Effects of Measurement Temperature on Radioluminescence Processes in Cerium-Activated Silica Glasses for Dosimetry Applications.

Cerium-doped-silica glasses are widely used as ionizing radiation sensing materials. However, their response needs to be characterized as a function of measurement temperature for application in various environments, such as in vivo dosimetry, space and particle accelerators. In this paper, the temperature effect on the radioluminescence (RL) response of Cerium-doped glassy rods was investigated in the 193-353 K range under different X-ray dose rates. The doped silica rods were prepared using the sol-gel technique and spliced into an optical fiber to guide the RL signal to a detector. Then, the experimental RL levels and kinetics measurements during and after irradiation were compared with their simulation counterparts. This simulation is based on a standard system of coupled non-linear differential equations to describe the processes of electron-hole pairs generation, trapping-detrapping and recombination in order to shed light on the temperature effect on the RL signal dynamics and intensity.

Properties of Gd-Doped Sol-Gel Silica Glass Radioluminescence under Electron Beams.

The radiation-induced emission (RIE) of Gd3+-doped sol-gel silica glass has been shown to have suitable properties for use in the dosimetry of beams of ionizing radiation in applications such as radiotherapy. Linear electron accelerators are commonly used as clinical radiotherapy beams, and in this paper, the RIE properties were investigated under electron irradiation. A monochromator setup was used to investigate the light properties in selected narrow wavelength regions, and a spectrometer setup was used to measure the optical emission spectra in various test configurations. The RIE output as a function of depth in acrylic was measured and compared with a reference dosimeter system for various electron energies, since the dose-depth measuring abilities of dosimeters in radiotherapy is of key interest. The intensity of the main radiation-induced luminescence (RIL) of the Gd3+-ions at 314 nm was found to well represent the dose as a function of depth, and was possible to separate from the Cherenkov light that was also induced in the measurement setup. After an initial suppression of the luminescence following the electron bunch, which is ascribed to a transient radiation-induced attenuation from self-trapped excitons (STEX), the 314 nm component was found to have a decay time of approximately 1.3 ms. An additional luminescence was also observed in the region 400 nm to 600 nm originating from the decay of the STEX centers, likely exhibiting an increasing luminescence with a dose history in the tested sample.

Radioluminescence Response of Ce-, Cu-, and Gd-Doped Silica Glasses for Dosimetry of Pulsed Electron Beams.

Radiation-induced emission of doped sol-gel silica glass samples was investigated under a pulsed 20-MeV electron beam. The studied samples were drawn rods doped with cerium, copper, or gadolinium ions, which were connected to multimode pure-silica core fibers to transport the induced luminescence from the irradiation area to a signal readout system. The luminescence pulses in the samples induced by the electron bunches were studied as a function of deposited dose per electron bunch. All the investigated samples were found to have a linear response in terms of luminescence as a function of electron bunch sizes between 10-5 Gy/bunch and 1.5×10-2 Gy/bunch. The presented results show that these types of doped silica rods can be used for monitoring a pulsed electron beam, as well as to evaluate the dose deposited by the individual electron bunches. The electron accelerator used in the experiment was a medical type used for radiation therapy treatments, and these silica rod samples show high potential for dosimetry in radiotherapy contexts.

Investigation of the Incorporation of Cerium Ions in MCVD-Silica Glass Preforms for Remote Optical Fiber Radiation Dosimetry.

The incorporation of Ce3+ ions in silicate glasses is a crucial issue for luminescence-based sensing applications. In this article, we report on silica glass preforms doped with cerium ions fabricated by modified chemical vapor deposition (MCVD) under different atmospheres in order to favor the Ce3+ oxidation state. Structural analysis and photophysical investigations are performed on the obtained glass rods. The preform fabricated under reducing atmosphere presents the highest photoluminescence (PL) quantum yield (QY). This preform drawn into a 125 µm-optical fiber, with a Ce-doped core diameter of about 40 µm, is characterized to confirm the presence of Ce3+ ions inside this optical fiber core. The fiber is then tested in an all-fibered X-ray dosimeter configuration. We demonstrate that this fiber allows the remote monitoring of the X-ray dose rate (flux) through a radioluminescence (RL) signal generated around 460 nm. The response dependence of RL versus dose rate exhibits a linear behavior over five decades, at least from 330 µGy(SiO2)/s up to 22.6 Gy(SiO2)/s. These results attest the potentialities of the MCVD-made Ce-doped material, obtained under reducing atmosphere, for real-time remote ionizing radiation dosimetry.

