Photocycle of point defects in highly- and weakly-germanium doped silica revealed by transient absorption measurements with femtosecond tunable pump.

We report pump-probe transient absorption measurements addressing the photocycle of the Germanium lone pair center (GLPC) point defect with an unprecedented time resolution. The GLPC is a model point defect with a simple and well-understood electronic structure, highly relevant for several applications. Therefore, a full explanation of its photocycle is fundamental to understand the relaxation mechanisms of such molecular-like systems in solid state. The experiment, carried out exciting the sample resonantly with the ultraviolet (UV) GLPC absorption band peaked at 5.1 eV, gave us the possibility to follow the defect excitation-relaxation dynamics from the femto-picosecond to the nanosecond timescale in the UV-visible range. Moreover, the transient absorption signal was studied as a function of the excitation photon energy and comparative experiments were conducted on highly- and weakly-germanium doped silica glasses. The results offer a comprehensive picture of the relaxation dynamics of GLPC and allow observing the interplay between electronic transitions localized on the defect and those related to bandgap transitions, providing a clear evidence that the role of dopant high concentration is not negligible in the earliest dynamics.

Distributed detection of hydrogen and deuterium diffusion into a single-mode optical fiber with chirped-pulse phase-sensitive optical time-domain reflectometry.

For some infrastructures such as oil and gas extraction boreholes or radioactive waste repositories, where distributed optical fiber sensors are employed to grant the safety of the facilities, the presence of gas species such as hydrogen or deuterium is one of the most relevant parameters to monitor. The possibility of employing the same kind of sensors for this purpose is of special interest, reducing the cost by employing a single interrogator, able to measure multiple parameters by simply employing adequate sensing fibers. To meet this goal, we present here a chemical sensor based on chirped-pulse phase-sensitive optical time-domain reflectometry (CP-φOTDR), which is able to detect these species while they diffuse into the silica fiber. The ability of chirped-pulse φOTDR to measure a change in refractive index with sensitivity around 10-8 has allowed determining hydrogen concentration with accuracy on the order of 10-3 mol/m3 and spatial resolution ∼6 m. Another experiment provides an indirect measurement of the solubility of deuterium in a standard telecom-grade optical fiber, which is found to be around 1.47×1024 m3/bar.

Novel Gd3+-doped silica-based optical fiber material for dosimetry in proton therapy.

Optical fibers hold promise for accurate dosimetry in small field proton therapy due to their superior spatial resolution and the lack of significant Cerenkov contamination in proton beams. One known drawback for most scintillation detectors is signal quenching in areas of high linear energy transfer, as is the case in the Bragg peak region of a proton beam. In this study, we investigated the potential of innovative optical fiber bulk materials using the sol-gel technique for dosimetry in proton therapy. This type of glass is made of amorphous silica (SiO[Formula: see text]) and is doped with Gd[Formula: see text] ions and possesses very interesting light emission properties with a luminescence band around 314 nm when exposed to protons. The fibers were manufactured at the University of Lille and tested at the TRIUMF Proton Therapy facility with 8.2-62.9 MeV protons and 2-6 nA of extracted beam current. Dose-rate dependence and quenching were measured and compared to other silica-based fibers also made by sol-gel techniques and doped with Ce[Formula: see text] and Cu[Formula: see text]. The three fibers present strong luminescence in the UV (Gd) or visible (Cu,Ce) under irradiation, with the emission intensities related directly to the proton flux. In addition, the 0.5 mm diameter Gd[Formula: see text]-doped fiber shows superior resolution of the Bragg peak, indicating significantly reduced quenching in comparison to the Ce[Formula: see text] and Cu[Formula: see text] fibers with a Birks' constant, k[Formula: see text], of (0.0162 [Formula: see text] 0.0003) cm/MeV in comparison to (0.0333 [Formula: see text] 0.0006) cm/MeV and (0.0352 [Formula: see text] 0.0003) cm/MeV, respectively. To our knowledge, this is the first report of such an interesting k[Formula: see text] for a silica-based optical fiber material, showing clearly that this fiber presents lower quenching than common plastic scintillators. This result demonstrates the high potential of this inorganic fiber material for proton therapy dosimetry.

