UV-Photoinduced Defects In Ge-Doped Optical Fibers

We investigated the effect of continuous-wave (cw) UV laser radiation on single-mode Ge-doped H2- loaded optical fibers. An innovative technique was developed to measure the optical absorption (OA) induced in the samples by irradiation, and to study its dependence from laser fluence. The combined use of the electron spin resonance (ESR) technique allowed the structural identification of several radiation-induced point defects, among which the Ge(1) (GeO4 -) is found to be responsible of induced OA in the investigated spectral region.

Direct sunlight facility for testing and research in HCPV

A facility for testing different components for HCPV application has been developed in the framework of "Fotovoltaico ad Alta Efficienza" (FAE) project funded by the Sicilian Regional Authority (PO FESR Sicilia 2007/2013 4.1.1.1). The testing facility is equipped with an heliostat providing a wide solar beam inside the lab, an optical bench for mounting and aligning the HCPV components, electronic equipments to characterize the I-V curves of multijunction cells operated up to 2000 suns, a system to circulate a fluid in the heat sink at controlled temperature and flow-rate, a data logging system with sensors to measure temperatures in several locations and fluid pressures at the inlet and ou…

One-pot synthesis of graphene quantum dots and simultaneous nanostructured self-assembly via a novel microwave-assisted method: impact on triazine removal and efficiency monitoring

One-step methods for fabricating green materials endowed with diverse functions is a challenge to be overcome in terms of reducing environmental risk and cost. We report a fast and easy synthesis of multifunctional materials composed of only fluorescent dots with structural flexibility and high sorption capability. The synthesis consists of a one-pot microwave-assisted reaction for the simultaneous formation of graphene quantum dots (GQDs) from organic precursors and their spontaneous self-assembly forming porous architectures. The GQD-assemblies are robust and no signs of degradation were observed with most organic solvents. The ensuing GQDs and their porous solids were fully characterized…

Decomposition Process of Carboxylate MOF HKUST-1 Unveiled at the Atomic Scale Level

HKUST-1 is a metal-organic framework (MOF) which plays a significant role both in applicative and basic fields of research, thanks to its outstanding properties of adsorption and catalysis but also because it is a reference material for the study of many general properties of MOFs. Its metallic group comprises a pair of Cu2+ ions chelated by four carboxylate bridges, forming a structure known as paddle-wheel unit, which is the heart of the material. However, previous studies have well established that the paddle-wheel is incline to hydrolysis. In fact, the prolonged exposure of the material to moisture promotes the hydrolysis of Cu-O bonds in the paddle-wheels, so breaking the crystalline n…

Isoelectronic series of oxygen deficient centers in silica: experimental estimation of homogeneous and inhomogeneous spectral widths

We report nanosecond time-resolved photoluminescence measurements on the isoelectronic series of oxygen deficient centers in amorphous silica related to silicon, germanium and tin atoms, which are responsible of fluorescence activities at approximately 4 eV under excitation at approximately 5 eV. The dependence of the first moment of their emission band on time and that of the radiative decay lifetime on emission energy are analyzed within a theoretical model able to describe the effects introduced by disorder on the optical properties of the defects. We obtain separate estimates of the homogeneous and inhomogeneous contributions to the measured emission line width, and we derive homogeneou…

Visible-ultraviolet vibronic emission of silica nanoparticles

We report the study of the visible-ultraviolet emission properties and the structural features of silica nanoparticles prepared through a laboratory sol-gel technique. Atomic force microscopy, Raman and Infrared investigations highlighted the 10 nm size, purity and porosity of the obtained nanoparticles. By using time resolved photoluminescence techniques in air and in a vacuum we were able to single out two contributions in the visible emission: the first, stable in both atmospheres, is a typical fast blue band centered around 2.8 eV; the second, only observed in a vacuum around the 3.0-3.5 eV range, is a vibrational progression with two phonon modes at 1370 cm(-1) and 360 cm(-1). By fully…

Micro-Raman characterization of graphene grown on SiC(000-1)

Graphene (Gr) was grown on the C face of 4H-SiC under optimized conditions (high annealing temperatures ranging from 1850 to 1950°C in Ar ambient at 900 mbar) in order to achieve few layers of Gr coverage. Several microscopy techniques, including optical microscopy (OM), ?Raman spectroscopy, atomic force microscopy (AFM) and atomic resolution scanning transmission electron microscopy (STEM) have been used to extensively characterize the lateral uniformity of the as-grown layers at different temperatures. ?Raman analysis provided information on the variation of the number of layers, of the stacking-type, doping and strain.

Photoluminescence activity in natural silica excited in the vacuum-UV range

Abstract We report an experimental study on the optical absorption and photoluminescence detected in samples of natural silica. Our results show that the two emission bands, β (∼3.1 eV) and α E (∼4.3 eV), have an excitation profile in the vacuum ultraviolet region with a maximum at ∼7.5 eV. This excitation profile indicates that, in terms of energy levels of the luminescent defect, there is a transition from a ground state, S 0 , to a second excited state, S 2 , able to excite PL emission, in addition to the well known transition corresponding to the optical absorption band, B 2β . Our data are in a quantitative agreement with `ab initio' calculations carried out for a two-fold coordinated …

Radiation Hardened Optical Frequency Domain Reflectometry Distributed Temperature Fiber-Based Sensors

International audience; We study the performance of Optical Frequency Domain Reflectometry (OFDR) distributed temperature sensors using radiation resistant single-mode optical fibers. In situ experiments under 10 keV X-rays exposure up to 1 MGy( SiO 2 ) were carried out with an original setup that allows to investigate combined temperature and radiation effects on the sensors within a temperature range from 30 ° C to 250 ° C. Obtained results demonstrate that optical fiber sensors based on Rayleigh technique are almost unaffected by radiation up to the explored doses. We show that a pre-thermal treatment stabilize the sensor performance increasing the accuracy on temperature measurement fro…

In-situ observation of beta-ray induced UV optical absorption in a-SiO2: radiation darkening and room temperature recovery

International audience; We studied the optical absorption in the 3.0-6.2 eV range induced in bulk amorphous SiO2 by beta-ray irradiation up to similar to 1 MGy at room temperature. The induced absorption was measured in situ both during irradiation and in the post irradiation time. Our data evidence E', center as the main defect induced by irradiation and the partial decay of their absorption band at about 5.8 eV after irradiation. A quantitative analysis of the time evolution of the induced absorption shows that the transmission recovery observed after irradiation is compatible with the reaction of radiation-induced defects with H-related (H-2, H2O) species diffusing in the amorphous matrix

Resonance Raman of oxygen dangling bonds in amorphous silicon dioxide

We investigate the origin of a resonance Raman band induced by ionizing radiation in amorphous silicon dioxide (silica glass), which can be detected under ultraviolet laser excitation. A silica sample, rich of oxygen-excess related defects, was prepared by treating some length of a pure-silica-core multimode fiber in an O2 atmosphere (at high temperature and pressure) and by irradiating it with X-rays at 10 MGy(SiO2) dose. A micro-Raman study revealed a gaussian band peaking at 896 cm−1 with a full width at half maximum of 32 cm−1, which could be detected by exciting the sample with the 325-nm line of a HeCd laser. This spectral feature is absent in the Raman spectra performed with the 442-…

Effect of thermal annealing on the luminescence of defective ZnO nanoparticles synthesized by pulsed laser ablation in water

This work concerns ZnO nanoparticles (NPs), with sizes of tens of nm, produced by ablation with a pulsed Nd:YAG laser of a Zn plate in H2O. TEM images evidence the formation of nanoparticles with sizes of tens of nm. Moreover, HRTEM images and Raman spectra show that the distance between the crystalline planes and the vibrational modes are consistent with ZnO nanocrystal in wurtzite structure. Their optical properties are characterized by two emission bands both excited above the energy gap (3.4 eV): the first at 3.3 eV is associated with excitons recombination, the second at 2.2 eV is proposed to originate from a singly ionized oxygen vacancy. The green emission is independent of water pH,…

Generation and excitation of point defects in silica by synchrotron radiation above the absorption edge

We report photoluminescence measurements carried out on amorphous SiO{sub 2} upon excitation by synchrotron light. Exposure of the as-grown material to above-edge light at low temperature induces the formation of nonbridging oxygen hole centers (NBOHC), localized in a thin layer below the surface limited by the penetration depth (tens of nm) of impinging light. After concluding the exposure to 11 eV light, stable defects are revealed by observing their characteristic 1.9 eV photoemission band excited at 4. 8eV. The local concentration of induced defects, supposedly formed by nonradiative decay of excitons, is very high (close to approx10{sup 21} cm{sup -3}) and independent of the previous h…

Influence of specific codopants and post-treatments on Erbium Doped Fibers: Radiation behavior characteristics by CML

Coating impact and radiation effects on optical frequency domain Reflectometry fiber-based temperature sensors

International audience; Temperature response of radiation-tolerant OFDR-based sensors is here investigated, with particular attention on the impact of coating on OFS. By performing consecutive thermal treatments we developed a controlled system to evaluate the performances of our distributed temperature sensor and to estimate the radiation impact. We show an important evolution of the temperature coefficient measurements with thermal treatments for non-irradiated fiber and that the amplitude of this change decreases increasing radiation dose. As final results, we demonstrate that sensor performances are improved if we performed a pre-thermal treatment on the fiber-based system permitting to…

Atomically Precise Distorted Nanographenes: The Effect of Different Edge Functionalization on the Photophysical Properties down to the Femtosecond Scale

Nanographenes (NGs) have been attracting widespread interest since they combine peculiar properties of graphene with molecular features, such as bright visible photoluminescence. However, our understanding of the fundamental properties of NGs is still hampered by the high degree of heterogeneity usually characterizing most of these materials. In this context, NGs obtained by atomically precise synthesis routes represent optimal benchmarks to unambiguously relate their properties to well-defined structures. Here we investigate in deep detail the optical response of three curved hexa-peri-hexabenzocoronene (HBC) derivatives obtained by atomically precise synthesis routes. They are constituted…

Characterization of protofibrillar aggregates of bovine serum albumin by tryptophans fluorescence lifetime

We report an experimental study on the thermally induced aggregation of Bovine Serum Albumin at basic pH. In these conditions, we observe the growth of simple protofibrillar structures via the formation of intermolecular beta-sheets promoted by the increased electrostatic repulsion. Here we present a study on the time resolved fluorescence of Tryptophans (Trp) along the aggregation kinetics in the above reported conditions. We use the lifetimes distribution approach as a useful tool for the interpretation of the fluorescence decay in terms of protein conformational substates and interconversion dynamics. Trp fluorescence lifetime depends from protein conformations, also in relation with sol…

Fluorescent Boron Oxide Nanodisks as Biocompatible Multi-messenger Sensors for Ultrasensitive Ni$^{2+}$ Detection

Boron-based nanocomposites are very promising for a wide range of technological applications, spanning from microelectronics to nanomedicine. A large variety of B-based nanomaterials has been already observed, such as borospherene, B nanotubes and nanoparticles, and boron nitride nanoparticles. However, their fabrication usually involves toxic precursors or leads to very low yields or small boron atom concentration. In this work, we report the synthesis of nanometric B$_{2}$O$_{3}$ nanodisks, a family of nanomaterials with a quasi-2D morphology capable of intense fluorescence in the visible range. Such as boron-based nanomaterial, which we synthesized by pulsed laser ablation of a boron tar…

Luminescent silicon nanocrystals produced by near-infrared nanosecond pulsed laser ablation in water

Abstract We report the investigation of luminescent nanoparticles produced by ns pulsed Nd:YAG laser ablation of silicon in water. Combined characterization by AFM and IR techniques proves that these nanoparticles have a mean size of ∼3 nm and a core–shell structure consisting of a Si-nanocrystal surrounded by an oxide layer. Time resolved luminescence spectra evidence visible and UV emissions; a band around 1.9 eV originates from Si-nanocrystals, while two bands centered at 2.7 eV and 4.4 eV are associated with oxygen deficient centers in the SiO 2 shell.

Ge-doped silica nanoparticles: production and characterisation

Silica nanoparticles were produced from germanosilicate glasses by KrF laser irradiation. The samples were investigated by cathodoluminescence and scanning electron microscopy, providing the presence of nanoparticles with size from tens up to hundreds of nanometers. The emission of the Germanium lone pair center is preserved in the nanoparticles and atomic force microscopy revealed the presence of no spherical particles with a size smaller than ~4 nm. The absorption coefficient enhancement induced by Ge doping is reputed fundamental to facilitate the nanoparticles production. This procedure can be applied to other co-doped silica materials to tune the nanoparticles features.