Cu/Ce-co-Doped Silica Glass as Radioluminescent Material for Ionizing Radiation Dosimetry.

Optically activated glasses are essential to the development of new radiation detection systems. In this study, a bulk glassy rod co-doped with Cu and Ce ions, was prepared via the sol-gel technique and was drawn at about 2000 °C into a cylindrical capillary rod to evaluate its optical and radioluminescence properties. The sample showed optical absorption and photoluminescence (PL) bands attributed to Cu+ and Ce3+ ions. The presence of these two ions inside the host silica glass matrix was also confirmed using PL kinetics measurements. The X-ray dose rate was remotely monitored via the radioluminescence (RL) signal emitted by the Cu/Ce scintillating sensor. In order to transport the optical signal from the irradiation zone to the detection located in the instrumentation zone, an optical transport fiber was spliced to the sample under test. This RL signal exhibited a linear behavior regarding the dose rate in the range at least between 1.1 mGy(SiO2)/s and 34 Gy(SiO2)/s. In addition, a spectroscopic analysis of this RL signal at different dose rates revealed that the same energy levels attributed to Cu+ and Ce3+ ions are involved in both the RL mechanism and the PL phenomenon. Moreover, integrated intensities of the RL sub-bands related to both Cu+ and Ce3+ ions depend linearly on the dose rate at least in the investigated range from 102 mGy(SiO2)/s up to 4725 mGy(SiO2)/s. The presence of Ce3+ ions also reduces the formation of HC1 color centers after X-ray irradiation.

F/Yb-codoped sol-gel silica glasses: toward tailoring the refractive index for the achievement of high-power fiber lasers.

Accurate control of both the doping distribution inside the fiber core and the low refractive index contrast between the fiber core and cladding materials is essential for the development of high-power fiber lasers based on the use of single-mode large-mode-area (LMA) optical fibers. Herein, sol-gel monolithic F/Yb3+-codoped silica glasses were prepared from porous large silica xerogels doped with ytterbium salt solution, which had been subjected to fluorination with hexafluoroethane gas, before subsequent sintering. The fluorine content inside the doped glass has been varied by adjusting the fluorination duration. The space homogeneity of fluorine and ytterbium concentrations in the cylindrical preforms has been checked by chemical analysis and Raman spectroscopy. Moreover, the glass with the lowest fluorine content has been successfully integrated as a core material in a microstructured optical fiber made using the stack-and-draw method. This fiber was tested in an all-fiber cavity laser architecture to evaluate potential lasing performances of the F/Yb3+-codoped silica glass. It presents a maximum efficiency of 70.4%, achieved at 1031 nm from a 1.16 m length fiber. These results confirm the potentialities of the obtained F/Yb3+-codoped glasses for the fabrication of LMA optical fiber lasers.

Benefit of Rare-Earth "Smart Doping" and Material Nanostructuring for the Next Generation of Er-Doped Fibers.

Erbium-doped fiber amplifiers (EDFAs) for harsh environments require to develop specific fabrication methods of Er 3+-doped fibers (EDFs) so as to limit the impact of radiation-induced absorption. In this context, a compromise has to be found between the concentration of Erbium and the glass composition. On the one hand, high concentration of Er 3+ ions helps to reduce the length of the EDF and hence the cumulated attenuation but generally leads to luminescence quenching mechanisms that limit the performances. On the other hand, so as to avoid such quenching effect, glass modifiers like Al 3+ or P 5+ ions are used in the fabrication of commercial EDFs but are not suitable for applications in harsh environment because these glass modifiers are precursors of radiation-induced structural defects and consequently of optical losses. In this work, we investigate the concept of smart doping via material nanostructuring as a way to fabricate more efficient optical devices. This approach aims at optimizing the glass composition of the fiber core in order to use the minimal content of glass modifiers needed to reach the suited level of performances for EDFA. Er 3+-doped alumina nanoparticles (NPs), as precursor of Er 3+ ions in the preform fabrication process, were used to control the environment of rare-earth ions and their optical properties. Structural and optical characterizations of NP-doped preforms and optical fibers drawn from such preforms demonstrate the interest of this approach for small concentrations of aluminum in comparison to similar glass compositions obtained by a conventional technique.

