Bulk photochromism in a tungstate-phosphate glass: A new optical memory material?

In this work, we present a new photochromic tungstate based glass which have both absorption coefficient and refractive index modified under laser exposure. The photosensitive effect is superficial under ultraviolet (UV) irradiation but occurs in the entire volume of the glass under visible irradiation. The effect can be obtained in any specific point inside the volume using an infrared femtosecond laser. In addition, the photosensitive phenomenon can be erased by specific heat treatment. This glass can be useful to substitute actual data storage supports and is a promising material for 3-dimensional (3D) and holographic optical storage.

Photochromic properties of tungstate-based glasses

Vitreous samples were prepared in the NaPO(3)-BaF(2)WO(3) ternary system with high WO(3) concentrations. These glasses exhibit a strong absorption in the visible due to the presence of reduced tungsten species and the use of oxidizing species is required. The couple Sb(2)O(3)/NaNO(3) was introduced in the composition and allowed to obtain transparent glasses. These oxidized samples were illuminated by visible laser radiation and showed an efficient volumetric photochromic effect. The photosensitive effect appeared as a dark spot throughout the entire volume of the glasses. The effect was investigated by several techniques such as, U-V-visible absorption, Raman and XANES at the L(1) and L(3) tungsten absorption edges. The results suggest a photoreduction of tungsten atoms without structural changes of the viteous network. Finally, the photochromic effect can be erased by thermal treatment at 200 degrees C for a few minutes. (C) 2007 Published by Elsevier B.V.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Microwave synthesis of YAG : Eu by sol-gel methodology

Yttrium-aluminum oxides are interesting compounds and they have been extensively used as host for lasers and phosphors, due to their stable physical and chemical properties. The fabrication of yttrium-aluminum garnet (YAG) has been investigated thoroughly. Single-crystal YAG is expensive and to produce it a new way has been investigated. This process consists of modifying the methodology of reagents mixture and the process of heating them. The microwave irradiation is used to heat-treat the oxide mixture. The traditional synthesis of YAG powders occurs through the reaction of aluminum and yttrium powders at high temperatures. With this work we investigated the preparation of YAG by non-hydrolytic sol-gel route as an alternative methodology to obtain yttrium-aluminum matrix from inorganic precursors (yttrium and aluminum chloride). The preparation of the gel was carried out in an oven-dried glassware. The AlCl3, YCl3 and ethanol were reacted in reflux under argon atmosphere. Europium III chloride was added as a structural probe. The powder was dried and heat-treated in modified microwaves. The samples were pre-treated at 50 and 800 C during I h and then heated in microwaves for 30 s, 2 and 4 min. The formation process and structure of the powders were studied by means of X-ray diffraction (XRD), photoluminescence (PL) and transmission electronic microscopy (TEM). XRD presents only picks corresponding to the YAG phase and confirmed by TEM. PL date showed that the YAG phase was formed in 2 min with the samples pre-treated at 50 C. For the samples pretreated at 800 degrees C, the YAG phase appears in 30s. The excitation spectra present a maximum of 394 nm corresponding to the L-5(6) level and emission spectra of Eu III ion present bands characteristic transitions arising from the D-5(0) -> F-7(J) (J= 1, 2, 3, 4) monifolds excited at their maximum. The magnetic dipole D-5(0) -> F-7(1) transition presents more intensity than the electric dipole D-5(0) -> F-7(2) transition. This methodology showed efficiency in obtaining YAG phase. (c) 2006 Elsevier B.V. All rights reserved.

Characterization of the reversible photoinduced optical changes in Sb-based glasses

Changes occurring in absorption coefficients when glasses in the SbPO4-WO3 binary system were irradiated by light, at the edge of the absorption band, were measured in real time. These glasses present good thermal and optical properties and photoinduced changes in the absorption coefficients are reversible by heat treatment around 150 degrees C. Subsequent recording/erasing cycles could be made without sample degradation. The sensitivity of the induced optical changes was studied for different wavelengths, light powers and energy of light dose exposures, and for different compositions of the glasses. The changes in the absorption coefficients of the glass samples were accompanied by a color change from yellow to blue, and were also characterized by visible spectroscopy. The color changes occurred through the entire volume of the glass (similar to 2 mm thickness) for the Ar-ion laser lines at the edge of the absorption band. (c) 2006 Elsevier B.V. All rights reserved.