Disclosing the emissive surface traps in green-emitting carbon nanodots

Abstract The bright photoluminescence of surface-functionalized carbon nanoparticles, known as carbon nanodots (CDs), has been studied for more than a decade because of its fundamental photo-physical interest and strong technological potential. However, the essential nature of the electronic states involved in their typical light emission remains very elusive. Here, we provide conclusive evidence that surface carboxylic moieties are the key to CD fluorescence. The synergy of nanosecond and femtosecond optical studies, cryogenic fluorescence, computational investigations and chemical engineering of a strategically chosen model CD system, allows to demonstrate that their visible-light transit…

Photoluminescence at 1.9 eV in synthetic wet silica

We report the effects of γ-irradiation on the optical activity of wet synthetic silica samples. As a function of γ-dose, the growth of a composite structure in the 4–6 eV spectral region of the absorption spectrum is observed. This structure can be resolved into two main contributions centered at 5.8 and 4.8 eV, respectively. The first component is usually attributed to an optical transition of the E′ centers. The second one is able to excite an emission band centered at 1.9 eV. The analysis of the growth kinetics, in the γ-dose range 20–1000 Mrad, of both emission at 1.9 eV and absorption at 4.8 eV shows that these two bands change in a similar way, reaching constant amplitudes, after an i…

Ultraviolet-induced paramagnetic centers and absorption changes in singlemode Ge-doped optical fibers

We investigated the laser-energy-density dependence of absorption changes and paramagnetic centers induced by a cw Ar+ laser operating at 5.1 eV, in both unloaded and H-2-loaded single mode Ge-doped optical fibers. The induced absorption is measured in the blue and near ultraviolet spectral range by using the 3.1 eV photoluminescence, ascribed to Ge lone pair center (GLPC), as an in situ probe source. We find that the Ge (1) center (GeO4-) is induced upon UV exposure by electron trapping on GeO4 precursors, where the free electrons are most likely produced by ionization of GLPC. Ge (1) is responsible of optical transmission loss of the fiber in the investigated range. Hydrogen loading stron…

Tailoring the Emission Color of Carbon Dots through Nitrogen-Induced Changes of Their Crystalline Structure

Nitrogen content in carbon dots (CDs) plays a crucial role both on the structure and on the optical properties. We synthesized two distinct families of CDs which differ both in structure and in optical emission, demonstrating how nitrogen determines the structure and the optical properties of N-CDs in two main cases: low content and high content of nitrogen. While the low-nitrogen-content family is characterized by blue-emitting nanoparticles with a N-doped hexagonal C-graphite crystalline core structure and a complex surface structure, the high-nitrogen-content family is composed of nanoparticles behaving as dual emitters (blue and green) with a hexagonal β-C3N4crystalline core structure a…

Vibronic structures in the visible luminescence of silica nanoparticles

Time resolved photoluminescence investigation in air and in vacuum atmosphere of the visible luminescence related to silica surface defects is here reported. Two contributions can be singled out: one, observed both in air and in vacuum, is the well-known blue band, peaked around 2.8 eV decaying in ∼5 ns; the other, only observed in vacuum, is a structured emission in the violet range characterized by two vibronic progressions spaced 1370 cm−1 and 360 cm−1 decaying in ∼100 ns. In contrast with previous attribution, the well distinguishable spectroscopic properties together with the observation of the effects induced by the interaction with nitrogen allow to state that the emission bands orig…

Optical properties of Ge-oxygen defect center embedded in silica films

The photo-luminescence features of Ge-oxygen defect centers in a 100nm thick Ge-doped silica film on a pure silica substrate were investigated by looking at the emission spectra and time decay detected under synchrotron radiation excitation in the 10-300 K temperature range. This center exhibits two luminescence bands centered at 4.3eV and 3.2eV associated with its de-excitation from singlet (S1) and triplet (T1) states, respectively, that are linked by an intersystem crossing process. The comparison with results obtained from a bulk Ge-doped silica sample evidences that the efficiency of the intersystem crossing rate depends on the properties of the matrix embedding the Ge-oxygen defect ce…

Effects induced by 4.7 eV UV laser irradiation on pure silica core multimode optical fibers investigated by in situ optical absorption measurements

We investigated by in situ optical absorption measurements the effects induced by 4.7 eV UV laser irradiation on pure silica core optical fibers. Laser irradiation with 100 MWcm−2 laser intensity generates in the fiber E′ centers which partially decay after irradiation due to their reaction with diffusing H2. An absorption band peaked at 5.3 eV is observed to grow in the post-irradiation stage with a kinetics anti-correlated to the decay of the 5.8 eV band of the E′ centers. The defect absorbing at 5.3 eV is proposed to be formed by trapping on pre-existing precursors of hydrogen atoms made available by breaking of H2 on E′.We also show by repeated irradiation experiments that the 5.3 eV-ab…

Gallium doped SiO2: Towards a new luminescent material

We show how the interaction between Ga atoms and silica samples in a hot environment gives rise to permanent inclusions of Ga inside the silica matrix which, in turn, produce typical luminescence features. The Ga doped silica is analyzed via laser induced fluorescence, photoluminescence and electron paramagnetic resonance spectroscopies. The results evidence the presence of modifications induced by the Ga inclusions inside the silica matrix and some preliminary hypothesis on their nature are advanced. Possible applications of such Ga doped silica are also mentioned.

Electron transfer between carbon dots and tetranuclear Dawson-derived sandwich polyanions

Among the photocatalysts which could be used for converting solar energy, polyoxometalates are often regarded as ideal candidates because of their remarkable performances in photocatalytic water splitting and photodegradation of pollutants. Nonetheless, these polyanions are only capable of absorbing UV light, unless coupled to a visible-light photosensitizer. Carbon nanodots are especially promising for this purpose because of their strong visible-light absorption, photostability, non-toxicity, and very low production costs. In this work we demonstrate the possibility of coupling carbon dots to polyoxometalates with different structures, by a simple self-assembly approach based on electrost…

Irradiation induced defects in fluorine doped silica

International audience; The role of fluorine doping in the response to UV pulsed laser and c radiation of silica preforms and fibers was studied using electron spin resonance (ESR) spectroscopy. Exposure to radiation mainly generates E0 centers, with the same effectiveness in fibers and in preforms. The E'concentration in F-doped silica fibers is found to increase with UV energy fluence till a saturation value, consistently with a precursor conversion process. These results show the fluorine role in reducing the strained Si–O bonds thus improving the radiation hardness of silica, also after drawing process.

Bleaching of optical activity induced by UV Laser exposure in natural silica

We report experimental data on two types of natural silica, differing for their OH content, irradiated with UV photons (4.66 eV) from a pulsed Nd:YAG laser. Irradiation induces a reduction of the absorption band at 5.12eV and of the associated emissions at 3.14eV and 4.28eV, ascribed to twofold coordinated Ge (=Ge'') centers pre-existing in our samples. The bleaching is mainly due to the post-irradiation conversion of =Ge'' into the paramagnetic H(II) center via trapping of a H atom. Comparison with literature data points out the peculiarities of silica with a low Ge concentration as regards UV induced transformations.

Influence du rayonnement X sur des fibres et préformes canoniques dopées au phosphore

γ-ray-induced bleaching in silica: Conversion from optical to paramagnetic defects

We report experimental results on optical and ESR measurements performed in $\ensuremath{\gamma}$-irradiated natural silica samples having different content of OH groups. A partial bleaching of the optical absorption band ${B}_{2\ensuremath{\beta}}$ at 5.15 eV and the related photoluminescence emissions at 3.1 eV and 4.2 eV is observed together with the growth of an ESR doublet split by 11.8 mT. The kinetics of the two processes as a function of the $\ensuremath{\gamma}$ dose are correlated and depend on the OH content. Our experiments indicate the occurrence of a $\ensuremath{\gamma}$-ray-induced conversion, from optically active centers to paramagnetic ones and vice versa, changing the re…

Unraveling exciton dynamics in amorphous silicon dioxide: Interpretation of the optical features from 8 to 11 eV.

Physical review / B 83, 174201 (2011). doi:10.1103/PhysRevB.83.174201

Substrate and atmosphere influence on oxygen p-doped graphene

Abstract The mechanisms responsible for p-type doping of substrate supported monolayer graphene (Gr) by thermal treatments in oxygen ambient have been investigated by micro-Raman spectroscopy, atomic force microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), considering commonly employed dielectric substrates, such as SiO 2 and Al 2 O 3 thin films grown on Si. While a high p-type doping (∼10 13  cm −2 ) is observed for Gr on SiO 2 , no significant doping is found for Gr samples on the Al 2 O 3 substrate, suggesting a key role of the Gr/SiO 2 interface states in the trapping of oxygen responsible for the Gr p-type doping. Furthermore, we investigated the doping stability of Gr on SiO…

Origins of radiation-induced attenuation in pure-silica-core and Ge-doped optical fibers under pulsed x-ray irradiation

We investigated the nature, optical properties, and decay kinetics of point defects causing large transient attenuation increase observed in silica-based optical fibers exposed to short duration and high-dose rate x-ray pulses. The transient radiation-induced attenuation (RIA) spectra of pure-silica-core (PSC), Ge-doped, F-doped, and Ge + F-doped optical fibers (OFs) were acquired after the ionizing pulse in the spectral range of [∼0.8–∼3.2] eV (∼1500–∼380 nm), from a few ms to several minutes after the pulse, at both room temperature (RT) and liquid nitrogen temperature (LNT). Comparing the fiber behavior at both temperatures better highlights the thermally unstable point defects contribut…

Optical frequency domain reflectometer distributed sensing using microstructured pure silica optical fibers under radiations

International audience; We investigated the capability of micro-structured optical fibers to develop multi-functional, remotely-controlled, Optical Frequency Domain Reflectometry (OFDR) distributed fiber based sensors to monitor temperature in nuclear power plants or high energy physics facilities. As pure-silica-core fibers are amongst the most radiation resistant waveguides, we characterized the response of two fibers with the same microstructure, one possessing a core elaborated with F300 Heraeus rod representing the state-of-the art for such fiber technology and one innovative sample based on pure sol-gel silica. Our measurements reveal that the Xray radiations do not affect the capaci…

Synthesis of multi-color luminescent ZnO nanoparticles by ultra-short pulsed laser ablation

Abstract Crystalline ZnO nanoparticles (NPs) are synthesized by ultra-short femtosecond (fs) pulsed laser ablation (PLA) of a zinc plate in deionized water, and are investigated by optical absorption and time resolved luminescence spectra in combination with the morphology and structure analysis. The comparison with previous experiments based on short nanosecond (ns) PLA highlights that pulse duration is a crucial parameter to determine the size and the optical properties of ZnO NPs. While short PLA generates NPs with average size S ‾ of ~ 30 nm, ultrashort PLA allows to achieve much smaller NPs, S ‾ ⩽ 10  nm, that evidence weak quantum confinement effects on both the absorption edge and th…

The structural disorder of a silica network probed by site selective luminescence of the nonbridging oxygen hole centre

We studied the inhomogeneous distribution of the luminescence band associated with the nonbridging oxygen hole centre in silica through site selective excitation/detection of the zero phonon line by a tunable laser source. Defects induced in the bulk of synthetic samples by γ and β exposure exhibit an increase of the inhomogeneous width from 0.071 to 0.086 eV on increasing the irradiation dose from 2 × 10(6) to 5 × 10(9) Gy. We also investigated two defect variants stabilized at the surface of the silica nanoparticles, (≡ Si-O)3 Si–O* and (≡ Si-O)2(H-O)Si-O*, whose inhomogeneous width was measured to be 0.042 eV and 0.060 eV, respectively. These results can be accounted for by the structura…

Oxidation of silicon nanoparticles produced by ns laser ablation in liquids

The investigation of nanoparticles produced by ns pulsed Nd:YAG laser ablation of silicon in liquids is reported. Combined characterization by morphological and structural techniques shows that these nanoparticles have a mean diameter of ~3 nm and a core-shell structure consisting of a Si-nanocrystal surrounded by a layer of oxidized Si. Time resolved luminescence spectra evidence visible and UV emissions: a broad band around 1.9 eV originates from Si-nanocrystals, while two bands centered at 2.7 eV and 4.4 eV are associated with oxygen deficient centers in the SiO2 shell.

Evidence of different red emissions in irradiated germanosilicate materials

International audience; This experimental investigation is focused on a radiation induced red emission in Ge doped silica materials, elaborated with different methods and processes. The differently irradiated samples as well as the pristine ones were analyzed with various spectroscopic techniques, such as confocal microscopy luminescence (CML), time resolved luminescence (TRL), photoluminescence excitation (PLE) and electron paramagnetic resonance (EPR). Our data prove that irradiation induces a red luminescence related to the presence of the Ge atoms. Such emission features a photoexcitation spectrum in the UV-blue spectral range and, TRL measurements show that its decrease differs from a …

Etude spectroscopique de fibres durcies pour un environnement radiatif sévère

Les nouveaux environnements radiatifs, comme LMJ, ITER, ILE/ELI, HiPER, réacteurs nucléaires des générations III+ et IV, nécessitent le développement de nouveaux composants pour le transport et le traitement des signaux. A cause de l’impossibilité d’utiliser les composants électroniques, la recherche est orientée vers les composants à fibres optiques comme vecteur d’information et aussi comme élément de diagnostic. Ils présentent de nombreux avantages, comme leur relative immunité électromagnétique, faible pois, large bande passante, mais les rayonnements gamma et les neutrons dégradent leur transmission. La dégradation dépend principalement de la composition de la fibre. Ainsi, il a été mo…

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

International audience; 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 …

Interstitial O2 distribution in amorphous SiO2 nanoparticles determined by Raman an Photoluminescence spectroscopy

The O2 content and emission properties in silica nanoparticles after thermal treatments in oxygen rich atmosphere have been investigated by Raman and photoluminescence measurements. The nanoparticles have different sizes with average diameter ranging from 7 up to 40 nm. It is found that O2 concentration in nanoparticles monotonically increases with nanoparticles size. This finding is independent on the measurement technique and evidences that oxygen molecules are not present in all the nanoparticles volume. This dependence is interpreted on the basis of a structural model for nanoparticles consisting of a core region able to host the oxygen molecules and a surface shell of fixed size and fr…

Coupled experiment/simulation approach for the design of radiation-hardened rare-earth doped optical fibers and amplifiers

We developed an approach to design radiation-hardened rare earth -doped fibers and amplifiers. This methodology combines testing experiments on these devices with particle swarm optimization (PSO) calculations. The composition of Er/Yb-doped phosphosilicate fibers was improved by introducing Cerium inside their cores. Such composition strongly reduces the amplifier radiation sensitivity, limiting its degradation: we observed a gain decreasing from 19 dB to 18 dB after 50 krad whereas previous studies reported higher degradations up to 0°dB at such doses. PSO calculations, taking only into account the radiation effects on the absorption efficiency around the pump and emission wavelengths, co…

Steady-State X-Ray Radiation-Induced Attenuation in Canonical Optical Fibers

The so-called canonical optical fibers (OFs) are samples especially designed to highlight the impact of some manufacturing process parameters on the radiation responses. Thanks to the results obtained on these samples, it is thus possible to define new procedures to better control the behaviors of OFs in radiation environments. In this article, we characterized the responses, under steady-state X-rays, of canonical samples representative of the most common fiber types differing by their core-dopants: pure silica, Ge, Al, and P. Their radiation-induced attenuation (RIA) spectra were measured online at both room temperature (RT) and liquid nitrogen temperature (LNT), in the energy range [~0.6…

Homogeneous and inhomogeneous contributions to the luminescence linewidth of point defects in amorphous solids: Quantitative assessment based on time-resolved emission spectroscopy

The article describes an experimental method that allows to estimate the inhomogeneous and homogeneous linewidths of the photoluminescence band of a point defect in an amorphous solid. We performed low temperature time-resolved luminescence measurements on two defects chosen as model systems for our analysis: extrinsic Oxygen Deficient Centers (ODC(II)) in amorphous silica and F+ 3 centers in crystalline Lithium Fluoride. Measurements evidence that only defects embedded in the amorphous matrix feature a dependence of the radiative decay lifetime on the emission energy and a time dependence of the first moment of the emission band. A theoretical model is developed to link these properties to…

Temperature dependence of decay process of luminescence activity in Sn-doped silica.

