Laser densification of medium pore size gel-silica glass

Type VI sol-gel silica monoliths with 32 Å and 45 Å pore radii were made using tetramethylsiloxane (TMOS) with HF as a catalyst. The pore texture was characterized using nitrogen absorption/desorption isotherms and BET analysis. Monoliths thermally stabilized to specific bulk densities of 1.67 g/cc to 2.00 g/cc were irradiated with a CO₂ laser to create microlenses. The densified spots were characterized using microscopic Fourier transform infrared (FTIR) spectroscopy. Full density microlenses were achieved; the peak position of the Si-O-Si vibrational mode was at 1122 cm^–1, equivalent to commercial optical silicas. The refractive index in the center of the densified spots was 1.46 at a wavelength of 632.8 nm with a gradient in refractive index of 0.07–0.08. The combinations of laser power and substrate bulk density that yield full density microlenses is expanded when compared with conditions previously established for small pore, 12 Å, gel-silica substrates. Dimensions of the laser densified region, magnitude of the index gradient, and shape of the GRIN profile are easier to control with the medium pore size gel-silica substrates.     

Mechanisms of hydroxyapatite formation on porous gel-silica substrates

The variables affecting the nucleation and crystallization of biological hydroxy carbonate apatite (HCA) on porous gel-silica substrates are examined. Texture is the critical variable with the rate of HCA formation increasing as pore size and pore volume increase, with pore sizes >2 nm required to achieve rapid kinetics (4–6 days) of fully crystallized HCA. The concentration of silanol groups on the silica surface does not control the rate of HCA formation although metastable surface defects, such as trisiloxane rings, may be involved in HCA nucleation.     

Emanation thermal analysis study of a sol-gel precursor for silica-titania waveguides

Emanation Thermal Analysis (ETA) was demonstrated as a tool for the characterization of microstructure changes of a sol-gel precursor for silica-titania layers deposited on the glass plate to be used as planar waveguides. Temperature ranges of 280-330 and 380-500°C, respectively, in which the densification of the layers took place, were determined by ETA under in situ conditions of the sample heating. Results of thermogravimetry were compared with the ETA data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Raman Spectroscopic Investigations of the Effects of Ag+ and Ce3 + Doping on the Densification of Nanoporous Silica Xerogels

Doped and undoped 50 Å porous silica xerogels were heat-treated at various annealing temperatures ranging from 800°C to 1150°C. The heating was performed in air for 1 hour at each temperature. Raman spectroscopy was used to follow the structural changes occurring at various stages of the gel-to-glass transformation, as well as to investigate the effects of metal ions on the densification of these nanoporous silica xerogels. Raman data and density measurements showed that while densification is completely achieved at 1050°C for undoped xerogels, it occurs at 950°C for Ag⁺-doped samples. On the other hand, Ce^{3 +} doping was found to slow down the densification process, with complete densification occurring at 1100°C.     

Laser Sintering of SnO2 : Sb Sol-Gel Coatings

Sb doped sol-gel SnO2 single layers (thickness 100 nm) were prepared from alcoholic solution and deposited via a dip coating process on fused silica substrates. The coatings have been sintered at a typical rate of 10–15 cm2/s by CO2 laser irradiation. The laser spot was scanned in one direction at a speed of 15,000 cm/s and the sample was moved in a perpendicular one at a speed up to 250 mm/s. The temperature of the topmost 10 m layer was monitored by a fast pyrometer (s resolution). The following properties of the coatings have been determined: the electrical resistivity , the carrier density n, and mobility , the structure, the thickness, the mesoscopic and micromorphology and the density. The sintering by CO2 laser radiation is mainly a thermal driven process. At T 500°C it allows to obtain coatings with a smaller resistivity (6.8×10–3 cm) than those produced by conventional furnace firing (el2.9×10–2 cm). The results are discussed in terms of particle size and packing density.     

Propagating transverse electric and transverse magnetic modes in liquid crystal-clad planar waveguides

ABSTRACT

In a planar dielectric waveguide, weak confinement of a propagating mode in a high index core leads to a measurable evanescent interaction with the cladding. In this work, we study the effect of a reorientable anisotropic cladding on the behaviour of Transverse Electric (TE) and Transverse Magnetic (TM) mode polarisations using a liquid crystal (LC)-clad waveguide architecture. The polarised evanescent field of a guided mode interacts with a voltage-tunable birefringent LC cladding to deflect an out-coupled beam. Experimental measurements are coupled with a theoretical framework and show good consistency with simulation results. We isolate the effect of mode confinement by changing the thickness of the high index core. Interactions between the LC index ellipsoid and the mode polarisation are probed by changing the initial alignment of the LC. Finally, we examine the difference in deflection between TE and TM modes, which incorporates both a change in mode confinement and a difference in LC index components.     