Investigations of the MGy dose level radiation effects on the photometric budget of a radiation-hardened CMOS-based camera.

We studied the impact of ionizing radiation at high dose levels (megagray, MGy) on the photometric budget of a radiation-resistant complementary metal oxide semi-conductor (CMOS)-based camera. This is achieved by measuring the radiation-induced degradation of each subpart, namely its illumination system, its optical system, and its CMOS image sensor. The acquired experimental results allow performing a rather realistic simulation of the radiation effects at the system level. Thanks to appropriate mitigation techniques, limited image darkening and color change are obtained at MGy dose levels. The presented results confirm the feasibility of a CMOS-based camera able to resist to MGy dose level of ionizing radiations with an acceptable degradation of the image quality, opening the way to its implementation in the most challenging harsh environments.

v-P2O5 micro-clustering in P-doped silica studied by a first-principles Raman investigation.

Synthetic vitreous silica is currently the preferred material for the production of optical fibres because of the several excellent properties of this glass, e.g. high transmission in the visible and IR domains, high mechanical strength, chemical durability, and ease of doping with various materials. For instance, fiber lasers and amplifiers exploit the light amplification properties provided by rare-earth ions employed as dopants in the core of silica-based optical fibers. The structure and composition of the nearest neighbor shell surrounding rare-earth ions in silica-based optical fibers and amplifiers have been intensively debated in the last decade. To reduce aggregation effects between rare-earth ions, co-dopants such as phosphorus and aluminium are added as structural modifiers; phosphorus-doping, in particular, has proved to be very efficient in dissolving rare-earth ions. In this work, we provide further insights concerning the embedding of P atoms into the silica network, which may be relevant for explaining the ease of formation of a phosphorus pentoxide nearest-neighbor shell around a rare-earth dopant. In particular, by means of first-principles calculations, we discuss alternative models for an irradiation (UV, x-, γ-rays) induced paramagnetic center, i.e. the so called room-temperature phosphorus-oxygen-hole center, and its precursors. We report that the most likely precursor of a room-temperature phosphorus-oxygen-hole center comprises of a micro-cluster of a few (at least two) neighboring phosphate tetrahedra, and correspondingly that the occurrence of isolated [(O-)2P(=O)2]- units is unlikely even at low P-doping concentrations. In fact, this work predicts that the symmetric stretching of P=O bonds in isolated [(O-)2P(=O)2]- units appears as a Raman band at a frequency of ~1110 cm-1, and only by including at least another corner-sharing phosphate tetrahedron, it is shown to shift to higher frequencies (up to ~40 cm-1) due to the shortening of P=O bonds, thereby leading to an improved agreement with the observed Raman band located at ~1145 cm-1.

Real time monitoring of water level and temperature in storage fuel pools through optical fibre sensors.

We present an innovative architecture of a Rayleigh-based optical fibre sensor for the monitoring of water level and temperature inside storage nuclear fuel pools. This sensor, able to withstand the harsh constraints encountered under accidental conditions such as those pointed-out during the Fukushima-Daiichi event (temperature up to 100 °C and radiation dose level up to ~20 kGy), exploits the Optical Frequency Domain Reflectometry technique to remotely monitor a radiation resistant silica-based optical fibre i.e. its sensing probe. We validate the efficiency and the robustness of water level measurements, which are extrapolated from the temperature profile along the fibre length, in a dedicated test bench allowing the simulation of the environmental operating and accidental conditions. The conceived prototype ensures an easy, practical and no invasive integration into existing nuclear facilities. The obtained results represent a significant breakthrough and comfort the ability of the developed system to overcome both operating and accidental constraints providing the distributed profiles of the water level (0-to-5 m) and temperature (20-to-100 °C) with a resolution that in accidental condition is better than 3 cm and of ~0.5 °C respectively. These new sensors will be able, as safeguards, to contribute and reinforce the safety in existing and future nuclear power plants.