Photobleaching and Recovery Kinetics of a Palette of Carbon Nanodots Probed by In Situ Optical Spectroscopy

Carbon dots (CDs) are a family of fluorescent nanoparticles displaying a wide range of interesting properties, which make them attractive for potential applications in different fields like bioimaging, photocatalysis, and many others. However, despite many years of dedicated studies, wide variations exist in the literature concerning the reported photostability of CDs, and even the photoluminescence mechanism is still unclear. Furthermore, an increasing number of recent studies have highlighted the photobleaching (PB) of CDs under intense UV or visible light beams. PB phenomena need to be fully addressed to optimize practical uses of CDs and can also provide information on the fundamental m…

Bright blue emission of synthesized silica nanoparticles conferred by surface defects

In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O-2-controlled atmosphere

The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect a…

Luminescence properties of III-V multi-junctions solar cells

The recent achievement of multi-junctions solar cells, based on III-V semiconductors, exceeding 43% efficiency, has stimulated a rapid growth of concentration photovoltaic (CPV) technology. The large efficiency of these cells is based on the matching between the semiconductors band gap and the solar spectrum and the capability of working under concentrated illumination, up to ~1000 suns. The research pays, therefore, attention to investigate in detail the mechanisms that affect the conversion efficiency, such as the non radiative losses that increase the cell temperature thus favoring the electron-hole (e-h) recombination. With the aim to clarify the performances of these III-V cells, here …

Photo-Activated Phosphorescence of Ultrafine ZnS:Mn Quantum Dots: On the Lattice Strain Contribution

We address the enhancement of orange-light luminescence of Mn-doped zinc sulfide nanoparticles (NPs) induced by exposure to UV light. Ultrafine ZnS:Mn NPs are prepared by microwave-assisted crystal growth in ethanol, without adding any dispersant agents. When exposed to UV light, their orange emission intensity undergoes a strong increase. This effect is observed when the NPs are deposited as a thin layer on a transparent substrate or dispersed in an ethanolic suspension. Such a feature was already observed on polymer- or surfactant-coated ZnS:Mn NPs and explained as a passivation effect. In this study, by coupling X-ray photoelectron, Fourier transform infrared, and electron paramagnetic r…

Processus fondamentaux de formation-transformation des défauts induits par insolation UV dans les fibres optiques

Time resolved photoluminescence associated with non-bridging oxygen hole centers in irradiated silica

Abstract We report time resolved photoluminescence spectra of irradiated silica under excitation with a laser tunable in the visible and UV range. The investigated samples exhibit the emission band at 1.9 eV associated with non-bridging oxygen hole centers, whose spectral and kinetics properties do not depend on the kind of irradiation (γ, β and neutrons). The 1.9 eV luminescence decay follows a multi-exponential curve with a characteristic lifetime that increases from 8.9 μs to 10.4 μs on increasing the emission energy. This dependence accounts for the blue-shift of the emission band during its decay and is interpreted as due to the inhomogeneous properties of silica leading to a distribut…

Fluorescent Carbon Nanodots as Sensors of Toxic Metal Ions and Pesticides

Carbon nanodots (CDs) are a new class of fluorescent carbon-based nanomaterials characterized by a plethora of morphologies and sizes. Among these, we can include two different types of CDs, namely, graphitic and diamond-like. This wide range of structures opens up the possibility to design different CDs, with tunable optical properties accordingly to the synthesis method and precursors used. We prepared two different CDs following a bottom-up approach by thermally induced decomposition of organic precursors (namely, citric acid and urea in different molar ratios), and using purification by Size Exclusion Chromatography (SEC). Obtained CDs were characterized by Raman, absorption and fluores…

Intrinsic defects induced by β-irradiation in silica

We report an electron paramagnetic resonance study of defects induced by β-irradiation in natural and synthetic samples of high purity commercial silica. Data are collected for the E′ centers and a resonance satellite signal split by 1.36 mT. By comparison with the effects of γ-irradiation it is shown that the mechanisms of defect generation are the same for the two irradiation sources and that in the high-dose limit they involve intrinsic defects of the glassy matrix. Moreover, the high concentration of defects generated by β-irradiation modifies the EPR spectrum due to spin–spin interaction.

Transient nutations decay: The effect of field-modified dipolar interaction

The anomalous behavior of transient nutations is experimentally investigated in a set of two-level $(S=\frac{1}{2})$ spin systems differing only in spin concentration. Our results show that the non-Bloch power dependence of the decay rate of transient nutations is a concentration-dependent effect, which is more and more pronounced in more and more concentrated samples. The experimental results are interpreted in the framework of the recent theory by Shakhmuratov et al. [Phys. Rev. Lett. 79, 2963 (1997)] and support the hypothesis that the anomalous decay of transient nutations in solids originates from radiation-induced changes of the dipolar field, rather than from residual fluctuations of…

Laser wavelength effects on the refractive index change of waveguides written by femtosecond pulses in silica glasses

We investigate the influence of two fs-laser wavelengths (343 and 800 nm) on the induced refractive index change (Δn) of waveguides written in silica materials. Results show that Δn is higher for waveguides photo-inscribed with UV photons.

Facile synthesis of a monolith of silicon nanocrystal embedded in silica

Inhomogeinity of Oxygen deficient centers in silica probed by nanosecond time-resolved luminescence measurements

Gamma ray induced 11.8 mT ESR doublet in natural silica

Abstract We report electron spin resonance (ESR) measurements in natural and synthetic vitreous SiO2 samples irradiated by γ rays. An 11.8 mT doublet, asymmetrically centered on the resonance line of the E′ center, was detected only in natural samples. The intensity of this doublet as a function of γ exposure tends to saturate for doses as low as 0.2 Mrad and is not related to the growth kinetics of the E′ centers. Photoluminescence (PL) measurements on the same samples have shown that two emissions at 3.15 and 4.26 eV bleach with the same kinetics as does the 11.8 mT doublet on increasing the γ ray dose. We tentatively suggest the presence of a conversion mechanism, activated by γ irradiat…

Electrical-optical characterization of multijunction solar cells under 2000X concentration

In the framework of the FAE "Fotovoltaico ad Alta Efficienza" ("High Efficiency Photovoltaic") Research Project (PO FESR Sicilia 2007/2013 4.1.1.1), we have performed electrical and optical characterizations of commercial InGaP/InGaAs/Ge triple-junction solar cells (1 cm2) mounted on a prototype HCPV module, installed in Palermo (Italy). This system uses a reflective optics based on rectangular off-axis parabolic mirror with aperture 45×45 cm2 leading to a geometrical concentration ratio of 2025. In this study, we report the I-V curve measured under incident power of about 700 W/m2 resulting in an electrical power at maximum point (PMP) of 41.4 W. We also investigated the optical properties…

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 highl…

In situ observation of UV absorption spectra induced in silica by beta irradiation

Near infrared emitting silica nanoparticles: O2 diffusion properties and excited state relaxation

Role of mobile hydrogen on relaxation processes in Ge-doped optical fibers

Heterogeneity of aggregates in the fibrillation mechanisms of proteins probed by time resolved fluorescence

Under appropriate conditions almost all proteins are able to aggregate to form long, well-ordered and beta-sheet rich arrays known as amyloid fibrils. The formation of such structures involves complex intra and intermolecular interactions modulated by the structure and dynamics of the native protein, and by the physico-chemical properties of the solvent. Multiple interactions and cross-feedback during the aggregation pathway cause different ultimate aggregates’ morphologies and the possible simultaneous occurrence of multiple species. The structural definition of such assemblies is complicated by the polymorphism of the amyloid fibrils. Aim of this study is to inquire on the different natur…

Optical properties of GeODC embedded in Ge-doped films on a-SiO2 substrate

Investigation by raman spectroscopy of the decomposition process of HKUST-1 upon exposure to air

We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF) HKUST-1 upon exposure to air moisture (T=300 K, 70% relative humidity). The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes take place, which are related to the occurrence of the hydrolysis of Cu-O bonds. These processes induce small but detectable variations of the peak positions and intensities of the main Raman bands of th…

Inhomogeneous width of oxygen-deficient centers induced by electron irradiation of silica

We report a study of the luminescence activity of oxygen-deficient centers stabilized in as-grown synthetic silica, as compared with the same defects induced by $\ensuremath{\beta}$ irradiation at increasing doses, ranging from $1.2\ifmmode\times\else\texttimes\fi{}{10}^{3}$ to $5\ifmmode\times\else\texttimes\fi{}{10}^{6}\text{ }\text{kGy}$. We experimentally observe a progressive broadening of the luminescence band with increasing total electron dose released on samples. By analyzing our data within a theoretical model capable of separating homogeneous and inhomogeneous contribution to the total luminescence linewidth, we observe that the increasing of the width is entirely ascribable to t…

Barrier inhomogeneity in vertical Schottky diodes on free standing gallium nitride

Abstract In this paper, the electrical behavior of a Ni/Au Schottky barrier on free standing GaN has been studied employing a variety of techniques and correlated with the material and interface quality. The temperature dependence of the ideality factor (n) and of the Schottky barrier height (ΦB) revealed a spatial inhomogeneity of the barrier. This behavior has been described by means of the Tung's model on inhomogeneous Schottky barriers. The origin of the barrier inhomogeneity can be likely associated to the surface quality of the GaN epilayer or to microstructure of the Ni/GaN interface.

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

AbstractWe 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, …

Generation of defects in amorphous SiO(2) assisted by two-step absorption on impurity sites.

Generation of the Si dangling bond defect in amorphous SiO(2) (E' centre) induced by tunable pulsed UV laser radiation was investigated by in situ optical absorption measurements. The defect generation efficiency peaks when the photon energy equals ∼5.1 eV, it depends quadratically on laser intensity and is correlated with the native linear absorption due to Ge impurities. We propose a model in which the generation of E' is assisted by a two-step absorption process occurring on Ge impurity sites.

NANO-EMETTITORI NIR A BASE DI SILICE PER APPLICAZIONI IN-VIVO E RELATIVO PROCESSO DI PRODUZIONE

Realizzazione di nano-sonde paramagnetiche e fosforescenti, ottenibili a partire da particelle nanometriche di silice mediante procedure di sintesi e arricchimento di O2 a seguito di opportuni trattamenti termici in ambiente controllato. Le nano-sonde così ottenute presentano emissioni nel vicino infrarosso (NIR), sono eccitabili nel visibile e nel NIR, e sono caratterizzate da un tempo di vita nell’ordine del secondo. Tali nano-sonde presentano un notevole potenziale scientifico e commerciale nel mercato della spettroscopia confocale per bio-imaging e nel mercato delle applicazioni medico-farmaceutiche di drug-labelling e drug-delivery.

Photochemical generation of E′ centres from Si–H in amorphous SiO2under pulsed ultraviolet laser radiation

In situ optical absorption spectroscopy was used to study the generation of E' centres () in amorphous SiO2 occurring by photo-induced breaking of Si–H groups under 4.7 eV pulsed laser radiation. The dependence on laser intensity of the defect generation rate is consistent with a two-photon mechanism for Si–H rupture, while the growth and saturation of the defects are conditioned by their concurrent annealing due to a reaction with mobile hydrogen arising from the same precursor. A rate equation is proposed to model the kinetics of the defects and is tested on experimental data.

Origin of the visible absorption in radiation-resistant optical fibers

In this work we investigated the point defects at the origin of the degradation of radiation-tolerant optical fibers used in the visible part of the spectrum for plasma diagnostics in radiation environments. For this aim, the effects of γ -ray irradiation up to the dose of 10 MGy(SiO2) and post-irradiation thermal annealing at 550◦C were studied for a Fluorinedoped fiber. An absorption peaking around 2 eV is mainly responsible for the measured radiation-induced losses, its origin being currently debated in the literature. On the basis of the unchanging shape of this band with the radiation dose, its correlation with the 1.9 eV photoluminescent band and the thermal treatment results we assig…

Silica Nanoparticles for Near-Infrared Imaging and Photonics Applications

Temperature dependence of O2 singlet photoluminescence in silica nanoparticles

Abstract The near infrared singlet emission and photoluminescence lifetime of O 2 molecules embedded in silica nanoparticles are studied from room temperature down to 10 K. The area of the photoluminescence band under infrared excitation decreases for temperature above 100 K and the lifetime is shortened. These observations provide evidence of a thermally activated relaxation channel with activation energy of about 40 meV. This relaxation mechanism adds to the already known temperature independent electronic-to-vibrational coupling involving high energy vibrational modes of the host matrix or its impurities. The thermally activated process is suggested to consist in the breakage of the O 2 …

Effects of radiation and hydrogen-loading on the performances of raman-distributed temperature fiber sensors

International audience; The integration of Raman-distributed temperature fiber-based sensors (RDTS) into the envisioned French deep geological repository for nuclear wastes, called Cigéo requires evaluating how the performances of RDTS evolve in harsh environments, more precisely in presence of H2 or γ-rays. Both H2 and radiations are shown to affect the temperature measurements made with the single-ended RDTS technology. The amplitudes of the observed effects depend on the different classes of multimode fibers varying in terms of composition and coatings. By selecting the most tolerant fiber structure for the sensing, we could maintain the RDTS performances for such application. A hardeni…

Luminescenza risolta in tempo del non bridging oxygen hole center in silice: proprietà di volume e di superficie

Influence of hydrogen on paramagnetic defects induced by UV laser exposure in natural silica

Diffusion limited reactions of point defects were investigated in amorphous SiO2 exposed to UV laser light. Electron spin resonance and in situ absorption measurements at room temperature evidenced the annealing of E' centers and the growth of H(II) centers both occurring in the post-irradiation stage and lasting a few hours. These transients are caused by reactions involving molecular hydrogen H2, made available by dimerization of radiolytic H0.

Nd:YAG laser induced E' centers probed by in situ absorption measurements

Oxidation of silicon nanoparticles produced by nanosecond laser ablation in liquids

We investigated nanoparticles produced by laser ablation of silicon in water by the fundamental harmonic (1064 nm) of a ns pulsed Nd:YAG. The silicon oxidation is evidenced by IR absorption features characteristic of amorphous SiO2 (silica). This oxide is highly defective and manifests a luminescence activity under UV excitation: two emission bands at 2.7 eV and 4.4 eV are associated with the twofold coordinated silicon, =SiO••.

Neutron-induced defects in optical fibers

We present a study on 0.8 MeV neutron-induced defects up to fluences of 1017 n/cm2 in fluorine doped optical fibers by using electron paramagnetic resonance, optical absorption and confocal micro-luminescence techniques. Our results allow to address the microscopic mechanisms leading to the generation of Silica-related point-defects such as E', H(I), POR and NBOH Centers.

