Yb2+-Doped Silicate Glasses as Optical Sensor Materials for Cryogenic Thermometry.

Optical sensors constitute attractive alternatives to resistive probes for the sensing and monitoring of temperature (T). In this work, we investigated, in the range from 2 to 300 K, the thermal behavior of Yb2+ ion photoluminescence (PL) in glass hosts for cryogenic thermometry. To that end, two kinds of Yb2+-doped preforms, with aluminosilicate and aluminophosphosilicate core glasses, were made using the modified chemical vapor deposition (MCVD) technique. The obtained preforms were then elongated, at about 2000 °C, to canes with an Yb2+-doped core of about 500 µm. Under UV excitation and independently of the core composition, all samples of preforms and their corresponding canes presented a wide visible emission band attributed to Yb2+ ions. Furthermore, PL kinetics measurements, recorded at two emission wavelengths (502 and 582 nm) under 355 nm pulsed excitation, showed an increase, at very low T, followed by a decrease in lifetime until room temperature (RT). A modified two-level model was proposed to interpret such a decay time dependence versus T. Based on the fit of lifetime data with this model, the absolute (Sa) and relative (Sr) sensitivities were determined for each sample. For both the preform and its corresponding cane, the aluminophosphosilicate glass composition featured the highest performances in the cryogenic domain, with values exceeding 28.3 µsK-1 and 94.4% K-1 at 30 K for Sa and Sr, respectively. The aluminophosphosilicate preform also exhibited the wider T operating range of 10-300 K. Our results show that Yb2+-doped silicate glasses are promising sensing materials for optical thermometry applications in the cryogenic domain.

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.

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.

Radiation hardening of sol gel-derived silica fiber preforms through fictive temperature reduction.

The impact of fictive temperature (Tf) on the evolution of point defects and optical attenuation in non-doped and Er3+-doped sol-gel silica glasses was studied and compared to Suprasil F300 and Infrasil 301 glasses before and after γ-irradiation. To this aim, sol-gel optical fiber preforms have been fabricated by the densification of erbium salt-soaked nanoporous silica xerogels through the polymeric sol-gel technique. These γ-irradiated fiber preforms have been characterized by FTIR, UV-vis-NIR absorption spectroscopy, electron paramagnetic resonance, and photoluminescence measurements. We showed that a decrease in the glass fictive temperature leads to a decrease in the glass disorder and strained bonds. This mainly results in a lower defect generation rate and thus less radiation-induced attenuation in the UV-vis range. Furthermore, it was found that γ-radiation "hardness" is higher in Er3+-doped sol-gel silica compared to un-doped sol-gel silica and standard synthetic silica glasses. The present work demonstrates an effective strategy to improve the radiation resistance of optical fiber preforms and glasses through glass fictive temperature reduction.

Coherent beam combining with an ultrafast multicore Yb-doped fiber amplifier.

Active coherent beam combination using a 7-non-coupled core, polarization maintaining, air-clad, Yb-doped fiber is demonstrated as a monolithic and compact power-scaling concept for ultrafast fiber lasers. A microlens array matched to the multicore fiber and an active phase controller composed of a spatial light modulator applying a stochastic parallel gradient descent algorithm are utilized to perform coherent combining in the tiled aperture geometry. The mitigation of nonlinear effects at a pulse energy of 8.9 µJ and duration of 860 fs is experimentally verified at a repetition rate of 100 kHz. The experimental combining efficiency results in a far field central lobe carrying 49% of the total power, compared to an ideal value of 76%. This efficiency is primarily limited by group delay differences between cores which is identified as the main drawback of the system. Minimizing these group delay issues, e.g. by using short and straight rod-type multicore fibers, should allow a practical power scaling solution for femtosecond fiber systems.

Anti-Stokes photoluminescence in Ga/Bi co-doped sol-gel silica glass.

Unusual temperature dependence of the anti-Stokes photoluminescence (ASPL) at 734 nm was found in Ga/Bi co-doped sol-gel silica glass. While in the temperature range of 450-873 K, the behavior of ASPL is completely determined by the thermal population of the excited state levels, its intensity is continuously increasing with decreasing temperature in the range of 77-430 K. By measuring the pump power dependence of ASPL at 300 K, we show that the latter can be described via the two-step intracenter excitation process and subsequent relaxation. Based on the measurements of temperature dependence of the excitation spectra of near infrared band (at 1140 nm) and that corresponding to the ASPL (at 734 nm), we propose a simple rate equation model to explain the unusual behavior of ASPL.

Photoluminescence in Ga/Bi co-doped silica glass.

Bismuth-Gallium co-doped silica glass fiber preform was prepared from nano-porous silica xerogels using a conventional solution doping technique with a heterotrinuclear complex and subsequent sintering. Ga-connected optical Bismuth active center (BAC) was identified as the analogue of Al-connected BAC. Visible and infrared photoluminescence (PL) were investigated in a wide temperature range of 1.46 - 300 K. Based on the results of the continuous wave (CW) and time resolved (TR) spectroscopy we identify the centers emitting in the spectral region of 480 - 820 nm as Bi(+) ions. The near infrared (NIR) PL around 1100 nm consists of two bands. While the first one can be ascribed to the transition in Bi(+) ion, the second band is presumably associated to defects. We put in evidence the energy transfer (ET) between Bi(+) ions and the second NIR emitting center via quadrupole-quadrupole and dipole-quadrupole mechanisms of interactions. Finally, we propose the energy level diagram of Bi(+) ion interacting with this defect.