Photoactivated processes in optical fibers: generation and conversion mechanisms of twofold coordinated Si and Ge atoms.

In this work we present an extensive investigation of nanoscale physical phenomena related to oxygen-deficient centers (ODCs) in silica and Ge-doped silica by means of first-principles calculations, including nudged-elastic band, electron paramagnetic resonance parameters calculations, and many-body perturbation theory (GW and Bethe-Salpeter equation) techniques. We show that by neutralizing positively charged oxygen monovacancies we can obtain model structures of twofold Si and Ge defects of which the calculated absorption spectra and singlet-to-triplet transitions are in excellent agreement with the experimental optical absorption and photo-luminescence data. In particular we provide an exhaustive analysis of the main exciton peaks related to the presence of twofold defects including long-range correlation effects. By calculating the reaction pathways and energy barriers necessary for the interconversion, we advance a double precursory origin of the [Formula: see text] and Ge(2) centers as due to the ionization of neutral oxygen monovacancies (Si-Si and Ge-Si dimers) and as due to the ionization of twofold Si and Ge defects. Furthermore two distinct structural conversion mechanisms are found to occur between the neutral oxygen monovacancy and the twofold Si (and Ge) atom configurations. Such conversion mechanisms allow to explain the radiation induced generation of the ODC(II) centers, their photobleaching, and also their generation during the drawing of optical fibers.

Radiation effects on optical frequency domain reflectometry fiber-based sensor.

We investigate the radiation effects on germanosilicate optical fiber acting as the sensing element of optical frequency domain reflectometry devices. Thanks to a new setup permitting to control temperature during irradiation, we evaluate the changes induced by 10 keV x rays on their Rayleigh response up to 1 MGy in a temperature range from -40°C up to 75°C. Irradiation at fixed temperature points out that its measure is reliable during both irradiation and the recovery process. Mixed temperature and radiation measurements show that changing irradiation temperature leads to an error in distributed measurements that depends on the calibration procedure. These results demonstrate that Rayleigh-based optical fiber sensors are very promising for integration in harsh environments.

Vulnerability of OFDR-based distributed sensors to high γ-ray doses.

Vulnerability of Optical Frequency Domain Reflectometry (OFDR) based sensors to high γ-ray doses (up to 10 MGy) is evaluated with a specific issue of a radiation-hardened temperature and strain monitoring system for nuclear industry. For this, we characterize the main radiation effects that are expected to degrade the sensor performances in such applicative domain: the radiation-induced attenuation (RIA), the possible evolution with the dose of the Rayleigh scattering phenomenon as well as its dependence on temperature and strain. This preliminary investigation is done after the irradiation and for five different optical fiber types covering the range from radiation-hardened fibers to highly radiation sensitive ones. Our results show that at these high dose levels the scattering mechanism at the basis of the used technique for the monitoring is unaffected (changes below 5%), authorizing acceptable precision on the temperature or strain measurements. RIA has to be considered as it limits the sensing range. From our vulnerability study, the OFDR sensors appear as promising candidates for nuclear industry even at doses as high as 10 MGy.

Identification of a soft tissue filler by ex vivo confocal microscopy and Raman spectroscopy in a case of adverse reaction to the filler.