Ultraviolet optical properties of silica controlled by hydrogen trapping at Ge-related defects

We studied the effects induced by the ultraviolet-laser and -lamp exposure sequences on the twofold coordinated germanium (=Ge{sup {center_dot}}{sup {center_dot}}) and the H(II) center (=Ge{sup {center_dot}}-H) in silica. The H(II) centers, generated after the first laser irradiation stage by the trapping of atomic hydrogen H{sup 0} at the (=Ge{sup {center_dot}}{sup {center_dot}}), are destroyed by the subsequent lamp exposure with efficiency depending on photon energy. The H(II) photodestruction is activated from {approx}4 eV, and its cross section is here quantitatively measured, so giving the absorption profile of this center. Consistent with the observed correlated recovering of (=Ge{su…

Photoluminescence in gamma-irradiated alpha-quartz investigated by synchrotron radiation

Abstract We report an experimental investigation of the photoluminescence, under excitation by synchrotron radiation within the absorption band at 7.6 eV , induced in γ-irradiated α-quartz. Two emissions centered at 4.9 and 2.7 eV are observed at low temperature: the former decreases above 40 K , whereas the second band exhibits an initial slight increase and its quenching is effective above 100 K . Furthermore, the decay kinetics of both emissions occur in a time scale of nanoseconds: at T=17.5 K we measured a lifetime τ∼1.0 ns for the photoluminescence at 4.9 eV and τ∼3.6 ns for that at 2.7 eV . These results give new insight on the optical properties associated with defects peculiar of c…

Temperature dependance of the generation and decay of E’ centers induced in silica by 4.7eV laser radiation

We report a study of the generation of silicon dangling bonds (E' centers) induced in fused silica by 4.7 eV laser irradiation in the 10 200 K the induced defects undergo a post-irradiation decay due to their reaction with mobile H(2). The interplay between generation and annealing gives rise to a bell-shaped temperature dependence of the concentration of induced E' centers, peaking at 250 K

β-ray irradiation effects on silica nanoparticles

By electron paramagnetic resonance (EPR) measurements, we examine the amplitude of the signal typically due to a combination of NBOHC (Non Bridging Hole Center) and POR (Peroxy Radical) defects induced by β-ray irradiation (from 1.2 to 1200 MGy) in silica nanoparticles with diameter ranging from 7 to 20 nm. Our data indicate that the signal line-shapes recorded at different doses is quite independent from the particles sizes and from the dose. Furthermore, for each considered nanoparticles size, the concentration of defects is also almost constant with respect to dose, and it does not change significantly if measured after 2 or 9 months from the irradiation. By contrast, we observed that th…

Efficiency of concentration photovoltaic cells governed by luminescence processes

The development of multi-junctions III-V semiconductors solar cells, that combine high conversion efficiency (over 40%) and capability of working under high illumination intensity (up to 1000 suns), has stimulated a rapid growth of concentrating photovoltaic (CPV) technology. The performance of these cells is based on the matching between the semiconductors band gap and the solar spectrum so as to optimize the current balancing between the subcells. This requirement is also important in connection with the CPV modules using lenses, mirrors, optical coupling compounds that introduce a wavelength dependent response to the sunlight. Therefore, care must be exercised in designing optimum cells …

Luminescence activity of irradiated SiO2-clathrate Melanophlogite

Nitrogen-doped carbon dots embedded in a SiO2 monolith for solid-state fluorescent detection of Cu2+ ions

We describe the simple fabrication of SiO2 sol-gel monoliths embedding highly luminescent carbon nanodots (CDs) sensitive to metal ions. The pristine CDs we synthesize display an intense dual emission consisting in two fluorescence bands in the green and violet region, and we demonstrate that this photoluminescence is substantially unchanged when the dots are incorporated in the SiO2 matrix. The emission of these CDs is quenched by interactions with Cu2+ ions, which can be used to detect these ions with a detection limit of 1 μM. The chromophores remain accessible to diffusing Cu2+ ions even after embedding CDs in the sol-gel monolith, where their detection capabilities are preserved. Such …

Diffusion and outgassing of O2 in amorphous SiO2 silica nanoparticles with specific surface properties

Silica nanoparticles with hydrophilic and hydrophobic surface and average diameter of 12 and 40 nm are investigated to study the surface group influence on the diffusion process of molecular oxygen. The O2 diffusion kinetics and molecular solubility are determined by Raman/Photoluminescence measurements. Thermal treatments up to 127°C in controlled atmosphere show that the surface chemistry of nanoparticles is not changed, the equilibrium emission of O2 depends on nanoparticles surface properties, whereas the dynamics of diffusion is surface independent suggesting that surface groups could only affect overall content or detectability of interstitial molecules. The post loading outgassing in…

Metal/Semiconductor Barrier Properties of Non-Recessed Ti/Al/Ti and Ta/Al/Ta Ohmic Contacts on AlGaN/GaN Heterostructures

This paper compares the metal/semiconductor barrier height properties of non-recessed Ti/Al/Ti and Ta/Al/Ta contacts on AlGaN/GaN heterostructures. Both contacts exhibited a rectifying behavior after deposition and after annealing at temperatures up to 550 &deg

Irradiation induced defects in fluorine doped silica

International audience

Creation of paramagnetic defects by gamma irradiation in amorphous silica

An electron spin resonance (ESR) study of the defects induced by γ-rays in various types of natural and synthetic silica is reported. Three main structures were identified: the E′ center and two doublets with field splitting of 7.4 and 11.8 mT, respectively, both centered around the E′ center signal. Another structure partially overlapping the E′ center line was also detected, consisting in three peaks with a maximum field splitting of 1.36 mT. We have investigated the growth kinetics of these centers on increasing the y-ray accumulated dose. In all investigated materials the growth of E′ centers can be interpreted as caused by γ-activated conversion of one or more precursors. The 1.36 mT s…

Highly Efficient Electron Transfer in a Carbon Dot–Polyoxometalate Nanohybrid

Using solar radiation to fuel catalytic processes is often regarded as the solution to our energy needs. However, developing effective photocatalysts that are active under visible light has proven to be difficult, often due to the toxicity, instability, and high cost of suitable catalysts. We engineered a novel photoactive nanomaterial obtained by the spontaneous electrostatic coupling of carbon nanodots with [P2W18O62]6-, a molecular catalyst belonging to the class of polyoxometalates. While the former are used as photosensitizers, the latter was chosen for its ability to catalyze reductive reactions such as dye decomposition and water splitting. We find the electron transfer within the na…

Harnessing Molecular Fluorophores in the Carbon Dots Matrix: The Case of Safranin O

The origin of fluorescence in carbon dots (C-dots) is still a puzzling phenomenon. The emission is, in most of the cases, due to molecular fluorophores formed in situ during the synthesis. The carbonization during C-dots processing does not allow, however, a fine control of the properties and makes finding the source of the fluorescence a challenging task. In this work, we present a strategy to embed a pre-formed fluorescent molecule, safranin O dye, into an amorphous carbonaceous dot obtained by citric acid carbonization. The dye is introduced in the melted solution of citric acid and after pyrolysis remains incorporated in a carbonaceous matrix to form red-emitting C-dots that are strongl…

Luminescent defects induced by sintering of silica nanoparticles

Neutron-induced defects in F-doped fibers

We present a study on 0.8 MeV neutron-induced defects up to fluences of 1017 n/cm² in fluorine doped fibers by using electron paramagnetic resonance, optical absorption and confocal micro-luminescence techniques. Our results allow to address the microscopic mechanisms leading to the generation of some Silica-related point-defects such as E’, H(I), POR and NBOH Centers.

Direct atomic layer deposition of ultrathin aluminium oxide on monolayer $MoS_2$ exfoliated on gold: the role of the substrate

In this paper we demonstrated the thermal Atomic Layer Deposition (ALD) growth at 250 {\deg}C of highly homogeneous and ultra-thin ($\approx$ 3.6 nm) $Al_2O_3$ films with excellent insulating properties directly onto a monolayer (1L) $MoS_2$ membrane exfoliated on gold. Differently than in the case of 1L $MoS_2$ supported by a common insulating substrate ($Al_2O_3/Si$), a better nucleation process of the high-k film was observed on the 1L $MoS_2/Au$ system since the ALD early stages. Atomic force microscopy analyses showed a $\approx 50\%$ $Al_2O_3$ surface coverage just after 10 ALD cycles, its increasing up to $>90\%$ (after 40 cycles), and an uniform $\approx$ 3.6 nm film, after 80 cycle…

Near-Infrared emission of O2 embedded in amorphous SiO2 nanoparticles

We report an experimental study on the emission properties of O2 molecules loaded by a thermal diffusion process at 200 °C into high-purity silica nanoparticles with mean diameters of 7 and 40 nm. The embedded O2 features a singlet to triplet emission band peaked at 1272 nm in agreement with the band observed for bulk silica materials. The photoluminescence excitation spectra have been determined in the visible and in the infrared range and are characterized by narrow bands peaked at 691, 764,and 1069 nm, respectively. By comparison of the transition energies, the vibrational quanta have been determined for the ground and for both the excited states; the values found are lower than the corr…

Influence of neutron and gamma-ray irradiations on rad-hard optical fiber

We investigated point defects induced in rad-hard Fluorine-doped optical fibers using both a mixed source of neutrons (fluences from 1015 to 1017 n/cm2) and γ-rays (doses from 0.02 to 2 MGy) and by a γ-ray source (dose up to 10 MGy). By combining several complementary spectroscopic techniques such as radiation-induced attenuation, confocal micro-luminescence, time-resolved photo-luminescence and electron paramagnetic resonance, we evidenced intrinsic and hydrogen-related defects. The comparison between the two irradiation sources highlights close similarities among the spectroscopic properties of the induced defects and the linear correlation of their concentration up to 1016 n/cm2. These r…

Transient absorption with a femtosecond tunable excitation pump reveals the emission kinetics of color centers in amorphous silica.

We report a set of femtosecond (fs) transient absorption (TA) measurements following the dynamics of the so-called nonbridging oxygen hole center in silica, a model color center in wide bandgap amorphous solids, characterized by a very large Stokes shift between the UV excitation and its associated red emission at 1.9 eV. The changes in the TA spectrum were probed in the UV-visible range at various delays after photoexcitation and analyzed as a function of the UV excitation energy, in single-photon absorption conditions. The combination of the experiments helps to clarify the defect photocycle, highlighting how TA measurements with tunable UV excitation could represent a powerful tool to in…

Graphene‐SiO2 Interaction from Composites to Doping

An overview of the interaction between monolayer graphene and SiO2 dielectric substrate is reported focusing on the effect this latter has on doping and strain induced by thermal treatments in controlled atmosphere. The disentanglement of strain and doping is highlighted and the comparison with another dielectric substrate of Al2O3 evidences the critical role that the substrate has in the electronic properties of graphene. The reported results pave the way for microelectronic devices based on graphene on dielectrics and for Fermi level tuning in composites of graphene and nanoparticles.

Properties of HO2• radicals induced by γ-ray irradiation in silica nanoparticles

Abstract We report an experimental investigation on the effects of γ -ray irradiation in several types of silica nanoparticles previously loaded with O 2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 10 18 HO 2 • /cm 3 interstitial radicals. These radicals are induced by reaction of interstitial O 2 molecules with radiolytic H atoms, as previously suggested for O 2 -loaded bulk a-SiO 2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO 2 • radical. In fact, by a detailed study of samples exposed to D 2 …

Laser spectroscopy and ESR analysis of the strong Ga atoms/SiO2 surface interaction

Temperature dependence of luminescence decay in Sn-doped silica

We report an experimental study on the temperature dependence, in the range 18-300 K, of the decay kinetics of the emission at 4.1 eV from the first excited electronic state of oxygen deficient centers in a 2000 ppm Sn-doped sol-gel silica. At low temperature, this luminescence decays exponentially with a lifetime of 8.4 ns, whereas, on increasing the temperature, the time decay decreases and cannot be fitted with an exponential function. These results are expected if there is a competition between the radiative and the thermally activated intersystem-crossing decay channels toward the associated triplet state. The comparison with previous data in pure oxygen-deficient and Ge-doped silica g…

Spectroscopy of an optical excited Ga doped SiO2 surface

Abstract We present the first spectroscopical analysis of the Ga/SiO2 surface interaction in hot environment. This interaction gives rise to inclusions of Ga atoms inside the silica matrix that produce structural changes and modify the SiO2 optical characteristics. This paper discusses both the time- and the frequency-resolved spectra of the fluorescence emission following UV pulsed laser excitation of the so “doped” silica in the range 15,000–28,000 cm−1. The investigation is completed by the electron paramagnetic resonance (EPR) spectra of two high-purity synthetic silica samples of commercial origin after thermal treatment in presence and in absence of a Ga atmosphere.

Electron Irradiation Effects on Single‐Layer MoS 2 Obtained by Gold‐Assisted Exfoliation

International audience; Mechanical exfoliation assisted by gold is applied to obtain good quality large lateral size single-layer MoS2. The effects of 2.5 MeV electron irradiation are investigated at room temperature on structural and electronic features by Raman and microluminescence spectroscopy. The exciton recombination emission in the direct bandgap of single-layer MoS2 is affected during irradiation starting from the minimum explored dose of 1 kGy. At higher doses, Raman bands show no relevant modifications whereas the exciton emission is quenched, suggesting that irradiation-induced point defects affect exciton dynamics.

Oxidation of Zn nanoparticles probed by online optical spectroscopy during nanosecond pulsed laser ablation of a Zn plate in H2O

We report online UV-Visible absorption and photoluminescence measurements carried out during and after pulsed laser ablation of a zinc plate in water, which clarify the events leading to the generation of ZnO nanoparticles. A transient Zn/ZnO core-shell structure is revealed by the coexistence of the resonance absorption peak around 5.0 eV due to Zn surface plasmon resonance and the edge at 3.5 eV of ZnO. The growth kinetics of ZnO, selectively probed by the exciton luminescence at 3.3 eV, begins only after a ∼30 s delay from the onset of laser ablation. We also detect the luminescence at 2.3 eV of ZnO oxygen vacancies, yet rising with an even longer delay (∼100 s). These results show that …

Radiation effects on silica-based preforms and optical fibers-I: Experimental study with canonical samples

International audience; Prototype samples of preforms and associated fibers have been designed and fabricated through MCVD process to investigate the role of fluorine (F) and germanium (Ge) doping elements on the radiation sensitivity of silica-based glasses. We characterized the behaviors of these canonical samples before, during and after 10 keV X-ray irradiation through several spectroscopic techniques, to obtain global information (in situ absorption measurements, electron paramagnetic resonance) or spatially-resolved information (confocal microscopy, absorption and luminescence on preform). These tests showed that, for the Ge-doped fiber and in the 300–900 nm range, the radiation-induc…

Effects of Pressure, Thermal Treatment, and O2 Loading in MCM41, MSU-H, and MSU-F Mesoporous Silica Systems Probed by Raman Spectroscopy

We present a Raman study of the effects induced by pressure, thermal treatments, and O2 loading in MCM41, MSU-H, and MSU-F representative mesoporous silica. We compared the starting powders with the mechanically pressed tablets produced applying pressures of ∼0.2 and ∼0.45 GPa. The spectra of the three untreated tablets evidence that the main value of the Si-O-Si angle decreases and that in the MCM41 and the MSU-H Si-O-Si hydrolysis occurs, whereas such a process is absent or much less efficient in the MSU-F. Despite their different networks, the three powders tend to crystallize in cristobalite when treatments are at 1000 °C. The MCM41 and MSU-H tablets exhibit behavior similar to their st…

Paramagnetic germanium-related centers induced by energetic radiation in optical fibers and preforms

International audience; We investigated the creation processes of Ge-related paramagnetic point defects in silica fibers and preforms, doped with different amounts of germanium, and X-ray irradiated at several radiation doses. Different paramagnetic defect species, like GeE0, Ge(1) and Ge(2), were revealed by electron paramagnetic resonance measurements and their concentration was studied as a function of the irradiation dose. The comparison with the optical absorption spectra points out the main role of Ge(1) on the optical transmission loss of fibers in the UV region.

