Optical Properties and Sensitivity of Xerogel Detection Layers for Fiber-Optic Hydrocarbon Sensors

Xerogel layers were prepared on fiber-optic substrates and glass slides by the dip-coating method from sols composed of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES) and phenyltriethoxysilane (PTES), ethanol or isopropan, HCl and water, and by drying the gels at 80°C.Layers with a thickness ranging from 200 to 1500 nm were prepared. Optical properties of the layers applied on the fibers and their sensitivity to toluene and hexane were determined from angular and temporal changes of the output power of the fibers excited by an inclined collimated light beam. These changes were measured at a wavelength of 670 nm and in a range of 1600–1800 nm.The results obtained at 670 nm show that the layers refractive index can be increased from 1.39 to 1.5 by using the PTES sols instead of the MTES or TEOS ones. High optical losses of the layers of the order of 10³ dB/cm can be explained by their porosity. The best detection limits of 0.01 vol.% of toluene and 0.2 vol.% of hexane were obtained for layers containing methyl groups. The presence of toluene in the layers was deduced from spectral bands of toluene in a range of 1600–1800 nm.     

Organopolysiloxanes as Chemically Sensitive Coatings for Optical Fibers

Various types of UV-curable organically modified siloxanes have been synthesized by the sol-gel method with the aim of fabricating chemically sensitive coatings for silica optical fibers. The refractive index of the coating material can be tailored in the range from 1.46 to 1.56 and sensitivity towards CO2 is achieved by incorporation of amino groups. The interaction of the cured layers with CO2 or with hydrocarbons has been studied in immersion experiments. Both the reaction of CO2 with incorporated amino groups and the penetration of hydrocarbons into the layer induce changes of the light absorption coefficient and the refractive index of the coating which are detected by measuring the output light intensity from the fiber.     

A Multilayer Model for Gold Nanoparticle Bioconjugates: Application to Study of Gelatin and Human IgG Adsorption Using Extinction and Light Scattering Spectra and the Dynamic Light Scattering Method

A new model of colloidal gold (CG) bioconjugates is proposed. The model consists of a gold core and a primary polymer shell formed during conjugate synthesis. Additionally, the conjugate includes a secondary shell formed during its interaction with target molecules. Each of the inhomogeneous shells is modeled by the arbitrary number of discrete layers. Using Mie theory for multilayered spheres, we calculated the extinction and static light scattering (SLS, at 90°) spectra, as well as differential spectra A(), I() describing the effects of primary and secondary shells. Our calculations are performed for the conjugates with gold particle diameters d = 10–160 nm and two 5-nm shells. The primary shell consists of two 2.5-nm layers with the refractive indices of 1.50 and 1.45; the secondary shell, of two 2- and 3-nm layers with the refractive indices of 1.45 and 1.40. The differential spectra are related to the adsorption of target molecules and possess a characteristic resonance that is shifted to the red region of spectra compared to the usual localized plasmon resonances of gold particles. The maximal values of differential resonances A _max and I _max are observed for gold particles with diameters about 40–60 nm (extinction spectra) or 70–90 nm (the SLS spectra). The adsorption of human gamma-globulin (hIgG) and gelatin onto 15- and 34-nm gold particles was studied using the SLS and extinction spectra in combination with the dynamic light scattering measurements. It is shown that the thickness of adsorbed layer is equal to 5–6 nm for hIgG and to 15–18 nm for gelatin. The experimental extinction and SLS spectra for CG + hIgG conjugates are well explained by a simple model with the gold core and homogeneous polymer coating. For the CG + gelatin conjugates, we used the new model with inhomogeneous polymer coating, which is modeled by 10 discrete layers with the total thickness of 16–18 nm and exponential spatial profile of shell refractive index.     

Theoretical Investigation of Transparent (3–5 μm) and High Reflective (1.3 μm) Filter by Sol-Gel Process

When designing a cut-off interference filter, extra layers are needed to add on each side of periodic symmetrical multilayer to match the incident medium and the substrate. In this paper, we use sol-gel film with adjustable refractive index as the match layer. The influence of the refractive index and thickness of the match layer on the film system is discussed in detail. As an example, a special filter which is transparent (>80%) at the wavelength 3–5 m and high reflective (>90%) at the wavelength 1.3 m is designed. Finally a series of optimized film parameters are presented. The whole design process is a good reference to the other multilayer special filter made by sol-gel process.     

