Fabrication of Yb-doped silica glass through the modification of MCVD process

A method to deliver Yb and Al compounds in vapor phase to the reaction/deposition zone has been devised for modified chemical vapor deposition (MCVD) process. By using this MCVD setup, we succeeded to prepare silica glass preforms presenting uniform dopants concentrations in the radial and longitudinal directions with good reproducibility. Preforms with a core diameter larger than 5 mm were easily prepared by depositing around 40 layers. By changing some parameters in the deposition step, such as carrier gases flow and temperatures of Yb(DPM)₃ and AlCl₃ furnaces, different concentrations of Yb and Al were incorporated into the core region of the silica glass preforms. By adjusting the Yb and Al concentrations, we succeeded to prepare preforms for large mode area (LMA) fiber with a change less than 10% of nominal refractive index.     

About the fluorine chemistry in MCVD: The mechanism of fluorine incorporation into SiO2 layers

Fluorine incorporation during the deposition of silica layers is studied under MCVD conditions using C₂F₃Cl₃ as fluorine source. The experimental results are compared with known models of the incorporation mechanism. It is found that a gas/solid equilibrium during the consolidation step determines the final fluorine content of the layers.     

About the Fluorine Chemistry in MCVD: The Influence of Fluorine Doping on SiO2 Deposition

In the fabrication of quartz glass fibers for optical communication, fluorine doping gets increasing importance. In contrast to other dopants, fluorine influences the deposition of SiO₂ in Modified Chemical Vapour Deposition. An equation is derived from considerations of equilibrium chemistry which yields the deposition efficiency of SiO₂ as function of fluorine doping. It is compared with experimental results.     

A computational fluid dynamics model for co-deposition of silica and germania in the MCVD process

The modified chemical vapor deposition (MCVD) process is used to create the doped silica preforms that are subsequently drawn to optical fiber. This paper reports on the extension of a computational fluid dynamics model of the MCVD process to include the simultaneous creation, transport and wall deposition of silica and germania particles. Simulations indicate the crucial role played by the interplay between chemical kinetics and equilibria along the substrate tube. Illustrative results show the likely impact of particle size on deposition patterns, along with a possible explanation for the observed high wastage of germanium in this process.     

Heterogeneous equilibria and distribution of elements in the MCVD process for making optical fiber

Thermodynamic calculations have been performed on systems relevant to doped silica optical fiber processing: SiCl₄---GeCl₄---POCl₃---O₂, SiCl₄---BBr₃---O₂, O₂---H₂O---CH₄---SOCl₂---SiO₂ and O₂---H₂O---CH₄---CF₄---SiO₂ by using the SOLGASMIX-PV computer program. Equilibrium distributions of Ge, P, Si, B and H species are given.     

The pentacene films on the glass/ITO surface: structure and optical properties

Abstract

The structure, morphology and optical transmittance spectra of pentacene films on the (glass/ITO) surface were studied. The films were grown by two methods - the thermal vacuum deposition (TVD) and pulsed laser deposition (PLD). The electron diffraction pattern from thermally deposited pentacene films confirms their polycrystalline structure while the diffraction pattern of PLD-coated layers has a diffusion character. The results obtained showed that layers deposited by the TVD method has an optical spectrum that is characteristic for the pentacene film in contrary to the layers deposited by the PLD method. It is found a sensitivity of the optical transmittance of pentacene films to the ammonia action, which may be used for development the optical gas sensor.     

FTIR spectroscopy to investigate the role of fluorine on the optical properties of pure and rare earth-doped sol–gel silica

FTIR spectroscopy is applied to monitor the effects caused by fluorinated precursors (1–10 mol%) in the sol–gel synthesis of silica glasses, either pure or doped with Ce and Er. In pure samples the Si–OH level is heavily reduced to ∼3 × 10⁻³ mol%. In doped samples the effect is more limited. The presence of residual fluorine, proved by the Si–F vibrational absorption at ∼950 cm⁻¹, causes deep changes in the rare-earth (RE) crystal field spectra, which are characterized by narrow absorption lines. The lines broaden if the temperature is increased from 9 to 300 K. The result is discussed in terms either of local ordering around the rare earth ion or by its partial decoupling from the disordered host matrix, due to the creation of network terminating sites.     

