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.     

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.     

Improved Composition for Sol-Gel Rare-Earth Doped Planar Waveguides

A multilayer sol-gel process has been developed in order to make highly doped rare-earth planar waveguides on silica or silicon substrates.Starting with a small range of constituents, such as SiO₂, TiO₂, P₂O₅ and Al₂O₃, we show that a large variety of gel compositions, with different spectroscopic behaviour, can be made when doped with rare-earths.We have doped the sol-gel films with neodymium and we have optimized their compositions by measuring the neodymium fluorescence lifetime. For a composition with 10 atom% of phosphorous, the lifetime evolution with neodymium concentration was studied and a quenching concentration was found at 1% of neodymium. We have also shown the strong influence of phosphorous or aluminium in the sol composition on the fluorescence lifetime, for a given neodymium concentration. First results on similar planar waveguides, doped with erbium, are also presented.The stability of the fluorescence lifetime over a long period of time is an other important point to be checked for these new materials: the lifetime evolution over a 9 months measurement period is presented.     

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%).     

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.     

Erbium-Activated Silica-Titania Planar Waveguides

(100 – x)SiO₂-(x)TiO₂-ErO_3/2 planar waveguides, with 7 x 20 have been prepared by sol-gel route using the dip-coating technique. The thickness of the films was optimized to support a single propagating mode at 1550 nm, with a confinement coefficient higher than 0.75. The process of densification of the gel and the devitrification with the growth of TiO₂ nanocrystals were studied by Raman scattering. Devitrification is important only for x 15, but it was not possible to obtain full densification of the samples, even at the lowest TiO₂ content, without the appearance of nanocrystals.Emission in the C telecom band was observed; the spectral width of the ⁴I_13/2 ⁴I_15/2 transition of Er³⁺ slightly increases with the titania content. For x 12 most of Er³⁺ ions (about 65%) decay exponentially with a lifetime of about 8 ms.     

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.     

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.     

Planar ZrO2 Waveguides Prepared by the Sol-Gel Process: Structural and Optical Properties

ZrO₂ waveguides are prepared by the sol-gel process from a solution containing zirconiumn-propoxide and acetylacetone in propanol-2. Structural characterizations are investigated for different annealing temperatures using suitable techniques including Waveguide Raman Spectroscopy, Electron Microscopy and Atomic Force Microscopy. Films are amorphous at 300°C and the pure ZrO₂ tetragonal crystalline phase appears beyond 400°C. Crystallized films present a dense, uniform and polycrystalline structure made up by randomly oriented nanocrystallites, the diameter of which increases from 38 Å at 400°C to 53 Å at 600°C. Waveguides are at least monomode TE₀ at 632.8 nm. At this wavelength, optical losses are about, 0.8±0.2dB/cm for amorphous layers and increase up to 2.5±0.4 dB/cm for 600°C heat-treated waveguides.     

Sintering Anomaly in Silica-Titania Sol-Gel Films

Sol-gel processing has been successfully applied to the preparation of silica-titania planar waveguides for integrated optics. In order to achieve low loss guides, proper densification is essential. A series of single layer silica-titania films were deposited by spin-coating on Si substrates from precursor sols prepared by mixing tetraethylorthosilicate (TEOS) with titanium tetra-iso-propoxide (TPOT). The thermal densification behavior of these thin gel films was followed by measuring their refractive index, by ellipsometry, as a function of the temperature, between 300–900°C and the heating time; an anomalous sintering behavior was found, consisting of a rapid initial rise in film density (calculated from the refractive index) at any heat-treatment temperature, followed by a pronounced minimum at times of the order of 3 minutes, after which the density slowly increased until the maximum plateau value, reached at each temperature.In order to explain the above sintering anomaly, a detailed compositional and structural characterization was performed on the films by infrared spectroscopy (IR) and X-ray photoemission spectroscopy (XPS). A redistribution of the Ti⁴⁺ ions within the film thickness was detected, which may in part explain the observed anomaly and has implications regarding the possible occurrence of phase separation during film sintering.     

Synthesis and Characterization of Silver Sulfide Nanoparticles Containing Sol-Gel Derived HPC-Silica Film for Ion-Selective Electrode Application

Silver sulfide nanoparticles dispersed in sol-gel derived hydroxypropyl cellulose (HPC)-silica films have been successfully synthesized using H₂S gas diffusion method. This is the first attempt to produce silver sulfide nanoparticles using this technique. Ag₂S nanoparticles are generated through reaction of H₂S gas with AgNO₃ precursor dissolved in the HPC-silica matrix. Transmission electron microscope (TEM) and atomic force microscope (AFM) analysis reveal nanoparticles size distribution from 2.5 nm to 56 nm for H₂S gas exposed sample. The surface chemistry of Ag₂S nanoparticles and sol-gel derived HPC-silica matrix is confirmed by X-ray photoelectron spectroscopy (XPS). The negative shifts in the core-level XPS Ag (3d) binding energy of Ag₂S nanoparticles are attributed to Ag : S surface atomic ratio exhibited by these nanoparticles with varying processing conditions. Following processing and characterization, suitability of the present method to produce silver sulfide ion-selective electrode is demonstrated by depositing Ag₂S nanoparticles on a graphite rod. The high reponse function of the electrode is due to the presence of nanoparticles.     

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.     