Laser-induced growth of nanocrystals embedded in porous materials.

Space localization of the linear and nonlinear optical properties in a transparent medium at the submicron scale is still a challenge to yield the future generation of photonic devices. Laser irradiation techniques have always been thought to structure the matter at the nanometer scale, but combining them with doping methods made it possible to generate local growth of several types of nanocrystals in different kinds of silicate matrices. This paper summarizes the most recent works developed in our group, where the investigated nanoparticles are either made of metal (gold) or chalcogenide semiconductors (CdS, PbS), grown in precursor-impregnated porous xerogels under different laser irradiations. This review is associated to new results on silver nanocrystals in the same kind of matrices. It is shown that, depending on the employed laser, the particles can be formed near the sample surface or deep inside the silica matrix. Photothermal and/or photochemical mechanisms may be invoked to explain the nanoparticle growth, depending on the laser, precursor, and matrix. One striking result is that metal salt reduction, necessary to the production of the corresponding nanoparticles, can efficiently occur due to the thermal wrenching of electrons from the matrix itself or due to multiphoton absorption of the laser light by a reducer additive in femtosecond regime. Very localized semiconductor quantum dots could also be generated using ultrashort pulses, but while PbS nanoparticles grow faster than CdS particles due to one-photon absorption, this better efficiency is counterbalanced by a sensitivity to oxidation. In most cases where the reaction efficiency is high, particles larger than the pores have been obtained, showing that a fast diffusion of the species through the interconnected porosity can modify the matrix itself. Based on our experience in these techniques, we compare several examples of laser-induced nanocrystal growth in porous silica xerogels, which allows extracting the best experimental conditions to obtain an efficient particle production and to avoid stability or oxidation problems.

H2-induced copper and silver nanoparticle precipitation inside sol-gel silica optical fiber preforms.

Ionic copper- or silver-doped dense silica rods have been prepared by sintering sol-gel porous silica xerogels doped with ionic precursors. The precipitation of Cu or Ag nanoparticles was achieved by heat treatment under hydrogen followed by annealing under air atmosphere. The surface plasmon resonance bands of copper and silver nanoparticles have been clearly observed in the absorption spectra. The spectral positions of these bands were found to depend slightly on the particle size, which could be tuned by varying the annealing conditions. Hence, transmission electron microscopy showed the formation of spherical copper nanoparticles with diameters in the range of 3.3 to 5.6 nm. On the other hand, in the case of silver, both spherical nanoparticles with diameters in the range of 3 to 6 nm and nano-rods were obtained.

Sol-gel derived ionic copper-doped microstructured optical fiber: a potential selective ultraviolet radiation dosimeter.

We report the fabrication and characterization of a photonic crystal fiber (PCF) having a sol-gel core doped with ionic copper. Optical measurements demonstrate that the ionic copper is preserved in the silica glass all along the preparation steps up to fiber drawing. The photoluminescence results clearly show that such an ionic copper-doped fiber constitutes a potential candidate for UV-C (200-280 nm) radiation dosimetry. Indeed, the Cu⁺-related visible photoluminescence of the fiber shows a linear response to 244 nm light excitation measured for an irradiation power up to 2.7 mW at least on the Cu-doped PCF core. Moreover, this response was found to be fully reversible within the measurement accuracy of this study ( ± 1%), underlying the remarkable stability of copper in the Cu⁺ oxidation state within the pure silica core prepared by a sol-gel route. This reversibility offers possibilities for the achievement of reusable real-time optical fiber UV-C dosimeters.

Direct-writing of PbS nanoparticles inside transparent porous silica monoliths using pulsed femtosecond laser irradiation.