Simulation of the optical properties of Tm:ZBLAN glass

The optical properties of Tm:ZBLAN glass have been simulated. The simulated optical spectra agreed substantially with the observed spectra. The population of the energy levels of the Tm³⁺ ion under dual-wavelength excitation for upconversion emission and amplification was evaluated by solving the rate equation with the simulated transition probabilities and spectral shapes of the transitions of which the initial levels were from the ³H₆ to ³P₂ levels. The large population of the ¹G₄ level, which is the upper level for 480 nm laser oscillation, was estimated for the conditions of laser oscillation at room temperature. We also proposed new combinations of the excitation wavelengths for the amplification of the 1470 nm signal.     

Cobalt phthalocyanine nanowires: Growth,crystal structure,and optical properties

Cobalt phthalocyanine nanowires with new crystal structure and broad optical absorption spectra were fabricated by using organic vapor phase deposition method. The morphology, crystal structure and optical properties of CoPc nanowires were characterized by SEM, X‐ray diffraction, Fourier transform infrared and UV‐visible spectroscopies. Analyses of X‐ray diffraction patterns and Fourier transform infrared spectra indicate that the crystal structure of CoPc nanowires represents a new polymorph, which is designated J‐CoPc. These J‐CoPc nanowires with high directionality (average diameter ∼50 nm) surprisingly possess much broader optical absorption spectra in the visible spectral region than those of the α‐ and β‐phase CoPc, enabling high potential for practical applications in novel molecular electronic/optical devices.     

Mechanical properties of optical glass fibers damaged by nanoindentation and water ageing

Mechanical properties of optical glass fibers are strongly influenced by cracks on glass surface. Cracks may be generated during manufacture and handling. The chemo-mechanical effect due to water may decrease the response of glass fibers because of surface degradation. In this work glass fibers were aged in a wet chamber at humidity of 85% in temperatures lower than 90 °C, during seven weeks. After being aged, the fibers were submitted to tension tests. The fracture loads were investigated by Weibull statistics. An increase in dynamic fatigue parameter was observed. Surface analysis by AFM indicated smooth surfaces. Small cracks on optical fiber glass surface were made by Vickers indentation and nanoindentation using a Berkovich indenter. A decrease on applied load to fracture indicates that the fiber was damaged by indentation. The influence of indentation load was investigated. As the deformation rate was very low during tension tests, the cracks grow during the test and the fiber fracture at loads lower than for not indented fibers. The effect of water and small indentation fracture on glass is discussed considering the surface damage induced by both methods. The size of the cracks from the different indentations and ageing are estimated.     

Fluorescence properties and laser demonstrations of Nd-doped high silica glasses prepared by sintering nanoporous glass

Porous glass with high-SiO₂ content was impregnated with Nd ions, and subsequently sintered at 1100 °C into a compact non-porous glass in air or reducing atmosphere. Sintering in a reducing atmosphere produced an intense violet–blue fluorescence at 394 nm. However, the sintering atmospheres almost did not affect the fluorescence properties in the infrared range. A good performance Nd³⁺-doped silica microchip laser operating at 1064 nm was demonstrated. The Nd-doped sintering glasses with high-SiO₂ content are potential host materials for high power solid-state lasers and new transparent fluorescence materials.     