Silicon-containing polymers for non-linear optics

A variety of novel poly[ethynediyl-arylidene-ethynediyl-silylene]s (PEAES), including those containing hypercoordinate silicon atom as well as donor and acceptor groups, has been synthesized. The presence of hypercoordinate silicon favours high values of fast Kerr-type non-linearities, and the incorporation of amide groups gives rise to good optical quality nanocomposites in a silica matrix. The inorganic-organic hybrid sol-gel film incorporating 5–14 mass% of the polymer containing pentacoordinate silicon showed Re ⁽³⁾ = –9.5 ×10^–11 esu. The predominant rôle of the electron nonlinear mechanism has been demonstrated by using test beams with linear and circular polarizations. The photorefractive properties of composites based on PEAES as optical chromophores, poly(9-vinylcarbazole) as photoconductor, N-ethylcarbazole and phenyltrimethoxysilane as plasticizer, and fullerenes as charge generators have been investigated. The nonlinear optical effects, including four-wave mixing and two-beam coupling were studied at 633 nm without preliminary electric poling. The photorefractive origin of the refractive index changes was confirmed by the high two-beam gain under an externally applied electric field. Refractive index gratings affording two-beam gain can also be written under zero field conditions. To explain this unique property of the materials it is suggested that chromophore orientation asymmetry arises either during film formation or is induced by the longitudinal intensity gradient.     

Investigations of MgF2 Optical Thin Films Prepared from Autoclaved Sol

MgF₂ thin films with ultra low refractive indices were obtained by sol–gel method using sols prepared from magnesium acetate and hydrofluoric acid. The sols were autoclaved in a Teflon cell at 100–180°C for 24 h and then coated on SiO₂ glass or CaF₂ crystal substrates by spin coating. Subsequently, the samples were heat treated at 150°C for 1 h. The optical properties of the thin films, such as refractive index and transmittance, were investigated in the UV region, especially in the deep UV (DUV, below 250 nm) region. Though the coatings consist of single layers, both samples exhibited high transmittance. In addition, they exhibit such antireflection effect over a very wide range of wavelength. Such a good antireflection effect was produced only by low refractive indices. It has also been confirmed that, even in the range of vacuum UV (VUV, 200–150 nm), CaF₂ samples with antireflection coatings could keep such a good antireflection effect.     

Wavelength dependencies in interferometric measurements of thin protein films

Summary The evaluation of the spectral modulation in reflectance measurements at thin dielectric films allows the characterisation of layers in the m-range. Diode array spectrometers make this technique a useful tool in sensor development. The variation of the optical pathlength in thin films due to change of refractive index or to change of physical thickness of a homogeneous layer has been applied to refractometry and detection of hydrocarbons by polymer swelling. More recently, the monitoring of solid-phase affinity reactions, like immunoassays has successfully been demonstrated. While the homogeneous layer concept is useful for data evaluation in the first two cases, it has its limitations for the treatment of adlayer formation as in the latter case. This is discussed with respect to results from affinity reactions carried out at optically different interference layers.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Influence of the Layer Morphology on the Electrical Properties of Sol Gel Transparent Conducting Oxide Coatings

Tranparent conducting coatings have been prepared by sol gel methods either by a conventional sol-gel process (Antimony doped Tin Oxide—ATO, Aluminium doped Zinc Oxide—AZO) or a new wet chemical process using fully dispersed crystalline nanoparticles (ATO, Indium Tin Oxide—ITO). The dip coating technique has been used as deposition technique with single coating thickness varying from a few nanometer to ca. 400 nm. The layers have been fired in a furnace. Structural properties have been determined by x-ray diffraction and TEM analysis and the electrical properties by the van der Pauw/Hall measurement. Three different coating procedures have been used to investigate the effect on the structure, morphology and the electrical properties of the coatings. It is shown that the individual layer thickness in multilayer coatings influences dramatically the mentioned properties. Very thin individual layers favour a heterogeneous nucleation with dense columnar growth of the crystallites leading to low electrical resistivity ( 10^–3 cm), while thick individual layers result in a porous morphology made of small crystallites leading to resistivities in the 10^–2 cm range.     

High Refractive-Index Microspheres as Optical Cavity Structure

Microspheres of refractive index of n_D > 2.0 have been investigated. The organic-inorganic hybrid microspheres of n_D = 1.72 were prepared by the vibrating orifice technique using titanium-tetra-n-butoxide (TTBu) and diphenyldimethoxysilane (DPhDMS). For lasing demonstration, Eu³⁺-doped microspheres were prepared using europium (III) thenoyltrifluoroacetonate [Eu(TTFA)₃] as the dopant. The particles have good spherical shape, smooth surface and high optical transparency. The diameters of the particles could be controlled to within 0.1 m. Subsequent heating of the microspheres at 550°C under oxygen atmosphere resulted in an increase in the refractive index up to n_D = 2.6 with retention of the spherical shape. Resonant emission was confirmed from Eu^{3 +}-doped microspheres after heating at 400–550°C, by pumping with the 514.5 nm line of a CW- Ar⁺laser.     