Pulsed femtosecond laser irradiation at low repetition rate, without any annealing, has been used to localize the growth of PbS nanoparticles, for the first time, inside a transparent porous silica matrix prepared by a sol-gel route. Before the irradiation, the porous silica host has been soaked within a solution containing PbS precursors. The effect of the incident laser power on the particle size was studied. X-ray diffraction was used to identify the PbS crystallites inside the irradiated areas and to estimate the average particle size. The localized laser irradiation led to PbS crystallite size ranging between 4 and 8 nm, depending on the incident femtosecond laser power. The optical properties of the obtained PbS-silica nanocomposites have been investigated using absorption and photoluminescence spectroscopies. Finally, the stability of PbS nanoparticles embedded inside the host matrices has been followed as a function of time, and it has been shown that this stability depends on the nanoparticle mean size.

Correlation between gelation time, structure and texture of low-doped silica gels.

It is shown how the properties of a porous silica xerogel prepared using a classical sol-gel synthesis can be fine-tuned by a minor modification of the composition. The addition of a doping cation (Cu(2+), Ca(2+), Na(+)) in trace quantities in the silica sol was found to exert a dramatic effect at all stages of material preparation. An investigation of both liquid and solid phases is presented, making it possible to highlight strong correlations. The time-resolved speciation of Si-containing moieties in the sol was found to be an indication of the structuration of the gel, which was reflected by the porosity and by the molecular structure of the resulting porous material. Based on a careful comparison of several slightly doped silica gels, a model is proposed which makes it possible to predict the structure and the texture of a silica gel from data recorded early in the liquid phase.

Ice mixtures formed by simultaneous condensation of formaldehyde and water: an in situ study by micro-Raman scattering.

Thin films of formaldehyde-water mixtures are co-deposited at 88 K and 10(-1) Torr from gas collected above formaldehyde aqueous solutions of different concentrations (5, 10, 15, 20, 30 mol%). They are analyzed in situ by micro-Raman scattering in the 2700-3800 cm(-1) spectral range. The spectral characteristic of H2CO distributed molecularly in amorphous solid water is obtained under vacuum conditions. As temperature is increased formaldehyde is released during the crystallization of ice between 118 and 138 K. On the other hand, under controlled nitrogen atmosphere, the deposits crystallize in hydrate phases (or solid H2CO(s)) during annealing. A new phase (metastable FOR-A) of H2CO(s) (or a low hydrate after rejection by crystallizing ice) can be spectroscopically identified at 138 K before transformation into a hydrate (with molecular H2CO distributed within the cages of the clathrate FOR-B) takes place at 148 K. This latter phase decomposes between ca. 180 and 200 K. The significant spectral differences between these hydrates and those formed in frozen formaldehyde aqueous solutions reflect the existence of H2CO-clusters of distinctive structural nature relative to those resulting from important oligomerization process in the liquid. Moreover, the structure, the gas distribution and relative gas population in the formaldehyde clathrate cages are influenced by the relative amount of trapped nitrogen at the surface, which moreover depends on the ice film morphology. The dependence on the crystallization temperature of the deposits is explained by the relative amounts of occluded H2CO/N2 and the external pressure conditions. The distinct behavior observed between vacuum and N2-atmosphere conditions certainly reflects a complex mechanism of surface mediated nucleation in which the transport of the reactants to the hydrate reaction zone is facilitated by the presence of a polar dopant.

Microstructures and structural properties of sol-gel silica foams.

Silica xerogels were synthesized and annealed at 1000 degrees C for different durations to yield stable silica materials. The samples were prepared through base-catalyzed hydrolysis and condensation of tetramethyl orthosilicate in methanol. After aging and drying steps, clear and solid xerogels exhibiting a narrow pore size distribution were achieved. The annealing treatment of these xerogels was performed at 1000 degrees C and proved in the present study to lead to a monolithic glass when a progressive heat-treatment procedure was employed to attain 1000 degrees C. In addition to the expected glass, silica foams and ordered phases were observed when the samples were instantaneously heat-treated at 1000 degrees C. Raman spectra of the foamed materials exhibit the classical features of amorphous silica, whereas transmission electronic microscopy pictures reveal the presence of crystallized domains within the vitreous matrix. These crystallites are prone to nucleation and growth processes, which jeopardize the believed stability of the silica foam. The assessment of the hydroxyl content by IR spectroscopy reveals the role played by the latter polycondensation of silanols. The occurrence of foaming process was thus found to result from two competitive phenomena occurring at 1000 degrees C: evacuation of water-related species and viscous sintering.