Preparation and Characterization of Germanium Sulfide Based Sol-Gel Planar Waveguides

Germanium sulfide based glass films have been deposited by spin-coating onto single crystal silicon wafers and silica glass disks, using the reaction between GeCl₄, either pure or doped with of 5 mol% of SbCl₃, dissolved in toluene, with H₂S. The films, heat-treated under different conditions, were characterized by X-ray diffraction, infrared spectroscopy, X-ray photoemission spectroscopy, mechanical profilometry and ellipsometry. Oxide contamination was found in these films, but this was reduced or even eliminated by a heat-treatment in H₂S gas, at 270°C. A maximum film thickness of 1.3 m was achieved and the refractive indices of the films were in the range of 1.9–2.8 at 633 nm. Propagated light was observed by butt-coupling, for waveguides deposited on silica glass disks, at = 633 nm. Optical losses in the range of 1.1–1.9 dB/cm were measured at this wavelength, for different regions of different planar waveguides. The present method has achieved reasonably low loss and low levels of oxide contamination, which are promising for active applications.     

Microstructural and Spectroscopic Studies of Sol-Gel Derived Silica-Titania Waveguides

Silica-titania planar waveguides were prepared via the sol-gel method from acid-catalyzed solutions of firstly, ÿ-Glycidoxypropyltrimethoxysilane mixed with tetrapropylorthotitanate (labeled as GT), and secondly, ÿ-Glycidoxypropyltrimethoxysilane mixed with both tetrapropylorthotitanate and tetraethoxysilane (labeled as GTT). Atomic force microscopy, thermal gravimetric analysis, differential thermal analysis, UV-visible spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy were used to study the structural and optical properties of the waveguide films prepared from the two types of sols. The obtained results showed that in both cases, crack-free and highly transparent silica-titania films with a thickness of more than 0.5 m could be obtained by a single spin-coating process after a heat treatment at 500°C. The GT derived films showed more shrinkage and a higher refractive index after annealing as compared to the GTT derived films. When such films were deposited on a silica-on-silicon substrate to act as a surface planar waveguide, the light propagation loss was measured to be about 0.9 dB/cm and 1.3 dB/cm respectively. Raman spectroscopy results indicated that the GTT derived waveguide films with 0.5 molar titanium content contained amorphous carbon phase after being heated at above 500°C in air directly.     

Er3+-doped Multicomponent Silicate Glass Planar Waveguides Prepared by Sol-Gel Processing

Erbium doped silica-titania planar waveguides, co-doped with ytterbium and aluminum, have been prepared by sol-gel processing, using multilayer spin-coating deposition on silicon or silica glass substrates. The Er3+ doping level varied between 0 and 2 at.%, while Yb3+ varied from 0 to 3 at.%. Aluminum was incorporated up to 15 at.% Al and it was found to have no significant effect on the refractive index of the silica-titania (80 : 20 mol%) matrix. The Er3+ fluorescence emission was flat within ±0.5 dB, between 1520 and 1560 nm. The corresponding 4I13/2 metastable level lifetime was found to decrease from 6.1 to 3.5 ms, as the Er concentration increased from 0.1 to 0.5 at.%, for films co-doped with 0.5 at.% Yb and 10 at.% Al and the fluorescence decay was essentially single exponential below a Er quenching concentration of 0.5 at.% (1.1 × 1020 ions/cm3). The lifetime appears to be limited by Er-Er interactions at higher rare-earth ion concentrations and by residual OH species in the sol-gel derived waveguides. Vacuum heat treatment at a temperature near 570°C was somewhat effective in increasing the Er fluorescence lifetime, whereas reactive atmosphere processing in CCl4 or Cl2 at a similar temperature appeared to be less effective.     

Fabrication of Channel Waveguides by Photochemical Self-Developing in Doped Sol-Gel Hybrid Glass

Sol-gel derived inorganic-organic hybrid glass (HYBRIMER) films doped with benzildimethylketal (BDK) were prepared. Refractive index and film thickness increase by UV exposure due to photoinduced polymerization and photolocking of high refractive index BDK. This enables the channel waveguides in HYBRIMER film to be fabricated without using a developing process, which is called photochemical self-developing (PSD). The waveguides consist of three layers with under-cladding and over-cladding of undoped HYBRIMER films and core of BDK-doped HYBRIMER film. A 1 × 4 splitter of waveguides was fabricated and demonstrated.     

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.     