Optical properties of phosphorous-related point defects in silica fiber preforms

Physical review / B 80, 205208 (2009). doi:10.1103/PhysRevB.80.205208

Photoluminescence time decay of surface oxygen deficient centers in un‐doped and Ge‐doped silica

We report a study of the emission decay from the singlet excited state of two fold coordinated Si and Ge centers stabilized on the surface of silica and Ge-doped silica. The PL lifetimes are of the order of nanoseconds and increase on decreasing the temperature. The results suggest that, for the surface centers, the phonon assisted intersystem-crossing process linking the excited states affects the decay rates, is effective down to low temperatures and is distributed because of the inhomogeneity of the defects. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Raman investigation of the drawing effects on Ge-doped fibers

International audience; We have investigated the Raman activity of various germanosilicate fibers and their associated preforms. Our data indicate an enhancement in small rings' (3-member rings) concentration in the silica-based matrix of the fibers during the drawing process. The generation of such rings appears compatible with an increase of the sample density and fictive temperature. The data regarding the drawing effects on the fiber stress appear less clear, and it is possible to suggest that in some cases the drawing could lower the tensile stress. Finally we have also provided evidence that changing the drawing conditions within the usual range of application leads to no significant …

Excitation processes of the blue luminescence in crystalline SiO 2 probed by synchrotron radiation measurements

Luminescence properties of crystalline α-quartz were investigated by time-resolved spectroscopy under pulsed synchrotron radiation excitation in the vacuum ultraviolet range. Our results evidence that two emission bands overlap at 2.7 eV, both being observed only at low temperature. The first contribution is excited by band-to-band transition and is related to the radiative recombination of a self trapped exciton occurring in a time scale of a few ms, the second is associated with defects induced in quartz by γ- and β-radiation, is excited at 7.6 eV and its lifetime is 3.6 ns at T = 10 K. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Optical and photonic material hardness for energetic environments

We studied the effects of dielectric change in the chemical composition and in the realization procedures under radiation exposure. We have compared the radiation effects on Ge-doped and F-doped fibers and preforms: the first play a crucial role in the photosensitivity property, the second improves the dielectric radiation hardness even at low concentrations. The use of different spectroscopic techniques (RIA, OA, EPR) allow the identification of the point defect formation mechanisms at the origin of the optical degradation properties.

Temperature-Dependence of Solvent-Induced Stokes Shift and Fluorescence Tunability in Carbon Nanodots

We carried out a cryogenic investigation on the optical properties of carbon dots, aiming to better understand their emission mechanism and the role of the solvent. The solvatochromic Stokes shift is quantified by a low temperature approach which allows freezing of the photo-excited state of carbon dots, preventing any solvation relaxation. Moreover, the reduction in temperature helps to identify the dynamical inhomogeneous contribution to the broadening of the emission band; therefore, disentangling the role of solvent from other types of broadening, such as the homogeneous and the static inhomogeneous contributions.

Stability of sol-gel silica glass for CPV and ultraviolet LED applications

This paper concerns the characterization of silica glass obtained by a sol-gel technique as to its suitability in the terrestrial and space concentrated photovoltaic (CPV), and ultraviolet light emitting diode (UV LED) industrial sectors. The sol-gel material tested is produced by Evonik Industries and marketed under the brand name SAVOSIL™. The tests performed were aimed at determining the endurance of the material to radiation exposure and consist of exposure to gamma radiation and 355 nm UV laser light. In these tests the transmittance of the glass was measured before and after the exposure to the radiation to determine the effect of the radiation treatment. In the case of the test with …

Performance Analysis of a Prototype High‐Concentration Photovoltaic System Coupled to Silica Optical Fibers

High-concentration photovoltaic (HCPV) systems are one of the most promising technologies for the generation of renewable energy with high-conversion efficiency. Their development is still at an early stage, but the possibility of integrating high-concentration systems into buildings offers new opportunities to achieve the net-zero-energy building goal. Herein, the optical and energetic performance of a hybrid daylighting−HCPV prototype based on pure- or doped-silica optical fibers (OFs) to guide 2000× concentrated sunlight inside the buildings is evaluated. There, the light can either be used to illuminate interior spaces or projected on solar cells to generate electricity. The system equi…

Luminescence Efficiency of Si/SiO 2 Nanoparticles Produced by Laser Ablation

Photoluminescence properties of Si(core)/SiO 2 (shell) nanoparticles produced by pulsed laser ablation in aqueous solution are investigated with the purpose to highlight the microscopic processes that govern the emission brightness and stability. Time resolved spectra evidence that these systems emit a µs decaying band centered around 1.95 eV, that is associated with the radiative recombination of quantum-confined excitons generated in the Si nanocrystalline core. Both the quantum efficiency and the stability of this emission are strongly dependent on the pH level of the solution, that is changed after the laser ablation is performed. They enhance in acid environment because of the H + pass…

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

International audience; 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] ~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 intern…

Substrate impact on the thickness dependence of vibrational and optical properties of large area $MoS_2$ produced by gold-assisted exfoliation

The gold-assisted exfoliation is a very effective method to produce large-area ($cm^2$-scale) membranes of molybdenum disulfide ($MoS_2$) for electronics. However, the strong $MoS_2/Au$ interaction, beneficial for the exfoliation process, has a strong impact on the vibrational and light emission properties of $MoS_2$. Here, we report an atomic force microscopy (AFM), micro-Raman ($\mu-R$) and micro-Photoluminescence ($\mu-PL$) investigation of $MoS_2$ with variable thickness exfoliated on Au and subsequently transferred on an $Al_2O_3/Si$ substrate. The $E_{2g}$ - $A_{1g}$ vibrational modes separation $\Delta\mu$ (typically used to estimate $MoS_2$ thickness) exhibits an anomalous large val…

DEFECTS FORMATION AND TRANSFORMATION IN GERMANOSILICATE OPTICAL FIBERS BY UV LASER IRRADIATION

Enhancing the luminescence efficiency of silicon-nanocrystals by interaction with H+ions

The emission of silicon nanocrystals (Si-NCs), synthesized by pulsed laser ablation in water, was investigated on varying the pH of the solution. These samples emit μs decaying orange photoluminescence (PL) associated with radiative recombination of quantum-confined excitons. Time-resolved spectra reveal that both the PL intensity and the lifetime increase by a factor of ∼20 when the pH decreases from 10 to 1 thus indicating that the emission quantum efficiency increases by inhibiting nonradiative decay rates. Infrared (IR) absorption and electron paramagnetic resonance (EPR) experiments allow addressing the origin of defects on which the excitons nonradiatively recombine. The linear correl…

Near-Infrared Emission of O2 Embedded in Amorphous SiO2 Nanoparticles

We report an experimental study on the emission properties of O2 molecules loaded by a thermal diffusion process at 200 °C into high-purity silica nanoparticles with mean diameters of 7 and 40 nm. The embedded O 2 features a singlet to triplet emission band peaked at 1272 nm in agreement with the band observed for bulk silica materials. The photoluminescence excitation spectra have been determined in the visible and in the infrared range and are characterized by narrow bands peaked at 691, 764, and 1069 nm, respectively. By comparison of the transition energies, the vibrational quanta have been determined for the ground and for both the excited states; the values found are lower than the co…

Importance of Spin-Orbit Interaction for the Electron Spin Relaxation in Organic Semiconductors

Despite the great interest organic spintronics has recently attracted, there is only a partial understanding of the fundamental physics behind electron spin relaxation in organic semiconductors. Mechanisms based on hyperfine interaction have been demonstrated, but the role of the spin-orbit interaction remains elusive. Here, we report muon spin spectroscopy and time-resolved photoluminescence measurements on two series of molecular semiconductors in which the strength of the spin-orbit interaction has been systematically modified with a targeted chemical substitution of different atoms at a particular molecular site. We find that the spin-orbit interaction is a significant source of electro…

The interaction of photoexcited carbon nanodots with metal ions disclosed down to the femtosecond scale

Fluorescent carbon nanodots are a novel family of carbon-based nanoscale materials endowed with an outstanding combination of properties that make them very appealing for applications in nanosensing, photonics, solar energy harvesting and photocatalysis. One of the remarkable properties of carbon dots is their strong sensitivity to the local environment, especially to metal ions in solution. These interactions provide a testing ground for their marked photochemical properties, highlighted by many studies, and frequently driven by charge transfer events. Here we combine several optical techniques, down to femtosecond time resolution, to understand the interplay between carbon nanodots and aq…

High-Efficiency Multi-Junction Photovoltaic Cells in School Physics Laboratory

Energy consumption in the world is increasing more and more due to the huge energy request coming from emerging countries such as China, India, etc. To face the challenge of sustainability, a solution may be the use of solar energy, since it is the most abundant renewable energy source on Earth. The electromagnetic energy coming from the Sun can be converted into usable energy (electricity) by solar cells, whose conversion efficiency is continuously increasing due to scientific and technological progress. The proposed activity is thought to be carried out with secondary as well as high school students to allow teachers to discuss sustainability issues, and to provide students with an introd…

X-ray irradiation influence on prototype Er3+-optical fibers: confocal luminescence study

International audience; The integration of rare-earth doped optical fibers as part of fiber-based systems in space implies the development of waveguides tolerant to the radiation levels associated with the space missions. We report the spatial distribution, the photoluminescence (PL) properties of color centers and the related changes induced by X-rays radiation at different doses (50, 500 and 1000 krad) for two different prototypes of Er-doped optical fibers. Each sample (in the version pristine, X-irradiated and H2 loaded prior to radiation exposure) was characterized by confocal microscopy luminescence (CML) measurements in Visible range with Visible (488 nm) or UV (325 nm) laser light e…

Photoluminescence properties of point defects in Ge-doped fibers and preforms

International audience; The optical properties of Ge-related point defects are often the most important parameter for the performances of silica based optical fibers. On one side their presence is often detrimental for the light transmission, on the other side some defect typologies exhibit modifications under radiation exposure thus offering the peculiar property of photosensitivity that is exploited to build technologically relevant devices such as fiber Bragg gratings.

UV laser irradiation of amorphous SiO_2 generation and conversion of point defects and post-irradiation processes

Luminescence properties of nonbridging oxygen hole centers at the silica surface

Abstract Two variants of the surface-nonbridging oxygen hole center, ( Si–O)3Si–O• and ( Si–O)2(H–O)Si–O•, stabilized in porous films of silica nano-particles were investigated by time resolved luminescence excited in the visible and UV spectral range by a tunable laser system. Both defects emit a photoluminescence around 2.0 eV with an excitation spectrum evidencing two maxima at 2.0 and 4.8 eV, this emission decreases by a factor ∼2 on increasing the temperature from 8 up to 290 K. However, the different local structure influences the emission lineshape, the quantum yield and the decay lifetime. Such peculiarities are discussed on the basis of the symmetry properties of these defects.

Heptagon-Containing Nanographene Embedded into [10]Cycloparaphenylene

We report the synthesis and characterization of a novel type of nanohoop, consisting of a cycloparaphenylene derivative incorporating a curved heptagon-containing π-extended polycyclic aromatic hydrocarbon (PAH) unit. We demonstrate that this new macrocycle behaves as a supramolecular receptor of curved π-systems such as fullerenes C60 and C70, with remarkably large binding constants (ca. 107 M−1), as estimated by fluorescence measurements. Nanosecond and femtosecond spectroscopic analysis show that these host-guest complexes are capable of quasi-instantaneous charge separation upon photoexcitation, due to the ultrafast charge transfer from the macrocycle to the complexed fullerene. These r…

Photoluminescence properties of S2 molecule trapped in Melanophlogite

We studied the photoluminescence properties of a sample of SiO2-clathrate Melanophlogite, a crystalline microporous material which is found in nature as a rare mineral. Upon β irradiation, the material displays an intense light emission under near-UV illumination. We studied in detail this optical activity by steady-state and time-resolved photoluminescence measurements as a function of temperature. The spectroscopic properties we find can be ascribed to a population of quasi-free molecules trapped within each of the two different types of cage available in the structure of this clathrate, although the spectroscopic properties of the guest molecules are affected by their interactions with t…

Phosphorous doping and drawing effects on the Raman spectroscopic properties of O=P bond in silica-based fiber and preform.

International audience; We report an experimental study of the doping and drawing effects on the Raman activities of phosphorus (P)-doped silica-based optical fiber and its related preform. Our data reveal a high sensitivity level in the full width at half maximum value of the 1330 cm−1 (O = P) Raman band to the P-doping level. Its increase with the P doping level does not clash with an increase in the disorder of the O = P surrendering matrix. In addition, we observe that in the central core region of the sample (higher doping level), the drawing process decreases the relative band amplitude. We tentatively suggest that this phenomenon is due to the change in the first derivate of the bond…

Diffusion and outgassing of O<inf>2</inf> in amorphous SiO<inf>2</inf> silica nanoparticles with specific surface properties

Structural and luminescence properties of amorphous SiO2 nanoparticles

We report an experimental study on the photoluminescence band peaked at 2.7 eV (blue band) induced by thermal treatments in nanometric amorphous SiO 2. In particular the emission dependence on the nanometric particles size as a function of their mean diameter from 7 nm up to 40 nm is investigated. We found that the emission amplitude increases on decreasing the particle diameter, showing a strong correlation between the blue band and the nanometric nature of the particles. By Raman spectroscopy measurements it is evidenced that the SiO2 nanoparticles matrix is significantly affected by the reduction of size. Basing on the shell-like model, these findings are interpreted assuming that the de…

Evolution of the sp2 content and revealed multilayer growth of amorphous hydrogenated carbon (a-C:H) films on selected thermoplastic materials

Amorphous hydrogenated carbon (a-C:H) films were gradually deposited on high-density polyethylene (HDPE), polyethylene terephthalate (PET) and polyoxymethylene (POM) via an indirect (f-type) and a direct (r-type) plasma-enhanced chemical vapor deposition (PECVD) process with acetylene plasma. The surface morphologies of the thicker r-depositions on the three different thermoplastics have been analyzed by atomic force microscopy (AFM) at varying micrometer scales. Absorbance spectroscopy has been used to characterize the optical properties of all coatings. Intrinsic stress release phenomena are revealed on thicker layers through the detection of characteristic surface corrugations. Based on …

Coupled irradiation-temperature effects on induced point defects in germanosilicate optical fibers

International audience; We investigated the combined effects of temperature and X-rays exposures on the nature of point defects generated in Ge-doped multimode optical fibers. Electron paramagnetic resonance (EPR) results on samples X-ray irradiated at 5 kGy(SiO2), employing different temperatures and dose rates, are reported and discussed. The data highlight the generation of the Ge(1), Ge(2), E0 Ge and E0 Si defects. For the Ge(1) and Ge(2), we observed a decrease in the induced defect concentrations for irradiation temperatures higher than *450 K, whereas the E0 defects feature an opposite tendency. The comparison with previous post-irradiation thermal treatments reveals peculiar effects…

Radiation induced generation of Non-Bridging Oxygen Hole Center: intrinsic and extrinsic processes

Optimization of the Optical Components in a Reflective High CPV Module

Coherent aspects of the local dipolar field in echo dynamics: A spectral narrowing effect.