Optical Nanocomposite Planar Waveguides Doped with Rare-Earth and Noble Metal Elements

The present paper is focused on multilayer Er³⁺-doped silica-titania planar waveguides, co-doped with silver, which were prepared by spin-coating on silica glass, or buffered single crystal silicon substrates. The single layer thickness (0.4 m) and refractive index (1.60–1.63) were measured by spectroscopic ellipsometry at 715 nm. The thickness of the waveguides (measured by mechanical profilometry) was 1 m and their optical propagation losses were measured at different laser wavelengths (488 nm, 514 nm and 633 nm), exhibiting an approximately Rayleigh-like behavior. The thermal precipitation of silver nanocrystallites was achieved, both in air and under a controlled atmosphere (dry nitrogen) and these were characterized by visible absorption spectroscopy, which clearly showed the development of a plasmon absorption band near 415 nm, by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). The Er³⁺ metastable level lifetimes for the emission at ca. 1.54 m were found to be ca. 4–6 ms, for Er³⁺ concentrations varying between 0.2–2.0 mol% (or (0.4–4.4) × 10²⁰ ions/cm³), but no significant variation was observed with the Ag concentration added (up to 2.5 mol%).     

Light induced refractive index changes in PMMA films doped with styrene

Solutions of poly(methyl methacrylate) in styrene are used to produce thin polymer films (1m–20m) saturated with styrene monomer. In the illuminated areas refractive index changes up to 10^–2 are achieved by photoinduced polymerisation. The index patterns may be fixed by annealing treatments removing the residual monomer.We thank P. Hertel, M. Kopietz, M. D. Lechner and D. Steinmeier for valuable discussions. Financial support of the Stiftung Volkswagenwerk is gratefully acknowledged.     

Raman-microanalysis of strain and crystal orientation in laser-crystallized silicon

Summary In this work we report on the use of Micro-Raman-Spectroscopy (MRS) to determine residual strain in cw-laser crystallized silicon on insulator (SOI)-thin layers and to measure slight deviations in crystal orientation which occur along the crystallization path during the crystallization process. The spatial resolution achieved is 0.8 m. Relative peak positions of the silicon phonon line have been measured with a reproducibility better than ±0.02 cm^–1. Frequency shifts in the crystalline layer were in the range of –1.5 cm^–1. This corresponds to a tensile biaxial stress of 3.8 kbar. Polarization dependent intensity monitoring has been carried out to measure the local tilt of crystal orientation in crystallized thin layers. For this we use polished cross-cut specimens which enable a change in observation direction, thus achieving an angular resolution of ±1°. At a crystallization path length of 90 m the measured backward tilt of the [001]-axis was 3°.     

MFTIR spectra of polyethylene synthesized on germanium surfaces

MFTIR spectra of thin layers of polyethylene synthesized on the surfaces of germanium monocrystals in the 700–3000 cm^–1 range have been investigated. The optical constants of the polymer n() and () have been calculated in the range of natural absorption corresponding to the C-H valence vibration bands. Dichroism of the 2848 and 2912 cm^–1 bands disclosed is caused by the orienting influence of the monocrystal surface and in value is comparable with values obtained for monoaxially oriented massive specimens of polyethylene having a high degree of crystallinity. There have been established reversible changes of the relative orientation function of the macromolecule surface layer during heating and cooling of the specimens in the temperature range 293–355 K. This is explained by the nematic state of the polymer in the thin layer, the macromolecules of which are chemically bonded to the surface of the germanium monocrystal.Deceased.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 3, pp. 380–383, May–June, 1988.The authors express their gratitude to K. K. Kalnin'sh for valuable discussion of material in the article and to M. E. Yudovich for his assistance in the calculations.     

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.     

Cyclic voltammetric behavior of Pd–Pt–Rh ternary alloys

The electrochemical behavior of Pd–Pt–Rh alloys has been investigated using cyclic voltammetry (CV). The alloys were prepared by electrochemical codeposition as limited volume electrodes (less than 1 m in thickness). The morphology of the alloy surface and bulk compositions were examined by the SEM/EDAX method. Surface oxides generation (oxygen adsorption) and oxides reduction (oxygen desorption) currents together with hydrogen adsorption and hydrogen absorption signals can be distinguished on CV curves. During potential cycling through the full hydrogen–oxygen potential range Rh and Pd are preferentially dissolved, which is reflected in a dramatic transformation in the voltammogram shape. The composition changes involve not only the surface but also some atomic layers beneath the surface.     