Third-Order Optical Nonlinearity Studies of p-Heptaphenyl Derivatives-Doped Sol-Gel Processed Composite Glass and THF Solution by Degenerate Four-Wave Mixing and Optical Kerr Gate Measurements

We have investigated the nonlinear optical performance of new UV photostable dyes, didecyl and didecyloxy substitutedpara-polyphenyl heptamers (DDPPH and DDOPPH hereafter, respectively) using the techniques of degenerate four-wave mixing (DFWM) and optical Kerr gate (OKG). The studies were performed on the dyes dissolved in THF solution and doped in sol-gel processed composite-glass. The magnitudes and the signs of the real and the imaginary components of the complex third-order optical susceptibilities were determined by the heterodyned OKG method and compared to the values obtained from concentration dependent homodyne Kerr gate and DFWM measurements. The observed effective second hyperpolarizability γ values are dependent on the optical intensity and the pulse width of the pumping source beam. Doping of the dyes in composite-glass allows to increase the interaction length providing the prospect of using them as building blocks for photonic devices.     

Structural and Optical Properties of Sol-Gel Derived Aluminosilicate Planar Waveguides Doped with Er3+ Ions

Er3+ doped-aluminosilicate thin films were prepared on silica and silica/Si substrates by the sol-gel process and dip-coating. The sol-gel aluminosilicate planar waveguides were prepared from silicon and aluminium alkoxides. Their structural characterization has been carried out by Raman spectroscopy, Atomic Force and Scanning Electron Microscopies. The results indicated that these films present an amorphous structure until an annealing temperature of 900°C, while at temperatures higher than 1000°C, crystallization occurs. An estimate of microcrystallite sizes using Raman spectroscopy is given, which agrees with data from scanning electron microscopy. The optical properties have been investigated by Fluorescence spectroscopy in the visible region.     

Sol-Gel Fabrication of Rare-Earth Doped Photonic Components

The use of sol-gel to fabricate silica-on-silicon waveguides, and particularly erbium-doped waveguide amplifiers, is reviewed. In particular, efforts to use sol-gel to improve molecular homogeneity in heavily Er-doped silica-based films is discussed. A variety of material studies carried out to investigate the gain limitations found in these materials is then presented. These include x-ray diffraction, ellipsometry and Rutherford backscattering. Excess heat treatment is used to force crystallisation of the films, and analysis of the resulting structure is used to infer properties of the glass before the additional heating. The use of erbium alkoxide precursors is shown to alter the erbium environment in the final glass, in comparison to the use of inorganic erbium salts.     

Sol-Gel Synthesis of Ge Nanocrystals-Doped Glass and Its Photoluminescence

Ge nanocrystal-embedded SiO₂ glasses were prepared by a sol-gel process. The glasses synthesized through the hydrolysis of Si(OC₂H₅)₄ and GeCl₄ were heated in H₂ gas atmosphere at 500 to 800°C, in which Ge⁴⁺ ions were reduced to precipitate nanosized Ge crystals with the size smaller than 10 nm diameter. Glasses doped with Ge nanocrystals of diameter of ≈5 nm showed the optical absorption edge at ≈2.8 eV and a broad photoluminescence exhibiting the peak at around 2.2 eV. Large Ge crystals precipitated by heating above 800°C showed no photoluminescence.     

Anhydrous Sol-Gel Synthesis of Titania-Doped Siloxane Polymer for Integrated Optics

Sol-gel synthesis of organic-inorganic hybrid materials for planar waveguides and devices has received growing interest due to its low-cost processing and good suitability for doping. Titania is an important optical dopant, but homogeneous incorporation of titania in silica is difficult to be achieved by the conventional sol-gel process (aqueous system) because of the significant difference between the hydrolysis rates of the precursors. In this paper, we report an anhydrous sol-gel process for synthesising titania-doped siloxane polymers. The process consists of a hydrolysis of 3-methacryloxypropyltrimethoxysilane (MPS) with boric acid under anhydrous conditions, and a condensation with dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPhDMS) and titanium ethoxide (TET). Optical characterisations for the produced titania-doped polymer were performed, and results showed that TET doping is useful for reducing the OH concentration of the synthesised polymer and is also effective for improving the optical quality of spin coatings. DMDMS and DPhDMS are favourable in reducing the birefringence and in increasing the thermostability of the material, and the methacryl groups of MPS are UV-polymerizable, which is useful for low cost fabrication of waveguides by photolithographic process. The results of ellipsometry scanning measurements show that titania is homogeneously incorporated in the hybrid matrix, suggesting that the anhydrous sol-gel process is useful for preparation of UV-sensitive titania-doped siloxane polymers for optical applications.     

