffraction results show that films are polycrystalline with crystallites of average size1-4nm. Decreasing the thickness of the films and increasing the Nb5+ concentration limits the crystallite size growth during firing. Complex impedance measurements reveal capacitive and resistive effects between adjacent crystallites or grains, characteristic of electrical potential barriers. The transfer of charge throughout these barriers determines the macroscopic electrical resistance of the layer. The analysis of the optical absorption spectra shows that the samples present more than 80% of their transmittance in the visible region and the value of the band gap energy increases with decreasing crystallite size. © 1997 Chapman & Hall.

EXAFS and XRD Study of the Structural Evolution during Isothermal Sintering of SnO2 Xerogels

The formation of an ordered (crystalline) phase during isothermal sintering of SnO2 monolithic xerogels, at 200, 250, 300, 400, 500, 600 and 700°C, has been analyzed by the combined use of EXAFS and XRD techniques. For the desiccated gel (110°C), EXAFS results show the formation of small microcrystallites with the incipient cassiterite structure. Between 110 and 250°C, the dehydratation reaction leads to an amorphization evidenced by a decrease of the long and short range crystallographic order. It is due to fissure formation in the xerogel network. For higher temperatures, a continuous coagulation of the crystallites occurs, leading to grain growth. Grain and pore growth obeys the same kinetic relation, so that the microstructure grows by simple enlargement while its morphology is static.

Influence of viscoelastic characteristics of the colloidal suspensions on the formation of SnO2 supported membranes

SnO2 supported membranes have been prepared by sol-casting on alumina tubular substrate, using aqueous colloidal suspensions prepared by sol-gel route. The viscoelastic behaviour during sol ageing was analyzed by dinamic rheologial measurements. The complex viscosity and the storage and loss moduli have been followed during the sol-gel transition and the results have been correlated with the linear aggregates growth and the scalar percolation models. The scanning electron microscopy has evidenced that the homogeneity and thickness of the membrane depend on the sol ageing time. Crack-free and homogeneous membranes have been obtained for coated layers of 0.5μm thickness. © 1997 Trans Tech Publications.

Photodesorption and electron trapping in n-type SnO2 thin films grown by dip-coating technique

Thin films of undoped and Sb-doped (2 atg%) SnO2 have been prepared by sol-gel dip-coating technique on borosilicate glasses. Variation of photoconductivity excitation with wavelength and optical absorption indicate indirect bandgap transition with energy of ≅ 3.5 eV. Conductance as function of temperature indicates two levels of capture with 39 and 81 meV as activation energies, which may be related to an Sb donor and oxygen vacancy respectively. Electron trapping by these levels are practically destroyed by UV photoexcitation (305 nm) and heating in vacuum to 200°C. Gas analysis using a mass spectrometer indicates an oxygen related level, which may not be desorbed in the simpler O2 form.