We have measured the spectral content of the echo radiation emitted by a two-level spin system ([${\mathrm{AlO}}_{4}$${]}^{0}$ centers in quartz), after a two-pulse excitation sequence, ${\mathrm{\ensuremath{\theta}}}_{1}$-\ensuremath{\tau}-${\mathrm{\ensuremath{\theta}}}_{2}$. In general, the experimental spectral shapes reproduce qualitatively those calculated for an inhomogeneous system of noninteracting spins. However, we found that in certain ranges of the sequence parameters (${\mathrm{\ensuremath{\theta}}}_{1}$, ${\mathrm{\ensuremath{\theta}}}_{2}$, and \ensuremath{\tau}) the widths of the experimental spectra are less than expected by a factor that amounts up to 0.5. The observed na…

Characteristics of industrially manufactured amorphous hydrogenated carbon (a-C:H) depositions on high-density polyethylene

Industrially high-density polyethylene (HDPE) was successively covered by two types of amorphous hydrogenated carbon (a-C:H) films, one more flexible (f-type) and the other more robust (r-type). The films have been grown by radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) technique with acetylene plasma. The surface morphology of both types has been studied by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Contact angle measurements and Raman spectroscopy analysis were done to investigate the surface wettability and carbon chemical composition. Both types display similar morphology and grain growth pattern. Contact angle measurements revealed surfa…

Spectral properties and lifetime of green emission in γ-ray irradiated bismuth-doped silica photonic crystal fibers

Abstract We report an experimental investigation focused on the green emission detected in γ-ray irradiated Bismuth-doped photonic crystal fibers. Our photoluminescence spectra, recorded at room temperature, provide evidence for the presence of two emission bands both located at ~ 530 nm (2.34 eV). One emission is detected only in the Bi-doped core while the other, is detected in the cladding. These two emissions feature different excitation spectra and a fast and a slow decay lifetime. The origin of the fast emission decay, about ten nanoseconds, is tentatively attributed to a silica intrinsic defect, whereas the slow component, having lifetime of about 2 μs and featuring anti-stokes emiss…

Sensing of Transition Metals by Top-Down Carbon Dots

Carbon quantum dots (CQDs) are a new class of carbon-rich materials with a range of unique optical and structural properties. They can be defined as carbon nanoparticles, with sizes in the range of 1–10 nm, displaying absorption and emission activities in the UV-VIS range. Depending on the structure, CQDs display a wide variability of properties, which provides the possibility of finely tuning them for several applications. The great advantages of CQDs are certainly the ease of synthesis, non-toxicity, and the strong interactions with the surrounding environment. Based on this, CQDs are especially promising as selective chemosensors. The present study reports on carbon quantum dots synthesi…

Temperature and time dependent electron trapping in Al2O3 thin films onto AlGaN/GaN heterostructures

In this article, the charge trapping phenomena in Al2O3 thin films grown by atomic layer deposition (ALD) on AlGaN/GaN heterostructures have been studied by time-dependent capacitance–voltage (C-V) measurements as a function of temperature. In particular, monitoring the transient of the capacitance enabled us to estimate the maximum depth of the insulating layer interested by the negative charge trapping effect under our bias stress conditions and to determine a charge traps density in the bulk Al2O3 in the order of 3 × 1019 cm−3. A temperature dependent C-V analysis up to 150 °C demonstrated the presence of two competitive mechanisms that rule the electron capture and emission in the Al2O3…

Photoluminescence of SiO2 under excitation by synchrotron radiation above the fundamental absorption edge

Temperature dependence of O2 singlet photoluminescence in silica nanoparticles

Defect-related visible luminescence of silica nanoparticles

The high photon emissivity in the visible spectral range is one of the most relevant phenomena emerging from the reduction of silica down to nanoscale; hence it is promising for the development of optical nanotechnologies (down converter, probes, display). It is well accepted that the origin of this luminescence is related to the high specific surface (~100 m2/g) that favors the formation of optically active defects at the nanosilica surface. With the aim to clarify the role of specific luminescent defects, here we report a detailed study of spectral and decay features by time-resolved photoluminescence spectra under a visible-UV tunable laser excitation. Our study is carried out on differe…

Phonon Coupling Properties of Non Bridging Oxygen Hole Centers at a Silica Surface Probed by Site-Selective Luminescence Excitation

Steady state γ-ray radiation effects on Brillouin fiber sensors

International audience; Brillouin optical time-domain analysis (BOTDA) sensors offer remarkable advantages for the surveillance of the planned French deep geological radioactive wastes repository, called Cigéo1,2. In this work we study the performances of Brillouin distributed sensors in harsh environment. We evaluate the radiation tolerance of different sensor classes and their responses evolution during γ-ray exposition with 1kGy/h dose rate (to reach ~0.2MGy) and after 1, 3, 6 and 10 MGy accumulated doses. Measurements on strained Ge-doped SMF are reported to highlight the variation on Brillouin scattering proprieties, both intrinsic frequency position of Brillouin shift and its dependen…

Optical absorption induced by UV laser radiation in Ge-doped amorphous silica probed by in situ spectroscopy

We studied the optical absorption induced by 4.7eV pulsed laser radiation on Ge-doped a-SiO2 synthesized by a sol-gel technique. The absorption spectra in the ultraviolet spectral range were measured during and after the end of irradiation with an in situ technique, evidencing the growth of an absorption signal whose profile is characterized by two main peaks near 4.5eV and 5.7eV and whose shape depends on time. Electron spin resonance measurements performed ex situ a few hours after the end of exposure permit to complete the information acquired by optical absorption by detection of the paramagnetic Ge(1) and Ge-E' centers laser-induced in the samples.

H(II) centers in natural silica under repeated UV laser irradiations

We investigated the kinetics of H(II) centers (=Ge'-H) in natural silica under repeated 266nm UV irradiations performed by a Nd:YAG pulsed laser. UV photons temporarily destroy these paramagnetic defects, their reduction being complete within 250 pulses. After re-irradiation, H(II) centers grow again, and the observed recovery kinetics depends on the irradiation dose; multiple 2000 pulses re-irradiations induce the same post-irradiation kinetics of H(II) centers after each exposure cycle. The analysis of these effects allows us to achieve a deeper understanding of the dynamics of the centers during and after laser irradiation.

Aging of MCM41, MSU-H and MSU-F mesoporous systems investigated through the Raman spectroscopy

Here we report an experimental investigation, based on the Raman spectroscopy, on the aging of some mesoporous silica based systems. In details, we studied the aging in air of the MCM41, the MSU-H and the MSU-F materials by acquiring the Raman spectra of as received and of mechanically pressed, at 0.2 and 0.45 GPa, powders. Our data evidenced that the starting powders of the MCM41 and of the MSU-H undergo structural modification when they are exposed to the ambient atmosphere, such modification consisting in the decrease of the D2 Raman band (originated by the three member rings). At variance the powders of the MSU-F appear to be stable. Furthermore, by pressing the starting powders to prod…

Investigation of Coating Impact on OFDR Optical Remote Fiber-Based Sensors Performances for Their Integration in High Temperature and Radiation Environments

The response of optical frequency-domain reflectometry-based temperature sensors is here investigated in harsh environments (high temperature, high radiation dose) focusing the attention on the impact of the fiber coating on the sensor performances in such conditions. Our results demonstrate that the various coating types evolve differently under thermal treatment and/or radiations, resulting in a small (<5%) change in the temperature coefficient of the sensor. The identified procedure, consisting of a prethermal treatment of the fiber at its maximum coating operating temperature, is here verified up to 150 °C for higherature acrylate and up to 300 °C for polyamide coating. This method allo…

In-situ observation of β-ray induced optical absorption in a-SiO2: radiation darkening and room temperature recovery

Nano-Oxides produced by ns laser ablation in liquids

Laser ablation in liquids was successfully applied to produce nanosized oxides from Si, Ti and Zn targets. The obtained colloidal solutions of nanoparticles were investigated by complementary techniques: AFM, IR and Raman spectroscopies; optical absorption and time resolved photoluminescence. The results demonstrate the production of SiO2, TiO2 and ZnO. The absorption and emission properties of these material have been also investigated and appear to be promising for optical applications.

Phonon coupling of non-bridging oxygen hole center with the silica environment: Temperature dependence of the 1.9 eV emission spectra

Abstract We report an experimental study on the shape of the 1.9 eV emission associated with non-bridging oxygen hole centers in silica and its temperature dependence, from 4 up to 300 K, under visible and ultraviolet excitation. Our analysis points out that these defects are coupled with their environment by phonons whose contribution can be described by the single mode of mean frequency between 300–400 cm −1 and Huang–Rhys factor of ∼3. On increasing the temperature, the luminescence intensity undergoes a thermal quenching caused by non-radiative processes, its deviation from a pure Arrhenius law can be accounted for by an uniform distribution of activation energy, from 0.002 to 0.05 eV. …

X-ray irradiation effects on a multistep Ge-doped silica fiber produced using different drawing conditions

International audience; We report an experimental study based on confocal microscopy luminescence (CML) and electron paramagnetic resonance (EPR) measurements to investigate the effects of the X-ray (from 50 krad to 200 Mrad) on three specific multistep Ge doped fibers obtained from the same preform by changing some of the drawing conditions (tension and speed). CML data show that, both before and after the irradiation, Germanium Lone Pair Center (GLPC) concentrations are similarly distributed along the diameters of the three fibers and they are partially reduced by irradiation. The irradiation induces also the Non Bridging Oxygen Hole Center (NBOHC) investigated by CML and other paramagnet…

Optical transitions associated with non bridging oxygen hole centers in irradiated silica

Influence of fluorine on the fiber resistance studied through the nonbridging oxygen hole center related luminescence

The distribution of Non-Bridging Oxygen Hole Centers (NBOHCs) in fluorine doped optical fibers was investigated by confocal microluminescence spectroscopy, monitoring their characteristic 1.9 eV luminescence band. The results show that these defects are generated by the fiber drawing and their concentration further increases after c irradiation. The NBOHC concentration profile along the fiber provides evidence for an exponential decay with the fluorine content. This finding agrees with the role of fluorine in the fiber resistance and is discussed, from the microscopic point of view, by looking at the conversion mechanisms from strained bonds acting as precursors.

Core‐Selective Silver‐Doping of Gold Nanoclusters by Surface‐Bound Sulphates on Colloidal Templates: From Synthetic Mechanism to Relaxation Dynamics

Funding Information: This work was carried out under the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), Academy of Finland's Centre of Excellence in Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland (No. 321443, 328942, 308647, and 318891) and Photonic Research and Innovation (PREIN) as well as FinnCERES flagships. L.F. and X.C. thanks for support from CSC (IT Center for Science, Finland) for providing computation resources. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/742829/EU//DRIVEN Ultra-small luminescent gold nanoclusters (AuNCs) have gained substantia…

Luminescence mechanisms of defective ZnO nanoparticles.

ZnO nanoparticles (NPs) synthesized by pulsed laser ablation (PLAL) of a zinc plate in deionized water were investigated by time-resolved photoluminescence (PL) and complementary techniques (TEM, AFM, μRaman). HRTEM images show that PLAL produces crystalline ZnO NPs in wurtzite structure with a slightly distorted lattice parameter a. Consistently, optical spectra show the typical absorption edge of wurtzite ZnO (Eg = 3.38 eV) and the related excitonic PL peaked at 3.32 eV with a subnanosecond lifetime. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which shows a power law decay kinetics. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Ra…

Radiation effects on antimonium-doped Yb-fibers

Irradiation temperature effects on the induced point defects in Ge-doped optical fibers

We present an experimental investigation on the combined effects of temperature and irradiation on Ge-doped optical fibers. Our samples were X-ray (10 keV) irradiated up to 5 kGy with a dose rate of 50 Gy(SiO2)/s changing the irradiation temperature in the range 233-573 K. After irradiation we performed electron paramagnetic resonance (EPR) and confocal microscopy luminescence (CML) measurements. The recorded data prove the generation of different Ge related paramagnetic point defects and of a red emission, different from that of the Ge/Si Non-Bridging Oxygen Hole center. Furthermore, by comparing the behaviour of the EPR signal of the Ge(1) as a function of the irradiation temperature with…

Influence of the manufacturing process on the radiation sensitivity of fluorine-doped silica-based optical fibers

International audience; In this work, we analyze the origins of the observed differences between the radiation sensitivities of fluorine-doped optical fibers made with different fabrication processes. We used several experimental techniques, coupling in situ radiation-induced absorption measurements with post mortem confocal microscopy luminescence measurements. Our data showed that the silica intrinsic defects are generated both from precursor sites and from strained regular Si-O-Si linkages. Our work also provides evidence for the preponderant role of the chlorine in determining the optical losses at about 3.5 eV. The results show that the manufacturing process of these fibers strongly af…

Character of the Reaction between Molecular Hydrogen and a Silicon Dangling Bond in Amorphous SiO2

The passivation by diffusing H2 of silicon dangling bond defects (E′ centers, O3tSi•) induced by laser irradiation in amorphous SiO2 (silica) is investigated in situ at several temperatures. It is found that the reaction between the E′ center and H2 requires an activation energy of 0.39 eV and that its kinetics is not diffusionlimited. The results are compared with previous findings on the other fundamental paramagnetic point defect in silica, the oxygen dangling bond, which features completely different reaction properties with H2. Furthermore, a comparison is proposed with literature data on the reaction properties of surface E′ centers, of E′ centers embedded in silica films, and with th…

Nd:YAG laser induced E′ centers probed by in situ absorption measurements

We investigated various types of commercial silica irradiated with a pulsed Nd:YAG laser radiation (4.66 eV), with exposure time ranging up to 10000 s. Transient E' centers were probed in situ by measuring the amplitude of the optical absorption band at 5.8 eV (due to E' centers) both during and after irradiation. The laser-induced absorption is observed only in natural samples, whereas the synthetic materials exhibit high toughness to radiation effect. The reported results evidence that the kinetics of E' centers is influenced by their reaction with diffusing molecular hydrogen H2 made available by dimerization of radiolytic H0.