Sol-Gel Glass from Organic Modified Silicates for Optics Applications

A room temperature sol-gel process starting from tetraethyl orthosilicate and triethoxy-vinyl silane is used to obtain dye doped organic modified glass, whose composition and optical properties are investigated by means of transmittance measurements in the VIS-IR range. Experimental conditions as the precursor ratio, the water amount, and the thermal treatment, are optimized to avoid the guest molecules degradation and to obtain good optical quality thin films, able to be micropatterned by embossing lithography. The photoluminescence of the patterned films, imaged on a m scale, is analysed by means of a CCD camera and compared with the emission of the unstructured films.     

Doped Sol-Gel Films for Silica-on-Silicon Photonic Components

Further expansion of optical communication systems depends strongly on the development of cheap component technologies for functions such as switching, demultiplexing and amplification. Silica-on-silicon is increasingly recognised as the best approach to low cost integrated optics for such applications, but so far the functionality is limited. The purpose of NODES, a basic research collaboration sponsored by the European Union under the programme ESPRIT, has been to examine the application of sol-gel to a highly functional silica-on-silicon technology. In particular, the project has investigated film processing and characterisation, rare-earth doping for amplification, and semiconductor nanocrystallite doping for nonlinear functions. This paper presents the background and context to this work, summarises the technical results obtained, and discusses requirements and challenges for successful application of sol-gel in photonics.     

Fabrication and Characterization of Sol-Gel GeO2-SiO2Erbium-Doped Planar Waveguides

GeO2-SiO2 sol-gel planar waveguides doped with Er were deposited by spinning on silica substrates. P2 O5 or Al2O3 were used as co-dopants to improve erbium dissolution in the GeO2-SiO2 matrix. Multilayer amorphous films were obtained at 600 or 700°C.Er ions in the planar waveguide pumped at 980 nm showed fluorescence features around 1530 nm. Narrow fluorescence spectra (20 nm) and long lifetimes (6 ms) were found in P2O5 co-doped samples, whereas Al2O3 co-doping gave wider spectra (50 nm) with slightly lower lifetimes (5 ms). The quenching concentration in the Al2O3 co-doped samples was 0.9 mol% Er.Heat treatments in CCl4 improve the active properties and the addition of Yb enhances the pump absorption efficiency.     

Synthesis of Fullerene-Containing Sol-Gel Glasses

Macroscopically homogeneous and visually transparent fullerene-containing glasses are fabricated from sol-gel mixtures of aminated C₆₀ derivatives and tetraethyl orthosilicate (TEOS) through physical blending and chemical reaction. The aminated fullerenes are synthesized by the amination reactions of C₆₀ with 6-amino-1-hexanol, cyclohexylamine, 2-(2-aminoethoxy)ethanol, and 3-aminopropyltriethoxysilane at 100°C under nitrogen. The amination products are purified by filtration, precipitation, and column chromatography and are isolated in good to excellent yields (32–82%). Characterization by NMR, MS, and TGA analyses reveals that the aminated fullerenes possess molecular structures H _x C₆₀[NH(CH₂)₆OH] _x , H _x C₆₀(NH-cyclo-C₆H₁₁) _x , H _x C₆₀[NH(CH₂CH₂O)₂H] _x , and H _x C₆₀[NH(CH₂)₃Si(OCH₂CH₃)₃] _x . All the aminated fullerenes except 2 are completely soluble in aqueous alcoholic solutions of TEOS and can be incorporated into silica gel networks by sol-gel process in the absence or presence of drying-control chemical additives, giving crack-free monoliths of large sizes (up to 60 mm). Electronic absorption spectrum of the fullerene glass continuously red shifts with an increase in the C₆₀ content, suggesting the formation of fullerene nanoclusters in the sol-gel process. The fullerene glasses are thermally and optically stable, resisting continuous attack of strong laser pulses of 532 nm for a prolonged period of time without losing their optical limiting power.     