Erbium-activated HfO2-based waveguides for photonics

Silica-based sol-gel waveguides activated by Er3+ ions are attractive materials for integrated optic devices. 70SiO(2)-30HfO(2) planar waveguides, doped with Er3+ concentrations ranging from 0.01 to 4 mol%, were prepared by sol-get route. The films were deposited on v-SiO2 and silica-on-silicon substrates, using dip-coating technique. The waveguides show a homogeneous surface morphology, high densification degree and uniform refractive index across the thickness. Emission in the C-telecommunication band was observed at room temperature for ill the samples upon excitation at 980 nm. The shape is found to be almost independent on erbium content, with a FWHM between 44 and 48 nm. The I-4(13/2) level decay curves presented a single-exponential profile, with a lifetime ranging between 1.1 and 6.7 ms, depending on the erbium concentration. The waveguide deposited on silica-on-silicon substrate supports one single propagation mode at 1.5 mum with a confinement coefficient of 0.85, and a losses of about 0.8 dB/cm at 632.8 nm. (C) 2003 Elsevier B.V. All rights reserved.

Structural studies of NaPO3-WO3 glasses by solid state NMR and Raman spectroscopy

Vitreous samples were prepared in the (100 2 x) NaPO3-x WO3 (0 <= x <= 70) glass forming system using conventional melting-quenching methods. The structural evolution of the vitreous network was monitored as a function of composition by thermal analysis, Raman spectroscopy and high resolution one- and two-dimensional P-31 solid state NMR. Addition of WO3 to the NaPO3 glass melt leads to a pronounced increase in the glass transition temperatures, suggesting a significant increase in network connectivity. At the same time Raman spectra indicate that up to about 30 mol% WO3 the tungsten atoms are linked to some non-bridging oxygen atoms (W-O- or W=O bonded species), suggesting that the network modifier sodium oxide is shared to some extent between both network formers. W-O- W bond formation occurs only at WO3 contents exceeding 30 mol%. P-31 magic angle spinning (MAS)-NMR spectra, supported by two-dimensional J-resolved spectroscopy, allow a clear distinction between species having two, one, and zero P-O-P linkages. The possible formation of some anionic tungsten sites suggested from the Raman data implies an average increase in the degree of polymerization for the phosphorus species, which would result in diminished P-31/Na-23 interactions. This prediction is indeed confirmed by P-31{Na-23} and Na-23{P-31} rotational echo double resonance (REDOR) NMR results, which indicate that successive addition of WO3 to NaPO3 glass significantly diminishes the strength of phosphorus-sodium dipole-dipole couplings.

Optical recording in Se(Te)/As2S3 multilayers

The development of Te containing nanoscaled, compositionally modulated Te/As2S3 multilayer structures enables the realisation of optical recording in real time with a CW He-Ne laser illumination (lambda=633 nm) with improved recording parameters in comparison with known Se/As2S3 structures. It is established that the efficiency of the recording process depends on the light stimulated interdiffusion and thickness of sub-layers.

3D hydrogen-bonded network built from copper(II) complexes of 1,3-propanediamine

The reaction of Cu(NO3)(2).3H(2)O with 1,3-propanediamine (pn), in the presence of NaN3, afforded a 1:1 co-crystal formed by [Cu(NO3)(2)(pn)(2)] and [Cu(N-3)(NO3)(pn)(2)] (1 and 2), which were characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction. In both compounds, the copper(II) centers are in a distorted octahedral environment, formed by four N atoms of two bidentate pn ligands in the basal plane, whereas the axial bonds are formed by two O atoms from the nitrate ligands in 1 and one O atom from the nitrate ligand and one N atom from the azide ion in 2. The asymmetric unit of the crystal consists of two crystallographically independent 1 and 2 complexes, which are held together in a 3D network by a series of N - H center dot center dot center dot O and N - H center dot center dot center dot N hydrogen bonds, as well C - H center dot center dot center dot O interactions. New supramolecular synthons are identified by the occurrence of two geometrically distinct molecular recognition patterns involving the NO3- ion and amino groups from pn ligands.