Optical sensing in microfluidic lab-on-a-chip by femtosecond-laser-written waveguides

We use direct femtosecond laser writing to integrate optical waveguides into a commercial fused silica capillary electrophoresis chip. High-quality waveguides crossing the microfluidic channels are fabricated and used to optically address, with high spatial selectivity, their content. Fluorescence from the optically excited volume is efficiently collected at a 90° angle by a high numerical aperture fiber, resulting in a highly compact and portable device. To test the platform we performed electrophoresis and detection of a 23-mer oligonucleotide plug. Our approach is quite powerful because it allows the integration of photonic functionalities, by simple post-processing, into commercial LOCs fabricated with standard techniques. Figure Femtosecond laser written waveguides can selectively excite fluorescence in a microfluidic channel of a commercial lab-on-a-chip. A compact scheme for on-chip detection by laser induced fluorescence is applied to capillary electrophoresis of a 23-mer Cy3-labeled oligonucleotide     

Space-Selective Precipitation of Au Nanoparticles Inside Silica Gel

Au colloids were prepared by irradiation with a Nd:YAG laser. Au nanoparticles were characterized by absorption spectra, transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. It is found that the wavelength of the laser has no effect on the size but the number of the Au nanoparticles. By irradiating a transparent silica gel doped with gold ions with the focused laser in the gel and subsequent exposing in air, a space-selective pattern of letter “P” consisting of Au nanoparticles was observed inside the silica gel.     

Preparation and Characterization of HgxCd1-xS and PbxCd1-xS Quantum Dots and Doped Thin Films

Thin silica and silica-titania films doped with sulfide nanocrystals of controlled size were fabricated by a method based on the preparation of colloidal particles and their introduction into a glassy matrix through the sol-gel method. Colloidal sols of composition Hg_xCd_1-xS and Pb_xCd_1-xS (with _x ranging from 0 to 1) were prepared and used to dope alkoxide solutions for the deposition of thin silica and silica-titania films. Optical absorption spectra were taken on both precursor colloidal sols and derived doped films. X-ray diffraction characterization gave structural information on the nature and size of particles in powders obtained by precipitation from colloidal sols and in doped films. The advantages and limits of the investigated systems are discussed in light of possible applications. The nonlinear properties of the most interesting PbS-doped planar waveguides have been investigated in the near-infrared, at 1.064 m. A reversible nonlinear effect was measured, with n ₂ values ranging from -5 to -20×10^-9 cm²/kW.     

Pentacyanoferrates(II) on the surface of organomodified silica gel: The matrix effect

Pentacyanoferrate(II) absorbed on a silica gel surface previously modified with 3-aminopropyl and 3-imidazolylpropyl groups were characterized by¹³C MAS/NMR, FT-IR, Mössbauer spectroscopy, and cyclic voltammetry. FT-IR and¹³C MAS/NMR data indicated that the pentacyanoferrate(II) complex is bonded to the surface by the nitrogen atom of the functional group. The differences in the isomeric shifts, the quandrupole splittings and the midpoint potentials of the adsorbed complexes in comparison with the model complexes were attributed to the matrix polar effect—i.e., the interaction of the complex with polar groups on the silica surface.     

Sol-Gel Glass Waveguides

Sol-gel processes show many promises for the development of low-loss, high-performance glass integrated optical circuits. Special attention is being paid to the preparation of composite glass film, where the properties of organic or inorganic dopant compounds included in the glass matrix are fully exploited. Nonlinear optical glass film waveguides have the potential to become key devices in the future, leading to further technical advances of fiber optic communication systems. This paper briefly reviews current activities in sol-gel glasses for integrated optics, with particular focus on silica-titania and semiconductor-doped films.     

Preparation of titania colloids by thermal hydrolysis of urea and densification behavior of the collid-derived monolithic titania gels

Hydrous titania colloids with different sizes and shapes were prepared from urea-containing TiCl₄ solutions by controlled thermal hydrolysis of urea. Very small colloidal particles (Sw=280–290 m²/g) with anatase structure were precipitated from aqueous HCl solutions of [TiCl₄] <1.0 mol/dm³ and [urea] >16.6 mol/dm³. Sols containing such colloids could be converted to translucent monolithic gels. A decrease in urea concentration ([urea]=8.3 mol/dm³) caused the production of aggregated rutile-type particles with a large aspect ratio, from which only titania powder was obtained. Heating of a monolithic gel above 500°C resulted in the accelerated densification of the gel. A highly densified titania with 96% of theoretical density was produced from the monolithic gel after heating at 700°C for 6 h.     

Laser Microbeams and Optical Tweezers in Ageing Research

We show how a technique developed within the framework of physics and physical chemistry—in a true interdisciplinary approach—can answer questions in life sciences that are not solvable by using other techniques. Herein, we focus on blood‐pressure regulation and DNA repair in ageing studies. Laser microbeams and optical tweezers are now established tools in many fields of science, particularly in the life sciences. A short glimpse is given on the wide field of non‐age‐research applications in life sciences. Then, optical tweezers are used to show that exerting a vertical pressure on cells representing the inner lining of blood vessels results in bursts of NO liberation concomitant with large changes in cell morphology. Repeated treatment of such human umbilical vein endothelial cells (HUVEC) results in stiffening, a hallmark of manifest high blood pressure, a disease primarily of the elderly. As a second application in ageing research, a laser microbeam is used to induce, with high spatial and temporal resolution, DNA damages in the nuclei of U2OS human osteosarcoma cells. A pairwise study of the recruitment kinetics of different DNA repair proteins reveals that DNA repair starts with non‐homologous end joining (NHEJ), a repair pathway, and may only after several minutes switch to the error‐free homologous recombination repair (HRR) pathway. Since DNA damages—when incorrectly repaired—accumulate with time, laser microbeams are becoming well‐used tools in ageing research.     