Photoluminescence of Point Defects in Silicon Dioxide by Femtosecond Laser Exposure

The nature of the radiation-induced point defects in amorphous silica is investigated through online photoluminescence (PL) under high intensity ultrashort laser pulses. Using 1030 nm femtosecond laser pulses with a repetition rate of 1 kHz, it is possible to study the induced color centers through their PL signatures monitored during the laser exposure. Their generation is driven by the nonlinear absorption of the light related to the high pulse peak powers provided by femtosecond laser, allowing to probe the optical properties of the laser exposed region. The experiment is conducted as a function of the laser pulse power in samples with different OH contents. The results highlight the dif…

Photoluminescence and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles

An experimental study by Raman and Photoluminescence (PL) spectroscopies on the emission and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles of commercial origin with diameters from 14 to 40 nm is reported. Stationary and time resolved PL measurements have been carried out to characterize the Near Infrared (NIR) emission at 1272 nm of O2. Emission features similar to those of bulk silica systems with a sharp PL band and excitation channels in the NIR, at 1070 nm, and in the visible, at 765 and 690 nm are found, with peculiarities arising from embedding O2 in nanostructures. The study of the NIR PL lifetime as a function of temperature down to 10 K enabled to reveal the …

Luminescence Properties of Non Bridging Oxygen Hole Centers at a Silica Surface

Oxidative changes in Sicilian extra virgin olive oil under heating treatment detected by FTIR spectroscopy, viscosimetry and time-resolved luminescence

Spectroscopic studies of the origin of the radiation-induced degradation in phosphorous-doped optical fiber and preforms

In this paper, we study the radiation-induced point defects related to the phosphorus element that is commonly used to improve the optical properties of silica-based glasses but is responsible of a dramatic increase in their radiation sensitivity. To this aim, the influence of x-ray irradiation on prototype phosphorus-doped canonical fibers and their related preforms was investigated by in situ radiation induced attenuation (RIA), optical absorption, and electron spin resonance (ESR) spectroscopy. The RIA spectra in the (1.5-5 eV) range, can be explained by the presence of at least three absorption bands induced by radiation exposure. Additionally the X-dose dependence of such bands was stu…

Temperature and excitation energy dependence of decay processes of luminescence in Ge-doped silica

We report experimental results on the time decay of photoluminescence at 4.2 eV in Ge-doped silica. This optical emission is assigned to a singlet-singlet transition between electronic states localized on an oxygen deficiency nearby a Ge atom and its radiative decay rate is in competition with an intersystem crossing mechanism that populates an excited triplet state. We investigate the dependence of the lifetime of this photoluminescence on the temperature, in the 6--295 K range, and on the excitation energy, in the ultraviolet and vacuum ultraviolet region. The mean value of the decay time decreases on increasing the temperature, in agreement with the phonon-assisted nature of the intersys…

Ultrafast spectroscopic investigation on fluorescent carbon nanodots: the role of passivation.

Disentangling the respective roles of the surface and core structures in the photocycle of carbon nanodots is a critical open problem in carbon nanoscience. While the need of passivating carbon dot surfaces to obtain efficiently emitting nanoparticles is very well-known in the literature, it is unclear if passivation introduces entirely new surface emitting states, or if it stabilizes existing states making them fluorescent. In this multi-technique femtosecond spectroscopy study, the relaxation dynamics of non-luminescent (non-passivated) carbon dots are directly compared with their luminescent (passivated) counterparts. Non-passivated dots are found to host emissive states, albeit very sho…

Photoluminescence of Si nanocrystals embedded in SiO2: Excitation/emission mapping

Time-resolved photoluminescence from Si nanocrystals produced by 1100∘C thermal annealing of SiOx/SiO2 multilayers were investigated by tunable laser excitation, achieving a detailed excitation/emission pattern in the visible and UV range. The emission lineshape is a gaussian curve inhomogenously broadened because of the size distribution of Si nanocrystals, the excitation spectrum consists of the overlap of two gaussian bands centered around 3.4 and 5.1 eV. The mapping of luminescence spectral components with the lifetime points out the energy cubic dependence of the spontaneous emission rate. These findings are interpreted on the basis of models proposed in literature that associate this …

The landscape of the excitation profiles of the αE and β emission bands in silica

Abstract We report data about the relevance of the conformational heterogeneity in determining the optical properties of oxygen deficiency point defects in natural silica samples. The spectral profiles of the photoluminescence emissions at about 4.2 eV (α E band) and at about 3.15 eV (β band), and the efficiency of the intersystem-crossing mechanism connecting them appear modified by a fine tuning of the excitation energy within the B 2β absorption band. Moreover, the relative excitation optically spectra indicate the presence of optically distinguishable contributions to the emission profile. The reported data are attributed to a distribution of centers that maps into a spectral inhomogene…

Effect of air on oxygen p-doped graphene on SiO2

Stability in ambient air or in vacuum-controlled atmosphere of molecular oxygen-induced p-type doping of graphene monolayer on SiO2 substrate on Si is investigated by micro-Raman spectroscopy and atomic force microscopy (AFM). The Raman 2D and G bands spectral positions and amplitude ratio are affected by the permanence in air atmosphere in a time scale of months whereas the vacuum safely maintains the doping effects determined through Raman bands. No morphological effects are induced by the doping and post-doping treatments. A reactivity of ambient molecular gas with stably trapped oxygen is suggested to induce the doping modification. (C) 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Role of vitreous matrix on the optical activity of Ge-doped silica

Abstract We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B 2β ) and on the two related emissions at ∼4.2 eV (α E ) and at ∼3.1 eV (β). From the temperature dependence of B 2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the …

Gamma and x-ray irradiation effects on different Ge and Ge/F doped optical fibers

International audience; We performed electron paramagnetic resonance (EPR) measurements on γ and X ray irradiated Ge doped and Ge/F co-doped optical fibers. We considered three different drawing conditions (speed and tension), and for each type of drawing, we studied Ge and Ge/F doped samples having Ge doping level above 4% by weight. The EPR data recorded for the γ ray irradiated fibers confirm that all the samples exhibit a very close radiation response regardless of the drawing conditions corresponding to values used for the production of specialty fibers. Furthermore, as for the X irradiated materials, in the γ ray irradiated F co-doped fibers, we observed that the Ge(1) and the Ge(2) d…

Hydrogen and radiation induced effects on performances of Raman fiber-based temperature sensors

International audience; Raman Distributed Temperature Sensors (RDTS) offer exceptional advantages for the monitoring of the envisioned French deep geological repository for nuclear wastes, called Cigéo. Here, we present experimental studies on how the performances of RDTS evolve in harsh environments like those associated with H2 or g-rays. Both of them are shown to strongly affect the temperature measurements made with RDTS. We showed that by adapting the characteristics of the used fiber for the sensing, we could limit its degradation but that additional hardening by system studies will have to be developed before integration of RDTS in Cigéo.

Raman based distributed fiber optic temperature sensors for structural health monitoring in radiation environment

Raman distributed temperature sensor (RDTS) measurements were performed during γ-radiation on three different classes of standard multimode fibers (pure, Ge-doped and F-doped). The sensor response is affected by the radiation induced attenuation phenomena leading to errors in the temperature measurements. The amplitude of this error strongly depends on the fiber type and the irradiation conditions. These results are promising in view of the integration of these RDTS into the deep geological repository for radioactive waste.

Generation and Annealing of Defects in Silica Probed by in Situ Absorption Measurements

Luminescence of γ-radiation-induced defects in α-quartz

Optical transitions associated with γ-radiation-induced defects in crystalline α-quartz were investigated by photoluminescence excited by both pulsed synchrotron radiation and steady-state light. After a 10 MGy γ-dose we observed two emissions at 4.9 eV (ultraviolet band) and 2.7 eV (blue band) excitable in the range of the induced absorption band at 7.6 eV. These two luminescence bands show a different temperature dependence: the ultraviolet band becomes bright below 80 K; the blue band increases below 180 K, but drops down below 80 K. Both emissions decay in a timescale of a few ns under pulsed excitation, however the blue band could also be observed in slow recombination processes and it…

Photoluminescence of Carbon Dots Embedded in a SiO2 Matrix

Abstract We synthetized carbon dots by a pyrolitic method, and studied their photoluminescence in aqueous environment and upon trapping in a solid matrix. To this aim, we devised a facile procedure allowing to embed the dots in amorphous SiO2, without the need of any pre-functionalization of the nanoparticles, and capable of yielding a brightly photoluminescent monolith. Experimental data reveal a remarkable similarity between the emission properties of carbon dots in water and in SiO2, suggesting that the chromophores responsible of the photoluminescence undergo only weak interactions with the environment. Time-resolved photoluminescence data reveal that the typical photoluminescence tunab…

Pulsed X‐Ray Radiation Responses of Solarization‐Resistant Optical Fibers

International audience; The transient radiation‐induced attenuation (RIA) of two different versions of pure‐silica‐core (PSC) multimode optical fibers (so‐called “solarization‐resistant” fibers) exposed to nanosecond 1 MeV X‐ray pulses are investigated. On‐line RIA spectra measurements at both room temperature (RT) and liquid nitrogen temperatures (LNT) in the range 1–3.5 eV are performed. Following the RIA kinetics, the properties of the metastable defects that are bleached just after the pulse are discussed. The spectral decomposition of the RIA is performed using known Gaussian bands associated to point defects absorbing in this spectral range. For both fiber types, the generation and th…

Luminescent Silicon nanocrystals produced by ns pulsed laser ablation

The reduction of Si down to nanoscale introduces a peculiar visible luminescence, surprisingly for a not highly emissive material. This feature is relevant in connection with several application fields (optoelectronics, medicine) and has lead the research towards the development of production methods successful to control the physical and chemical properties of the nanosized Si so as to enhance and tune the luminescence. To this purpose, the laser ablation in liquids is particularly promising since it provides effective controlling parameters (laser photon energy, fluence, repetition rate, liquid reactivity) for the morphology and the structure of Si-related products. Here we report a study…

Combined High Dose and Temperature Radiation Effects on Multimode Silica-Based Optical Fibers

International audience; We investigate the response of Ge-doped, P-doped, pure-silica, or Fluorine-doped fibers to extreme environments combining doses up to MGy(SiO $_{{{2}}}$) level of 10 keV X-rays and temperatures between 25 C and 300 C . First, we evaluate their potential to serve either as parts of radiation tolerant optical or optoelectronic systems or at the opposite, for the most sensitive ones, as punctual or distributed dosimeters. Second, we improve our knowledge on combined ionizing radiations and temperature (R&T) effects on radiation-induced attenuation (RIA) by measuring the RIA spectra in the ultraviolet and visible domains varying the R&T conditions. Our results reveal the…

Micro-Raman investigation of X or gamma irradiated Ge doped fibers

International audience; Micro-Raman spectra have been recorded on Ge doped optical fibers before and after 10 keV-X or c-ray irradiation up to doses of 1 MGy (X-ray) or 7.8 MGy (-ray). Our data provide evidence that, at such dose levels, the glass matrix is not modified in a detectable way. We observed that varying the Ge doping levels from 0 to about 11 wt.%, X or radiation sensitivity of the overall matrix remains unchanged. Such results are observed for fibers obtained with drawing conditions within the usual range used for the fabrication of specialty fibers as radiation-tolerant waveguides. Our data support the potentiality of fiberbased sensors using glass properties, e.g. Raman sc…

Study of silica-based intrinsically emitting nanoparticles produced by an excimer laser

International audience; We report an experimental study demonstrating the feasibility to produce both pure and Ge-doped silica nanoparticles (size ranging from tens up to hundreds of nanometers) using nanosecond pulsed KrF laser ablation of bulk glass. In particular, pure silica nanoparticles were produced using a laser pulse energy of 400 mJ on pure silica, whereas Ge-doped nanoparticles were obtained using 33 and 165 mJ per pulse on germanosilicate glass. The difference in the required energy is attributed to the Ge doping, which modifies the optical properties of the silica by facilitating energy absorption processes such as multiphoton absorption or by introducing absorbing point defect…

Spectral heterogeneity of oxygen-deficient centers in Ge-doped silica

Abstract We report an experimental investigation of the emission spectra of a 1000 mol ppm sol–gel Ge-doped silica by fine tuning the excitation energy in the ultraviolet (UV) range, around 5 eV , and in the vacuum-UV range, around 7.3 eV , at room temperature and at 10 K . The sample is characterized by a blue (centered at ∼3.2 eV ) and an UV (centered at ∼4.3 eV ) bands. We have found that the ratio between the area of the blue and the UV bands depends on the temperature and on the excitation energy in both the vacuum-UV and the UV range. At both temperatures the spectral features of the blue and the UV bands are weakly affected when the excitation is varied in the vacuum-UV. At variance,…

Luminescence of gamma-radiation-induced defects in alpha-quartz

Optical transitions associated with gamma-radiation-induced defects in crystalline a-quartz were investigated by photoluminescence excited by both pulsed synchrotron radiation and steady-state light. After a 10 MGy gamma-dose we observed two emissions at 4.9 eV (ultraviolet band) and 2.7 eV (blue band) excitable in the range of the induced absorption band at 7.6 eV. These two luminescence bands show a different temperature dependence: the ultraviolet band becomes bright below 80 K; the blue band increases below 180 K, but drops down below 80 K. Both emissions decay in a timescale of a few ns under pulsed excitation, however the blue band could also be observed in slow recombination processe…

Radiation hardening techniques for rare-earth-based optical fibers and amplifiers

Er/Yb doped fibers and amplifiers have been shown to be very radiation sensitive, limiting their integration in space. We present an approach including successive hardening techniques to enhance their radiation tolerance. The efficiency of our approach is demonstrated by comparing the radiation responses of optical amplifiers made with same lengths of different rare-earth doped fibers and exposed to gamma-rays. Previous studies indicated that such amplifiers suffered significant degradation for doses exceeding 10 krad. Applying our techniques significantly enhances the amplifier radiation resistance, resulting in a very limited degradation up to 50 krad. Our optimization techniques concern …

Role of Ce3+ as sensitizer for the infrared luminescence of phosphosilicate Er/Yb doped glasses

The luminescence properties of the Yb/Er-doped phosphosilicate preforms used for the design of active optical fibers were investigated under a tunable laser excitation from ultraviolet to infrared domain. We demonstrated that codoping the glass matrix with Ce3+ ions strongly influences the infrared emission associated with Er3+ ions, it enhances the energy transfer from Yb3+ to Er3+ ions, and it provides an additional ultraviolet excitation channel for the emission of both Yb3+ and Er3+ ions. The excitation/emission pathways are discussed on the basis of models proposed in literature for other systems.