Influence of UV-exposure on the crystallization and optical properties of photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a photosensitive multi-component silicate glass. Photoinduced crystalline phase precipitation results in refractive index variations in UV exposed areas of PTR glass. The precipitation of silver containing particles which occurs during photo-thermo-refractive process increases the optical absorption of the samples in the range 350 nm to NIR wavelengths and the growth of sodium fluoride crystals and their aggregation increases light scattering in visible and NIR regions. We show that one effect of the UV-exposure is a decrease in the crystallization temperature by ～50 °C compared to the unexposed areas as measured by differential scanning calorimetry, which we attribute to an increase in nucleation rate. Using spectro-photometric measurements, a linear function is fitted to the changes in the amplitude of the absorption band of the silver containing particles versus the UV-dosage. The root mean square scatter of the data from the linear function is better than 0.99 and the slope of the function is 0.32 ± 0.01 cm/J. The IR absorption of PTR sample, measured by laser calorimetry shows that the increase of the absorption in infrared region at 1.1 μm, is due to the tail of the absorption band of silver containing particles having maximum at 465 nm. We finally show that after hyper-development, one effect of UV-exposure at 325 nm on the crystallization kinetics of PTR glasses is a decrease in particle sizes from micron size to nanometers size. But additional investigations demonstrate that smaller dosage UV-exposures (a few tens of milliwatts) increase the optical scattering by one order of magnitude. Optical micrographs taken after UV-exposure and hyper-development reveal the use of smaller dosages enhances nucleation rate without preventing the growth of large crystals and therefore induces higher scattering.     

Role of bromine on the thermal and optical properties of photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a photosensitive silicate glass doped with cerium, silver, and fluorine. The precipitation of a minor crystalline phase after UV-exposure and thermal treatment induces a refractive index change, which is large enough to create diffractive optical elements. In this work we present a first attempt to understand the role of bromine on thermal and optical properties of PTR glass. We reveal that at least 75% of the concentration of bromine of commercial PTR glass is necessary to produce photo-induced crystallization. We also show that an increase of the bromine concentration will increase the mean refractive index of virgin PTR glass. Further thermal treatments induce a decrease of the mean refractive index of PTR glass. This decrease is finally shown to be larger in UV-exposed glass if photo-induced crystallization is present. We also show that bromine concentration will decrease water concentration in PTR glass and have an impact on the losses in visible. We demonstrate that the higher the bromine concentration, the higher the shift of the silver containing particles absorption band. In addition, if bromine concentration is high enough to produce photosensitivity, an increase of scattering due to the crystallization process is observed.     

Predicted structure,thermo-mechanical properties and Li ion transport in LiAlF4 glass

Materials with the LiAlF₄ composition are of interest as protective electrode coatings in Li ion battery applications due to their high cationic conductivity. Here classical molecular dynamics calculations are used to produce amorphous model structures by simulating a quench from the molten state. These are analysed in terms of their individual pair correlation functions and atomic coordination environments. This indicates that amorphous LiAlF₄ is formed of a network of corner sharing AlF₆ octahedra. Li ions are distributed within this network, primarily associated with non-bridging fluorine atoms. The nature of the octahedral network is further analysed through intra‐ and interpolyhedral bond angle distributions and the relative populations of bridging and non-bridging fluorine ions are calculated. Network topology is considered through the use of ring statistics, which indicates that, although topologically well connected, LiAlF₄ contains an appreciable number of corner‐linked branch‐like AlF₆ chains. Thermal expansion values are determined above and below the predicted glass transition temperature of 1340 K. Finally, movement of Li ions within the network is examined with predictions of the mean squared displacements, diffusion coefficients and Li ion activation energy. Different regimes for lithium ion movement are identified, with both diffusive and sessile Li ions observed. For migrating ions, a typical trajectory is illustrated and discussed in terms of a hopping mechanism for Li transport.     

Role of sol-gel networking and fluorine doping in the silica Urbach energy

We present the results of the analysis of the ultraviolet (UV) absorption edge of fluorine-modified sol-gel silica. UV transmission data, obtained by means of synchrotron radiation, have been analyzed in the spectral range 7.5–8.5 eV, with a spectral resolution of about 10 meV. Data on silica samples with different F content (from 0 to few 10^? 1 mol%) have been analyzed and compared with literature data on quartz and pure synthetic commercial silica. The analysis allows us to discriminate between the effects of the fluorine addition and those ascribable to structural peculiarities of the sol-gel networking. The estimated Urbach energy E_U(T = 0) ranges between 45 and 55 meV, higher that in crystalline quartz and lower than in commercial synthetic silica. The study of the temperature dependence of E_U(T) shows that the fluorine modification of the silica network causes the lowering of the static disorder and the widening of the energy gap. However, there is also a relevant effect of the production process, since sol-gel silica samples show lower E_U values with respect to other types of silica, quite independently of the fluorine content. The analysis of the Raman spectra however shows that the starting amount of fluorine-modified molecular precursor influences the network condensation process, independently of the final fluorine content into the matrix.     