Excited state dynamics of the Ho3+ ions in holmium singly doped and holmium, praseodymium-codoped fluoride glasses

The deactivation of the two lowest excited states of Ho3+ was investigated in Ho3+ singly doped and Ho3+, Pr3+-codoped fluoride (ZBLAN) glasses. We establish that 0.1-0.3 mol % Pr3+ can efficiently deactivate the first excited (I-5(7)) state of Ho3+ while causing a small reduction of similar to 40% of the initial population of the second excited (I-5(6)) state. The net effect introduced by the Pr3+ ion deactivation of the Ho3+ ion is the fast recovery of the ground state of Ho3+. The Burshstein model parameters relevant to the Ho3+-> Pr3+ energy transfer processes were determined using a least squares fit to the measured luminescence decay. The energy transfer upconversion and cross relaxation parameters for 1948, 1151, and 532 nm excitations of singly Ho3+-doped ZBLAN were determined. Using the energy transfer rate parameters we determine from the measured luminescence, a rate equation model for 650 nm excitation of Ho3+-doped and Ho3+, Pr3+-doped ZBLAN glasses was developed. The rate equations were solved numerically and the population inversion between the I-5(6) and the I-5(7) excited states of Ho3+ was calculated to examine the beneficial effects on the gain associated with Pr3+ codoping. (c) 2007 American Institute of Physics.

Thermal characterization of bacterial cellulose-phosphate composite membranes

Cellulose-phosphate composite membranes have been prepared from bacterial cellulose membranes ( BC) and sodium polyphosphate solution. The structure and thermal behavior of the new composites were evaluated by X-ray diffraction (XRD), P-31-nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry (TG) and thermomechanical analysis (TMA). From XRD analyses the I alpha and I beta cellulose crystalline phases were identified together with crystalline sodium phosphate that covers the cellulose microfibrils as revealed by SEM. P-31 NMR spectra show peaks assigned to Q(0) and Q(1) phosphate structures to be compared to the Q(2) units that characterize the precursor polyphosphate. Glass transition temperature, T-g, obtained from TMA curves and thermal stability obtained from TG and DSC measurements, were observed to be dependent on the phosphate content.

1.5 mu m emission and infrared-to-visible frequency upconversion in Er+3/Yb+3-doped phosphoniobate glasses

Sodium phosphoniobate glasses with the composition (mol%) 75NaPO(3)-25Nb(2)O(5) and containing 2 mol% Yb3+ and x mol% Er3+ (0.01 <= x <= 2) were prepared using the conventional melting/casting process. Er3+ emission at 1.5 mu m and infrared-to-visible upconversion emission, upon excitation at 976 nm, are evaluated as a function of the Er3+ concentration. For the lowest Er3+ content, 1.5 mu m emission quantum efficiency was 90%. Increasing the Er3+ concentration up to 2 mol%, the emission quantum efficiency was observed to decrease to 37% due to concentration quenching. The green and red upconversion emission intensity ratio was studied as a function of Yb3+ co-doping and the Er3+-Er3+ energy transfer processes. (c) 2006 Elsevier B.V. All rights reserved.

NMR structural study on the As-P-S glassy system

Glasses having the composition As2S3(1-x)-P2S5(x) with x ranging from 0 to 0.7 have been investigated to determine the compositional effect on properties and local structure. Glass transition temperature (T,) decreases and molar volume (V,,) increases with an increase in P content. Using P-31 NMR, we measured the strength of the P-31-P-31 magnetic dipolar interaction in the glass samples and the AsPS4 crystallized phase. Based on these data, we observed the formation of the As2P2S8 network, which reflects an increase in the average coordination number and a decrease in the degree of rigidity.

Erbium- and ytterbium-doped sol-gel SiO2-HfO2 crack-free thick films onto silica on silicon substrate

Aware of the difficulties in applying sol-gel technology on the preparation of thin films suitable for optical devices, the present paper reports on the preparation of crack-free erbium- and ytterbium-doped silica: hafnia thick films onto silica on silicon. The film was obtained using a dispersion of silica-hafnia nanoparticles into a binder solution, spin-coating, regular thermal process and rapid thermal process. The used methodology has allowed a significant increase of the film thickness. Based on the presented results good optical-quality films with the required thickness for a fiber matching single mode waveguide were obtained using the erbium- and ytterbium-activated sol-gel silica:hafnia system. The prepared film supports two transversal electric modes at 1550 nm and the difference between the transversal electric mode and the transversal magnetic mode is very small, indicating low birefringence. Photoluminescence of the I-4(13/2) -> I-4(15/2) transition of erbium ions shows a broad band centered at 1.53 mu m with full width at a half maximum of 28 nm. Up-conversion emission was carried out under different pump laser powers, and just one transition at red region was observed. (c) 2006 Elsevier B.V. All rights reserved.