Microstructural and Dielectric Characterization of Sol-Gel Derived Silicon Oxycarbide Glass Sheets

Thin (50—1000 m) silicon oxycarbide glass sheets were synthesized by the pyrolysis of gel sheets obtained from a methyl-modified silica sol containing colloidal silica under inert atmosphere between 900 and 1450°C. The microstructure of these glass sheets was investigated with the help of high resolution scanning and transmission electron microscopy (HR-SEM and HR-TEM), X-ray diffraction and Raman spectroscopy and their dielectric properties were determined. The surface morphology as observed with HR-SEM did not exhibit a notable temperature dependence. HR-TEM studies showed that the glass sheets sintered up to 1200°C are amorphous, whereas those sintered at 1450°C contain uniformly dispersed crystallites of SiC and graphite. X-ray diffraction studies were found in agreement with the HR-TEM results. Raman spectroscopy showed that free carbon is present as an amorphous phase till a temperature of 1000°C, whereas at temperatures 1200°C, the presence of graphitic carbon was observed. Silicon oxycarbide glass sheets heat treated at temperatures up to 1200°C, showed a dielectric constant between 4.1 ± 0.11 and 4.6 ± 0.15 in the frequency range from 75 kHz to 5 MHz, with corresponding losses between 0.0008 and 0.1100. Such silicon oxycarbide glass sheets sintered at 1200°C could find an application as substrates for electronic packaging.     

Control of Semiconductor Particle Size in Sol-Gel Thin Films

Thin silica and silica-titania films containing CdS and PbS quantum size particles were obtained by separate preparation of the matrix and the colloidal sols and successive mixing. Sulfide particles were obtained by reaction of metal acetates with thioacetamide and control of particle size was achieved by surface capping agents. Powders and thin films deposited on soda-lime slides were prepared and characterized by XRD. Absorption spectra were recorded on films. The nonlinear refractive index was measured by anm-line technique on a CdS-doped sample. The nonlinear effect was found to be reversible and an ₂ value of −3 10⁻⁹ cm²/kW was measured.     

Measurement of Thermo-Optic Coefficients in Sol-Gel Hybrid Glass Films

Thermo-optic coefficients (TOC) of inorganic-organic hybrid glass (HYBRIMER) films prepared by sol-gel process of organoalkylsilanes were measured using the prism coupler equipped with auto-controlled hot stage. The spin coated HYBRIMER films composing of silica and methacrylate networks were fabricated for the measurement. Their TOCs are negative and as high as the order of 10^–4, which are comparable to those of optical polymers. It was found that composition of the films, formation of organic network and addition of other elements in the HYBRIMER affect TOCs of the films.     

Synthesis of Fullerene Derivatives for Incorporation in Sol-Gel Glasses

We report on the synthesis of fullerene derivatives containing a trialkoxysilane moiety that exhibit enhanced solubility in solvents commonly used for sol-gel processing. These derivatives have been successfully embedded in glassy bulk samples and thin films that show very promising optical limiting properties.     

Development of the SC-RTA Process for Fabrication of Sol-Gel Based Silica-on-Silicon Integrated Optic Components

The SC-RTA process for fabricating silica-on-silicon PLCs from sol-gel glass is described. A wide range of glasses has been deposited, process temperatures have been reduced, and components fabricated by reactive ion etching, reflow and burial of channel guides have shown steadily decreasing loss. Propagation losses are 0.2 dB/cm at = 1.523 m in a high n system. Passive components demonstrated include tree-structured power splitters and thermo-optic switches.     

Sol-Gel Synthesis and Microstructural Characterization of Silicon Oxycarbide Glass Sheets with High Fracture Strength and High Modulus

A synthesis route to silicon oxycarbide glass sheets (thickness 40 to 1000 m and area up to 20 × 35 cm2) has been developed for the first time starting from a methyl modified sol containing nano-particulate SiO2 and having a solid content of 70 wt%. The gel sheets obtained by casting and drying of this sol were sintered in N2 atmosphere at temperatures between 900–1650°C. Only by the incorporation of colloidal silica (0.10–0.35 mole per mole alkoxide) to the sol could crack-free, large area glass sheets be obtained. Fracture strength (three point bending) was found to attain a maximum (200–300 MPa) for the sheets sintered at 1000°C. Young's modulus attained a peak value between 120 and 130 GPa for the sheets sintered at 1200°C. HR-TEM studies showed an amorphous and homogeneous matrix up to a sintering temperature of 1200°C, whereas at 1450°C and 1650°C, crystallites of SiC and lamellar graphite were formed. It is concluded that addition of colloidal silica to the sol does not lead to inhomogeneities after sintering and therefore does not decrease the strength and elastic modulus.