Synthesis of Blood Compatible PDMS-Based Organic-Inorganic Hybrid Coatings

Erbium tris 8-hydroxyquinoline (ErQ) was successfully incorporated into the sol–gel hybrid material (HYBRIMER) synthesized by using methyltriethoxysilane, vinyltriethoxysilane, and phenyltrimethoxysilane even though it has poor solubility in general organic solvent. The composition and microstructure of the HYBRIMER film doped with ErQ was analyzed using Rutherford backscattering method and scanning electron microscope. The refractive index of the HYBRIMER film was also investigated with ErQ concentration. The HYBRIMER film doped with ErQ showed a clear photoluminescence (PL) at 1.5 m. PL intensity increased with ErQ concentration without concentration quenching until Er/Si ratio reached 5 at%.     

Preparation and Characteristics of Porous Silica Films by a Modified Base-Catalyzed Sol-Gel Process Containing PVA: II. Film Preparation

Porous SiO₂ films were successfully deposited on silicon substrates by a modified base-catalyzed Sol-Gel process (MBCP) containing polyvinyl alcohol (PVA). The process conditions, such as the gelation time, the synthesis temperature, the stabilizing agent of the precursor solution and the spin coating speed, the heat-treatment, the annealing temperature of the film on the microstructure and porosity of porous SiO₂ films were systematically investigated by SEM, XRD and ellipsometry techniques. This study provides a novel preparation technique for the porous SiO₂ film. Using this process, the resultant film can reach a thickness of 3.6 m for one layer, a porosity of 25–50%, a low thermal conductivity of 0.11 W/m·K. This film will be used as a low dielectric layer, an thermal-insulating layer and a low refractive index layer.     

Micropatterning of Inorganic-Organic Hybrid Coating Films from Various Tri-Functional Silicon Alkoxides with a Double Bond in Their Organic Components

Inorganic-organic hybrid coating films were prepared from various trifunctional silicon alkoxides with a C=C double bond in their organic components, such as vinyltriethoxysilane (VTES), allyltriethoxysilane (ATES) or trimethoxysilylpropylmethacrylate (TMSPM), and zirconium n-tetrapropoxide modified with methacrylic acid. UV light from a high-pressure mercury lamp was irradiated through a photomask on the hybrid films, and this irradiation increased refractive index and microhardness of the films and decreased solubility of the films in alcohol or alkaline solution. IR spectra of the coating films have shown that C=C bonds in these trifunctional silicon alkoxides were polymerized with the UV irradiation. Patterns with a width of about 10 m and thickness of about 5–15 m were formed by the etching of unirradiated region of the films. Since VTES and ATES have a shorter organic chain than TMSPM, the hybrid films prepared from VTES or ATES are expected to show small optical loss in the near-infrared region due to C—H bonds in their use as waveguides.     

Multipesticide residue method for fruits and vegetables: California Department of Food and Agriculture

Summary This procedure describes the CDFA method for multipesticide residue analysis of fresh fruits and vegetables. An aliquot of chopped sample is blended with acetonitrile. The resulting aqueous acetonitrile extract is filtered and cleaned up via reverse phase solid phase extraction apparatus. The pH of the filtrate is adjusted to neutral using phosphate buffer and the acetonitrile layer is separated from the aqueous layer by a salting out process. An aliquot of the acetonitrile layer is concentrated with a K-D evaporator by forming an azeotrope with n-hexane. The prepared sample is assayed for pesticide residues using GLC and HPLC. The performance of this method was evaluated by fortifying 6 representative fruits and vegetables with 7 chlorinated hydrocarbons, 7 organophosphate and 7 N-methylcarbamate pesticides at 0.1–0.2 ppm. No matrix interference was observed and the recovery of residues varied among different samples as well as different pesticides. Chlorothalonil results varied widely with irreproducible recoveries. In general, the method appears to be fast, rugged, and able to detect routinely at the 0.01 ppm level.     

Surface characterization of functional poly(diacetylene) and poly(butadiene) mono- and multilayers

The surface properties of Langmuir-Blodgett mono- and multilayers of a variety of amphiphilic poly(diacetylene)s and poly(butadiene)s were investigated by contact angle, streaming potential, ellipsometry, and X-ray photoelectron spectroscopic (XPS) measurements. Captive air and octane angles varied between approximately 60° and 105° for hydrophobicx-layers and 31° to 46° for hydrophilic surfaces depending on the particular head group, whereas advancing angles determined via the vertical plate method are considerably higher. Negative streaming potentials were obtained for all surfaces. Positively charged monolayers yielded less negative- potential values (–28 mV) than negatively charged (–52 mV) or hydrophobic (–50 mV) layers. Ellipsometry measurements yielded an average layer thickness of 27±6 Å for 3 to 11 layers. X-ray photoelectron spectroscopy results qualitatively confirmed the expected composition. All of the samples, which were handled and stored in air after deposition and polymerization, were surface oxidized.Dedicated to Prof. Dr. F. H. Müller.