The hydroxyl content of silica gel

Thermogravimetric analysis of silica gel has shown that the loss in weight between 30° and 910°C can be quantitatively explained on the basis of water being lost from three distinct and different populations of sites on the silica gel surface. The results indicate that the site energies of the three different populations are randomly distributed and, consequently, the resulting weight loss steps from each population can be described by the integral of a simple normal distribution with temperature. The calculated weight loss obtained by assuming three different site-groups having randomly distributed adsorption energies is, within experimental error, coincident with the experimental data. It is also shown that the water evolved from the second population of sites originates from strongly bound water and may also contain water generated by the condensation of (geminal) silanol groups contained in the overlapping and neighbouring population.     

Use of Benzoylthiourea Immobilized on Silica Gel for Separation and Preconcentration of Uranium(VI)

Benzoylthiourea immobilized on silica gel was prepared by two-step post-synthesis modification. The capacity of the chelating silica gel, which was characterized by FTIR, was 3.21 mmol · g⁻¹. The separation and enrichment of uranium(VI) from solutions was investigated. Effective extraction conditions were optimized in both batch and column methods prior to determination by spectrophotometry using arsenazo(III). The optimum pH range for quantitative adsorption is 4–7. Quantitative recovery of U(VI) was achieved by stripping with 0.1 mol · L⁻¹ HCl. The sorption capacity of modified silica gel was 0.85 mmol · g⁻¹ uranium(VI). Recovery of U(VI) was 99.1 ± 2.3% with a detection limit of 2 μg · L⁻¹. The preconcentration factor was 250, and the relative standard deviation was 1.53% for a 1 μg · L⁻¹ U(VI) solution. The method was used for the determination of uranium in synthetic samples and a soil sample.     

Amplified Spontaneous Emission Threshold Dependence on Determination Method in Dye-Doped Polymer and Lead Halide Perovskite Waveguides

Nowadays, the search for novel active materials for laser devices is proceeding faster and faster thanks to the development of innovative materials able to combine excellent stimulated emission properties with low-cost synthesis and processing techniques. In this context, amplified spontaneous emission (ASE) properties are typically investigated to characterize the potentiality of a novel material for lasers, and a low ASE threshold is used as the key parameter to select the best candidate. However, several different methods are currently used to define the ASE threshold, hindering meaningful comparisons among various materials. In this work, we quantitatively investigate the ASE threshold dependence on the method used to determine it in thin films of dye-polymer blends and lead halide perovskites. We observe a systematic ASE threshold dependence on the method for all the different tested materials, and demonstrate that the best method choice depends on the kind of information one wants to extract. In particular, the methods that provide the lowest ASE threshold values are able to detect the excitation regime of early-stage ASE, whereas methods that are mostly spread in the literature return higher thresholds, detecting the excitation regime in which ASE becomes the dominant process in the sample emission. Finally, we propose a standard procedure to properly characterize the ASE threshold, in order to allow comparisons between different materials.     

Optical Properties of Highly Fluorinated and Photosensitive Organically-Modified Silica Films for Integrated Optics

We report the synthesis and optical properties (refractive index and absorption) of a class of highly fluorinated, photosensitive ormosils, and investigate their refractive index, absorption and UV-imprinting properties to assess them for optical waveguide applications.     

Fluorescence and Nonlinear Optical Response of Graphene Quantum Dots Produced by Pulsed Laser Irradiation in Toluene

Graphene quantum dots (GQDs), the zero dimensional (0D) single nanostructures, have many exciting technological applications in diversified fields such as sensors, light emitting devices, bio imaging probes, solar cells, etc. They are emerging as a functional tool to modulate light by means of molecular engineering due to its merits, including relatively low extend of loss, large outstretch of spatial confinement and control via doping, size and shape. In this article, we present a one pot, facile and ecofriendly synthesis approach for fabricating GQDs via pulsed laser irradiation of an organic solvent (toluene) without any catalyst. It is a promising synthesis choice to prepare GQDs due to its fast production, lack of byproducts and further purification, as well as the control over the product by accurate tuning of laser parameters. In this work, the second (532 nm) and third harmonic (355 nm) wavelengths of a pulsed nanosecond Nd:YAG laser have been employed for the synthesis. It has been found that the obtained GQDs display fluorescence and is expected to have potential applications in optoelectronics and light-harvesting devices. In addition, nonlinear optical absorption of the prepared GQDs was measured using the open aperture z-scan technique (in the nanosecond regime). These GQDs exhibit excellent optical limiting properties, especially those synthesized at 532 nm wavelength.