Synthesis,structure and optical properties of zinc oxide hexagonal microprisms

Zinc oxide (ZnO) pencil‐head‐like (PHL) microprisms were synthesized by a hydrothermal route using a zinc (Zn) plate as a source and substrate. The structural analysis confirmed the formation of ZnO with hexagonal wurtzite phase on the hexagonal Zn substrate and the growth of the ZnO microparticles along the [101] direction. The room temperature photoluminescence (PL) of the ZnO microprisms showed a sharp UV emission band located at around 380 nm, which is expected to originate from the radiative recombination of free excitons. The sharp UV emission band, with a full width at half‐maximum of about 15 nm and an extremely weak visible emission, confirms the high crystal quality of the synthesized ZnO microprisms. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of cooling on the optical properties and crystallization of UV-exposed photo-thermo-refractive glass

Photo-thermo-refractive (PTR) glass is a multi-component silicate glass that undergoes a refractive index change after UV-exposure and thermal treatment. This photo-thermo-refractivity is due to the precipitation of sodium fluoride nano-crystals; thus the glass remains highly transparent in the visible and near-IR regions. Up to now, most studies focused on the influence of temperature and duration of thermal treatment on the PTR glass properties, but no attention was given to the cooling step after thermal treatment. In this paper, the influence of cooling on crystallization and resulting optical properties of UV-exposed PTR glass is studied. We show that cooling between the nucleation and growth treatments is a mandatory step to achieve the full benefits of the first heat-treatment, i.e., a large number of small crystals. We also show that the main part of the refractive index change occurs on the cooling path after pre-nucleation. Non-isothermal DSC study associated with in situ pre-nucleation treatment shows that pre-nucleation enhances crystallization only if the temperature is decreased below T_g before the second (development) treatment. Using high temperature photometric measurements of the absorption spectra of UV-exposed PTR glasses, we tentatively associate that effect with the presence of liquid drops of a silver containing phase during regular pre-nucleation treatment. This fact explains the necessity to cool such drops below their melting point to obtain nucleation centers for efficient precipitation of NaF nano-crystals.     

Dopant concentration dependence of structure,optical, and magnetic properties of ZnO:Fe thin films

The effects of Fe-dopant concentration on the structure, optical, and magnetic properties of ZnO thin films were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), optical transmittance, absorption, photoluminescence (PL), and magnetic measurements. XRD spectra indicated that the doping of Fe atoms could not only change the lattice constant of ZnO but also improve the crystalline quality of ZnO thin films. And the Zn (0 0 2) diffraction peak at round 36.34°(2θ) was detected with increasing Fe content for the substitution of the Zn in the ZnO film. The band gap edge shifted toward longer wavelength with increase in Fe doping. Moreover, near band edge emission gradually increased with increase in Fe content (up to about 0.82 wt%), and then abruptly decreased due to the concentration quenching effect. Magnetic measurements confirmed that the ferromagnetic behavior of Fe-doped ZnO was correlated with the dopant concentration.     

Preparation of silica and soda-silica glasses by the sol-gel process

Samples of silica glass and soda-silica glasses (containing 1 wt% and 13 wt% Na₂O) were prepared by hydrolysis of alkoxides to form gels, followed by heating the gels at low temperatures, below the glass transformation. The water necessary for hydrolysis was either taken from the atmosphere or added to the starting solution to accelerate the process. In the latter case the gelation time exhibited a minimum for a certain quantity of water added. The heat treatment process to form a glass from a gel was studied by DTA and TGA. At low temperatures (below 100°C) an endothermic DTA peak was observed due to the loss of organic volatiles and water. A large exothermic peak was also found at 276°C for the silica and at 365–395°C for the soda-silica gels. At higher temperatures the 13Na₂O87SiO₂ (wt%) composition gave a DTA trace very similar to the same composition conventionally melted which had been rapidly quenched from well above the transformation range (i.e. with a high fictive temperature). The preparation of bulk samples of the glasses is discussed.