Few mode Er(3+)-doped fiber with micro-structured core for mode division multiplexing in the C-band.

Design and experimental characterization of Er(3+)-doped fiber amplifiers supporting 6 spatial modes in wavelength division multiplexing regime are reported. The study is first focused on Er(3+)-doped circular ring-structured profiles accessible with conventional fiber manufacturing techniques. However, these fiber designs, optimized for gain equalization, prove to be difficult to obtain experimentally. So as to go beyond these limits, an alternative approach based on a "pixelated" Er(3+)-doped core is proposed. Several possible designs are theoretically investigated and a first fabrication of micro-structured fiber is presented.

Comparison of photo- and Cu(I)-catalyzed "click" chemistries for the formation of carbohydrate SPR interfaces.

Understanding interactions of glycans with proteins in key biological events has seen the development of various analytical methods such as microarray techniques. Label-free approaches, such as surface plasmon resonance (SPR) techniques are particularly attractive and we explore here the potential of a novel interface composed of lamellar Ti/Au/silicon dioxide derivatized with sugars to probe lectin-sugar interactions by SPR. Two parallel surface functionalization strategies have been developed: one in which azide-functionalized surfaces are linked via a Cu(I) "click" method to alkynyl-derivatized glycan partners and another wherein perfluorophenyl azide-functionalized surfaces are reacted through a C-H insertion photocoupling reaction with underivatized glycans. The effectiveness of the two interfaces is assessed for their lectin-recognition abilities in an SPR format.

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.

Development of a metal-chelated plasmonic interface for the linking of His-peptides with a droplet-based surface plasmon resonance read-off scheme.

Monolayers of metal complexes were covalently attached to the surface of lamellar SPR interfaces (Ti/Ag/a-Si(0.63)C(0.37)) for binding histidine-tagged peptides with a controlled molecular orientation. The method is based on the activation of surface acid groups with N-hydroxysuccinimide (NHS), followed by an amidation reaction with (S)-N-(5-amino-1-carboxypentyl)iminodiacetic acid (NTA). FTIR and X-ray photoelectron spectroscopy (XPS) were used to characterize each surface modification step. The NTA modified SPR interface effectively chelated Cu(2+) ions. Once loaded with metal ions, the modified SPR interface was able to bind specifically to histidine-tagged peptides. The binding process was followed by surface plasmon resonance (SPR) in a droplet based configuration. The Cu(2+)-NTA modified interface showed protein loading comparable to commercially available NTA chips based on dextran chemistry and can thus be regarded as an interesting alternative. The sensor interface can be reused several times due to the easy regeneration step using ethylenediaminetetraacetic acid (EDTA) treatment.

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.

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.

Tailoring CW supercontinuum generation in microstructured fibers with two-zero dispersion wavelengths.

We theoretically study broadband supercontinuum generation in photonic crystal fibers exhibiting two zero dispersion wavelengths and under continuous-wave pumping. We show that when the pump wavelength is located in between the zero-dispersion wavelengths, a wide and uniform spectral broadening is achieved through modulation instability, generation of both blue-shifted and red-shifted dispersive waves and subsequently through soliton self-frequency shift. This supercontinuum is therefore bounded by these two dispersive waves which allow the control of its bandwidth by a suitable tuning of the fiber dispersion. As a relevant example, we predict that broadband (1050-1600 nm) continuous-wave light can be generated in short lengths of microstructured fibers pumped by use of a 10-W Ytterbium fiber laser.

SPR biosensing coupled to a digital microfluidic microstreaming system.

This article reports on a proof-of-concept system composed of a droplet based surface plasmon resonance (SPR) system coupled to a surface acoustic wave (SAW) microfluidic plateform. It is now well established that surface based binding analyses such as SPR are highly influenced by the transport of analyte to the sensing surface. Further, obtaining reliable equilibrium in flow cells to realize quantification studies is not straightforward. An original solution compared to generally used pressure driven flows is then proposed to favourably cope with these issues. Efficiency of SAW microstreaming coupled to SPR biosensing is considered, in order to improve the accuracy of kinetic parameter estimation in mass transport limited regime and to realize reliable quantification studies. First, the droplet based SPR technique and its advantages are presented. Then, the integration of the microstreaming on the system is discussed. Streptavidin binding is then monitored in static mode and under SAW streaming mode.

On the nature of photoluminescence in Bismuth-doped silica glass.

We report on the investigation of Bismuth-doped pure silica glass without other co-dopant by the tech- nique of magnetic circular dichroism (MCD), which allows the direct probing of the ground state of optical centres. Taking into account the results of conventional optical spectroscopy, we show that the observed MCD bands belong to the centre responsible for the red photoluminescence in this material. Measurements of the temperature and field dependences indicate that the MCD effect is caused by the even-electron system. This, however, opposes the widespread opinion that Bi2+ ions are the origin of red photoluminescence in Bismuth-doped silica glasses. On the other hand, the lasing centre responsi- ble for the near infrared photoluminescence does not exhibit any magnetic optical activity connected to its ground state. As a consequence, we conclude that the ground state of lasing centre is a magnetic singlet with the effective spin S = 0.

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.