Photosensitivity of Sol-Gel Derived Aluminosilicate Planar Waveguides Doped with Ce3+ Ions

Aluminosilicate planar waveguides doped with Ce³⁺ ions have been prepared by combining a sol gel process and the dip-coating technique. Characterization of the samples has proven their good optical quality and their amorphous structure. For the first time to our knowledge, the photosensitivity of these materials has then been studied. The effect of hydrogen loading on the photosensitivity has been worked out. High fluence irradiation led to the photoablation of the film, but low fluence irradiation demonstrated a variation of the refractive index of n = 5.10^–4 for the hydrogenated Ce³⁺-doped waveguides. These results confirm the potentiality of this material for use in integrated optics. From a fundamental point of view, the versatility of the sol-gel process will allow the study of the effect of the chemical parameters on the photosensitivity of this material and thus a better understanding of the mechanisms of its photorefractivity.     

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.     

Sol-Gel Preparation and Raman Characterization of CdTiO3

Cadmium titanate (CdTiO₃) has been prepared by a room-temperature sol-gel technique. The powders were characterized by means of X-Ray Diffraction. Samples treated at 800°C give rise only to the ilmenite-like phase, but, after a treatment at 1100°C for about four hours, the orthorhombic perovskite is the only crystalline phase observed. The Raman spectrum of the perovskite phase is reported for the first time and that of the ilmenite phase is compared with the spectrum of CdTiO₃ bulk crystals. The effects of the starting stoichiometry on the purity of the final phases, relative to the presence of TiO₂ (anatase and rutile) or CdO, are investigated.     

Preparation and Characterization of TiO2 Thin Films by Sol-Gel Method

Titanium dioxide (TiO₂) thin films have been deposited on silicon and glass substrates by the sol-gel process using titanium iso-propoxide [Ti(O-i-C₃H₇)₄]. The bond configuration of the TiO₂ thin films was analyzed by using FTIR in the wavenumber range from 400 to 4000 cm^–1. The spectral transmittance of as-deposited TiO₂ films deposited on fused silica glass was measured in the wavelength range from 200 to 900 nm. X-ray diffraction measurements were performed to determine the crystallinity of the TiO₂ films. As-deposited films were amorphous. As the film was annealed at higher temperature, the structure was transformed from amorphous to the anatase crystalline state. The chemical composition of the deposited film was investigated using X-ray photoelectron spectroscopy (XPS). The films are essentially stoichiometric with carbon as the dominant impurity on the surface. Raman spectra show the characteristic of TiO₂ anatase phase. The electrical properties of the TiO₂ films were measured using capacitance-voltage (C-V) and current-voltage techniques. From C-V measurements, the dielectric constants were calculated to be approximately 26 for the as-deposited films and 75–82 for films annealed at 700°C in different atmosphere. For the as-deposited samples, the breakdown voltage was 2.7 MV/cm, and for an electric field of 1 MV/cm, the leakage current was 5 × 10^–5 A/cm² and the resistivity was 2.2 × 10¹⁰ -cm.     

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.     

Preparation and Characterization of Compositions Based on PbO-MgO-Nb2O5 Using the Sol-Gel Method

Lead Magnesium Niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb₂O₅, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH₃COO)₂, Mg(CH₃COO)₂, Nb(OC₂H₅)₅ as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb₂O₅. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase.     

Preparation and Characterization of Molybdenum Oxide Thin Films by Sol-Gel Process

This paper presents a new sol-gel process to prepare molybdenum oxide thin films. A molybdenum acetylacetonate sol was prepared by employing the system CH₃COCH₂COCH₃/MoO₃/C₆H₅CH₃/HOCH₂CH₂OCH₃. A molybdenum acetylacetonate gel was prepared by addition of aqueous NH₃. Thermal gravimetry (TG) and differential thermal analyses (DTA) of the gel suggested that crystallization of MoO₃ occurs in a 140 K temperature range around 508°C. MoO₃ films were prepared on fused silica, Si (111) and Al₂O₃ (012) substrates by annealing spin coating films of the sol in oxygen environment at 508°C. X-ray diffraction (XRD) showed that all films crystallize in -MoO₃ structure, and crystallites on fused silica substrate are arbitrarily oriented while those on Si (111) and Al₂O₃(012) substrates oriented in the (010) direction. SEM investigations showed that MoO₃ grains of all films are randomly distributed, with a longitudinal dimension of about 1–5 m and the film thickness is about 1 m.     

Preparation and Characterization of a Sol-Gel Prepared Ferroelectric Sandwich Structure

A novel silicon-based PbTiO₃/Pb(Zr,Ti)O₃/PbTiO₃ (PT/PZT/PT) sandwich structure has been prepared using a sol-gel method. The annealing temperature is greatly reduced compared with those structures without PT layers. Capacitance-voltage (C-V), leakage current-voltage (I-V), polarization-field (P-E), dielectric-frequency response and polarization fatigue of the sandwich structure are examined. The relative dielectric constant, the coercive field and the remanent polarization of the PZT films are measured to be about 900, 18 kV/cm and 16 C/cm² respectively. The current density is less than 5 × 10^–9 A/cm² below 200 kV/cm. The dielectric constant of the structure remains constant at low frequency, and decreases to some degree at high frequency. The retained polarization does not change significantly after 8 × 10⁹ read/write cycles. The PZT films are proved to have very good dielectric and ferroelectric properties. The new PT/PZT/PT sandwich structure can be valuable for memory devices and other applications.