BACKGROUND: Soft tissue fillers are usually identified in the skin using the conventional histopathologic examination. Ex vivo RCM has been used in one case and Raman spectroscopy (RS), which has been recently applied for the identification of skin foreign bodies, has never been employed for fillers. We report the use of both these new techniques, ex vivo RCM and RS, to confirm the diagnosis of adverse reaction to a soft tissue filler and to identify its composition. METHODS: We excised a skin nodule suspicious of adverse reaction to soft tissue filler, and we performed an ex vivo reflectance confocal microscopy (RCM) and an histopathologic examination, followed by a RS analysis. RESULTS: Ex vivo RCM showed numerous hypo-reflective microspheres in the dermis that corresponded to rounded vacuoles at histopathologic examination, suggestive of polymethylmethacrylate (PMMA). RS showed a series of peaks at 600, 813, 970 1252, 1450, 1728, and 2951 cm(-1) in correspondence to the microspheres, confirming the presence of PMMA. CONCLUSION: These results suggest that ex vivo RCM and RS are additional tools to conventional histopathologic examination to characterize soft tissue fillers in case of adverse reaction. RCM has the advantage compared with the histopathologic examination that can be extemporaneously performed on a fresh surgical specimen. RS allow a precise chemical identification of the filler.

Radiation-hard erbium optical fiber and fiber amplifier for both low- and high-dose space missions.

We present a new structure for erbium-doped optical fibers [hole-assisted carbon-coated, (HACC)] that, combined with an appropriate choice of codopants in the core, strongly enhances their radiation tolerance. We built an erbium-doped fiber amplifier based on this HACC fiber and characterize its degradation under γ-ray doses up to 315 krad (SiO2) in the ON mode. The 31 dB amplifier is practically radiation insensitive, with a gain change of merely -2.2×10(-3) dB/krad. These performances authorize the use of HACC doped fibers and amplifiers for various applications in environments associated with today's missions (of doses up to 50 krad) and even for future space missions associated with higher dose constraints.

Radiation tolerant fiber Bragg gratings for high temperature monitoring at MGy dose levels.

We report a method for fabricating fiber Bragg gratings (FBG) resistant to very severe environments mixing high radiation doses (up to 3 MGy) and high temperatures (up to 230°C). Such FBGs have been written in two types of radiation resistant optical fibers (pure-silica and fluorine-doped cores) by exposures to a 800 nm femtosecond IR laser at power exceeding 500 mW and then subjected to a thermal annealing treatment of 15 min at 750°C. Under radiation, our study reveals that the radiation induced Bragg wavelength shift (BWS) at a 3 MGy dose is strongly reduced compared to responses of FBGs written with nonoptimized conditions. The BWS remains lower than 10 pm for temperatures of irradiation ranging from 25°C to 230°C without noticeable decrease of the FBG peak amplitude. For an applicative point of view, this radiation induced BWS corresponds to an additional error on the temperature measurements lower than 1.5°C, opening the way to the development of radiation-tolerant multi-point temperature sensors for nuclear industry.

Oxygen deficient centers in silica: optical properties within many-body perturbation theory.

The electronic and optical properties of neutral oxygen vacancies, also called oxygen deficient centers (ODC(I)s), have been investigated in pure and germanium doped silica (both amorphous and α-quartz) through first-principles calculations. By means of density functional theory and many-body perturbation theory (GW approximation and the solution of the Bethe-Salpeter equation), we obtain the atomic and electronic structures as well as the optical absorption spectra of pure and Ge-doped silica in the presence of ODCs (SiODC(I)s and GeODC(I)s); our study allows us to interpret and explain the very nature of the optical features in experimental absorption spectra. The theoretical optical absorption signatures of these defects show excellent agreement with experiments for the SiODC(I)s, i.e. two absorption bands arise around 7.6 eV due to transitions between the defect levels. Our theoretical results also explain the experimental difficulty in measuring the GeODC(I) absorption band in Ge-doped silica, which was in fact tentatively assigned to a broad and very weak absorption signature, located between 7.5 and 8.5 eV. The influence of Ge-doping induced disorder on the nature of the defect-related optical transitions is discussed. We find that even if the atomic and electronic structures of SiODC(I) and GeODC(I) defects are relatively similar, the slight network distortion induced by the presence of the Ge atom, together with the increase in the Ge-Si bond asymmetry, completely changes the nature of the optical absorption edge.

Transient radiation-induced effects on solid core microstructured optical fibers.

We report transient radiation-induced effects on solid core microstructured optical fibers (MOFs). The kinetics and levels of radiation-induced attenuation (RIA) in the visible and near-infrared part of the spectrum (600 nm-2000 nm) were characterized. It is found that the two tested MOFs, fabricated by the stack-and-draw technique, present a good radiation tolerance. Both have similar geometry but one has been made with pure-silica tubes and the other one with Fluorine-doped silica tubes. We compared their pulsed X-ray radiation sensitivities to those of different classes of conventional optical fibers with pure-silica-cores or cores doped with Phosphorus or Germanium. The pulsed radiation sensitivity of MOFs seems to be mainly governed by the glass composition whereas their particular structure does not contribute significantly. Similarly for doped silica fibers, the measured spectral dependence of RIA for the MOFs cannot be correctly reproduced with the various absorption bands associated with the Si-related defects identified in the literature. However, our analysis confirms the preponderant role of self-trapped holes with their visible and infrared absorption bands in the transient behaviors of pure-silica of F-doped fibers. The results of this study showed that pure-silica or fluorine-doped MOFs, which offers specific advantages compared to conventional fibers, are promising for use in harsh environments due to their radiation tolerance.

Influence of reduction processes on the colour and photochromism of amorphous mesoporous TiO(2) thin films loaded with a silver salt.

Silver nanoparticles were created inside mesoporous titania thin films by different reduction processes. We investigated the influence of the reduction method on the colour and photochromism of these amorphous TiO(2) films. The results highlight brown films by optical reduction, gray films by thermal reduction, and red, purple or orange films by chemical reduction. The different size distributions and localizations of the nanoparticles, characterized by UV-visible spectroscopy and electron microscopy, give various photochromic behaviours when exposed to visible laser light. We especially report the bleaching of different film colours under laser exposure.

Evolution of photo-induced defects in Ge-doped fiber/preform: influence of the drawing.

We have studied the generation mechanisms of two different radiation-induced point defects, the Ge(1) and Ge(2) centers, in a germanosilicate fiber and in its original preform. The samples have been investigated before and after X-ray irradiation using the confocal microscopy luminescence and the electron paramagnetic resonance techniques. Our experimental results show the higher radiation sensitivity of the fiber as compared to the perform and suggest a relation between Ge(1) and Ge(2) generation. To explain our data we have used different models, finding that the destruction probability of the Ge(1) and Ge(2) defects is larger in fiber than in preform, whereas the generation one is similar. Finally we found that the higher radiation sensitivity of the fiber at low doses is essentially related to the presence of germanium lone pair center generated by the drawing.

Nanosize structural modifications with polarization functions in ultrafast laser irradiated bulk fused silica.

Laser-induced self-organization of regular nanoscale layered patterns in fused silica is investigated using spectroscopy and microscopy methods, revealing a high presence of stable broken oxygen bonds. Longitudinal traces are then generated by replicating static irradiation structures where the nanoscale modulation can cover partially or completely the photoinscribed traces. The resulting birefringence, the observed anisotropic light scattering properties, and the capacity to write and erase modulated patterns can be used in designing bulk polarization sensitive devices. Various laser-induced structures with optical properties combining guiding, scattering, and polarization sensitivity are reported. The attached polarization functions were evaluated as a function of the fill factor of the nanostructured domains. The polarization sensitivity allows particular light propagation and confinement properties in three dimensional structures.

Influence of the drawing process on the defect generation in multistep-index germanium-doped optical fibers.

Variation of germanium lone pair center (GLPC) concentration in germanosilicate multistep-index optical fibers and preforms was studied using confocal microscopy luminescence technique. The experimental results provide evidence that in the central core region ([Ge] approximately 11 wt.%) of our specific canonical samples the ratio [GLPC]/[Ge] is five times larger in fiber than in preforms. The relative influence of the glass composition and of the drawing process on the generation efficiency of the GLPC defects that drive the glass photosensitivity is discussed. The radial distribution of these defects suggests a possible enhancement of the defect creation related to the internal stress of the fiber core.