Hydrogen-related conversion processes of Ge-related point defects in silica triggered by UV laser irradiation

The conversion processes of Ge-related point defects triggered in amorphous SiO2 by 4.7eV laser exposure were investigated. Our study has focused on the interplay between the (=Ge&#8226;-H) H(II) center and the twofold coordinated Ge defect (=Ge&#8226;&#8226;). The former is generated in the post-irradiation stage, while the latter decays both during and after exposure. The post-irradiation decay kinetics of =Ge&#8226;&#8226; is isolated and found to be anti-correlated to the growth of H(II), at least at short times. From this finding it is suggested that both processes are due to trapping of radiolytic H0 at the diamagnetic defect site. Furthermore, the anti-correlated behavior is preserve…

Influence of oxide substrates on monolayer graphene doping process by thermal treatments in oxygen

Abstract The structural and the electronic properties of monolayer graphene made by chemical vapor deposition and transferred on various oxide substrates ( SiO 2 , Al 2 O 3 , and HfO 2 ) are investigated by Raman Spectroscopy and Atomic Force Microscopy in order to highlight the influence of the substrate on the features of p-doping obtained by O 2 thermal treatments. By varing the treatment temperature up to 400 °C, the distribution of the reaction sites of the substrates is evaluated. Their total concentration and the consequent highest doping available is determined and it is shown that this latter is linked to the water affinity of the substrate. Finally, by varing the exposure time to …

Ultrafast Interface Charge Separation in Carbon Nanodot-Nanotube Hybrids

Carbon dots are an emerging family of zero-dimensional nanocarbons behaving as tunable light harvesters and photoactivated charge donors. Coupling them to carbon nanotubes, which are well-known electron acceptors with excellent charge transport capabilities, is very promising for several applications. Here, we first devised a route to achieve the stable electrostatic binding of carbon dots to multi- or single-walled carbon nanotubes, as confirmed by several experimental observations. The photoluminescence of carbon dots is strongly quenched when they contact either semiconductive or conductive nanotubes, indicating a strong electronic coupling to both. Theoretical simulations predict a favo…

Gold Au(I)6 Clusters with Ligand-Derived Atomic Steric Locking: Multifunctional Optoelectrical Properties and Quantum Coherence

Funding Information: This work was supported by the ERC Advanced grant (DRIVEN, ERC‐2016‐AdG‐742829), the ERC grant (834742), the EU H2020‐MSCA‐RISE‐872049 (IPN‐Bio), the Academy of Finland's Centre of Excellence in Molecular Engineering of Biosynthetic Hybrid Materials Research (HYBER, 2014–2019), and Life‐Inspired Hybrid Materials (LIBER, 346108), Academy of Finland project fundings (No. 352900, 314810, 333982, 336144, 352780, 352930 and 353364), FinnCERES and Photonics Research and Innovation (PREIN) flagship programs. The authors acknowledge the provision of facilities and technical support by Aalto University OtaNano – Nanomicroscopy Center (Aalto‐NMC). | openaire: EC/H2020/834742/EU//…

Thermal oxidative process in extra-virgin olive oils studied by FTIR, rheology and time-resolved luminescence

Abstract With the aim to characterise the antioxidant properties of different extra-virgin olive oils and to understand in more detail the mechanisms of oil degradation, we have made an experimental study on thermal induced oxidative processes of extra-virgin olive oils by using different techniques: Fourier Transform Infrared (FTIR) spectroscopy, rheology and time-resolved luminescence. The oxidation process was followed at three different heating temperatures (30, 60 and 90 °C) as a function of time up to 35 days. Thermal treatment induced changes in the FTIR spectra in the wavenumbers region 3100–3600 cm −1 : in particular, the absorption profiles show an initial formation of hydroperoxi…

Controlling the oxidation processes of Zn nanoparticles produced by pulsed laser ablation in aqueous solution

We used online UV-VIS optical absorption and photoluminescence spectra, acquired during and after pulsed laser ablation of a Zinc plate in aqueous solution, to investigate the effect of the laser repetition rate and liquid environment on the oxidation processes of the produced nanoparticles. A transient Zn/ZnO core-shell structure was revealed by the coexistence of an absorption peak around 5.0 eV due to Zn surface plasmon resonance and of an edge at 3.4 eV coming from wurtzite ZnO. The growth kinetics of ZnO at the various repetition rates, selectively probed by the excitonic emission at 3.3 eV, began immediately at the onset of laser ablation and was largely independent of the repetition …

Effect of Halogen Ions on the Photocycle of Fluorescent Carbon Nanodots

Carbon dots (C-dots) are well-known for their strong sensitivity to the environment, which reflects on intensity and shape changes of their fluorescence, induced by various interacting ions and molecules in solution. Although these interactions have been extensively studied in the last few years, especially in view of their possible sensing applications, the existing works have mostly focused on the quenching of C-dot fluorescence induced by metal cations. In fact, these latter easily bind to C-dots surfaces, which are negatively charged in most cases, promoting an electron transfer from the surface to them. Much less is known from the literature on the effect induced on C-dots by prototypi…

Printable Thermo- and Photo-stable Poly(D,L-lactide)/Carbon Nanodots Nanocomposites via Heterophase Melt-Extrusion Transesterification

We propose for the first time an one-pot synthesis of carbon nanodots-poly(D,L-lactide) (CDs-PLA) nanocomposites, obtained by a simple reactive melt-extrusion process involving polar surface groups of multicolor CDs and ester bonds of PLA chains. Apart from providing an excellent method to produce polyester-coated CDs, our protocol allows obtaining perfect PLA@CDs blends giving rise to homogeneous extruded PLA@CDs filaments (ePLA@CDs) suitable for 3D printing applications (e.g., additive manufacturing for biomaterials and biodegradable encoded polymer ink technology). We demonstrate that ePLA@CDs filaments can be used to build a huge range of fluorescent objects with increasing architectura…

Luminescence of the surface nonbridging oxygen hole center in silica: Spectral and decay properties

We investigated the red luminescence in a porous film of silica nanoparticles, originating from surface nonbridging oxygen hole centers. The excitation spectrum was measured from 1.8 to 8.0 eV by a tunable laser system and a synchrotron radiation source; this spectrum evidences a peak at 2.0 eV, nearly overlapping with the emission, and an ultraviolet broadband with peaks at 4.8 and 6.0 eV. The emission is characterized by a spectrum with two subbands split by 0.07 eV, its decay occurs with lifetime longer than 30 microsec and undergoes a thermal quenching by a factor aboout 2 with increasing temperature from 10 to 290 K. The optical characteristics of surface and bulk centers are discussed…

Radiation effects on optical frequency domain reflectometry fiber-based sensor

International audience; 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 …

Visible luminescence of nanosilica: slow and fast contributions

Different natures of surface electronic transitions of carbon nanoparticles

The photoluminescence behaviour of carbon-based nanodots is still debated. Both core and surface structures are involved in the emission mechanism, and the electronic transitions can be modified by external agents such as metal ions or pH, but the general relation between the structure and the optical function is poorly understood. Here, we report a comparative study on the effects of these variables, changing the core structure from crystalline to amorphous, and modifying the surface structure by different passivation procedures. Our results highlight that the emission mechanism of the tunable visible fluorescence is identical for crystalline and amorphous samples, indicating the independe…

Effetto della nicotina sulla produzione di gelatinasi B(MMP-9) in cheratinociti della mucosa orale

Thioflavin-T doped silica nanoparticles by basic-catalyzed sol-gel synthesis

We developed a basic-catalyzed sol-gel procedure that allows to synthesize silica nanoparticles functionalized with Thioflavin-T (ThT). During the synthesis, the formation of the doped silica nanoparticles was monitored by absorbance spectra indicating that the catalyst does not cause the total hydroxylation of the dye. Fluorescence measurements carried out on the ThT doped silica nanoparticles proved the attachment of ThT on silica and Raman spectroscopy provided information about the dye structure.

Vacuum ultraviolet excitation of the 1.9-eV emission band related to nonbridging oxygen hole centers in silica

Physical review / B 69, 153201 (2004). doi:10.1103/PhysRevB.69.153201

Bleaching and thermal recovery of PL emissions in natural silica

Abstract We have investigated the bleaching of two photoluminescence (PL) emissions at 3.1 and 4.2 eV and the related growth of an electron spin resonance (ESR) signal, consisting in a hyperfine doublet split by 11.8 mT, in natural silica γ-irradiated by low doses, up to 1 Mrad. These observations definitely support the existence of a conversion mechanism, from optically active defects to paramagnetic ones. To further investigate this conversion process and the stability of the γ-induced paramagnetic centers, we performed PL and ESR measurements in samples that, after a γ exposure at 1 Mrad dose, were thermally treated at various temperatures ranging from 330 to 430 K. We found that the int…

Photoinduced charge transfer from Carbon Dots to Graphene in solid composite

Abstract The emission in solid phase of Carbon Dots (CDs) deposited by drop-casting technique is investigated by means of micro-photoluminescence. Graphene and SiO2 are used as substrates, and the influence of their different nature – conductive or insulating – on the emission of CDs is highlighed. In particular, a systematic loss of efficiency in the emission of CDs on graphene is found, suggesting a CD-graphene interaction possibly due to a photoinduced electron transfer between the surface states of CDs and the conduction band of graphene. Finally, thanks to the negligible influence on CDs emission, SiO2 substrate is used as support to perform thermal processing of CDs in solid phase, sh…

Intrinsic Point Defects in Silica for Fiber Optics Applications

Due to its unique properties, amorphous silicon dioxide (a-SiO2) or silica is a key material in many technological fields, such as high-power laser systems, telecommunications, and fiber optics. In recent years, major efforts have been made in the development of highly transparent glasses, able to resist ionizing and non-ionizing radiation. However the widespread application of many silica-based technologies, particularly silica optical fibers, is still limited by the radiation-induced formation of point defects, which decrease their durability and transmission efficiency. Although this aspect has been widely investigated, the optical properties of certain defects and the correlation betwee…

Hydrogen diffusion limited reactions of paramagnetic defects induced by UV laser exposure in amorphous SiO2

Highly Homogeneous 2D/3D Heterojunction Diodes by Pulsed Laser Deposition of MoS2 on Ion Implantation Doped 4H-SiC

In this paper, 2D/3D heterojunction diodes have been fabricated by pulsed laser deposition (PLD) of MoS2 on 4H-SiC(0001) surfaces with different doping levels, i.e., n− epitaxial doping (≈1016 cm−3) and n+ ion implantation doping (&gt;1019 cm−3). After assessing the excellent thickness uniformity (≈3L-MoS2) and conformal coverage of the PLD-grown films by Raman mapping and transmission electron microscopy, the current injection across the heterojunctions is investigated by temperature-dependent current–voltage characterization of the diodes and by nanoscale current mapping with conductive atomic force microscopy. A wide tunability of the transport properties is shown by the SiC surface dopi…

Engineered Ferritin with Eu3+ as a Bright Nanovector: A Photoluminescence Study

Ferritin nanoparticles play many important roles in theranostic and bioengineering applications and have been successfully used as nanovectors for the targeted delivery of drugs due to their ability to specifically bind the transferrin receptor (TfR1, or CD71). They can be either genetically or chemically modified for encapsulating therapeutics or probes in their inner cavity. Here, we analyzed a new engineered ferritin nanoparticle, made of the H chain mouse ferritin (HFt) fused with a specific lanthanide binding tag (LBT). The HFt-LBT has one high affinity lanthanide binding site per each of the 24 subunits and a tryptophane residue within the tag that acts as an antenna able to transfer …

UV and vacuum-UV properties of ge related centers in gamma irradiated silica

Photochemical inhomogeneity in the reduction process of the optical activity related to Ge oxygen deficient point defects in silica, characterized by an absorption band centered at 5.15 v eV and two emission bands centered at 3.2 v eV and 4.3 v eV, have been investigated. We have made a comparative study of the stationary and time dependent photoluminescence under excitation in the UV (5 v eV) and in the vacuum-UV (7.4 v eV) ranges in natural silica samples with native and with n -irradiation bleached optical activity. Our measurements evidence that the same spectral features are observed in the native and in the irradiated samples, but for an intensity reduction in the irradiated ones. Mor…

Multiphoton process investigation in silica by UV femtosecond laser

We investigated the interaction processes between high intensity femtosecond ultraviolet laser pulses and amorphous silica, leading to permanent refractive-index changes that are at the basis of advanced manufacturing for photonics devices. The experiment, carried out as a function of the laser power, improves our understanding on the strong-field ionization process by the monitoring of the 1.9 eV and 2.65 eV emissions, related to nonbridging oxygen hole centers and self-trapped exciton, respectively, induced in the exposed glass region. Our results clearly proved that the UV laser light band-to-band absorption is allowed in the multiphoton ionization limit, whose consecutive relaxation lea…

Carbon Dots Dispersed on Graphene/SiO2/Si: A Morphological Study

Low-dimensional carbon materials occupy a relevant role in the field of nanotechnology. Herein, the authors report a study conducted by atomic force microscopy and Raman spectroscopy on the deposition of carbon dots onto graphene surfaces. The study aims at understanding if and how the morphology and the microstructure of chemical vapor deposited graphene on Si/SiO2 may change due to the interaction with the carbon dots. Potential alteration in the graphene's electrical properties might be detrimental for optoelectronic applications. The deposition of carbon dots dispersed in water and ethanol solvents are explored to investigate the effect of solvents with different fluidic properties. The…

Existence of metastable intermediate lysozyme conformation highlights the role of alcohols in altering protein stability.

Alcohols have a manifold effect on the conformational and thermodynamic stability of native proteins. Here, we study the effect of moderate concentrations of trifluoroethanol (TFE) on the thermal stability of hen egg-white lysozyme (HEWL), by far-UV circular dichroism and by steady-state and time-resolved photoluminescence of intrinsic tryptophans. Our results highlight that TFE affects lysozyme stability by preferential solvation of the protein molecule. Furthermore, we discovered the existence at 20% TFE of an equilibrium partially folded state of lysozyme, intermediate between the native and the unfolded state. A three-state model is therefore used to interpolate the thermal denaturation…

Time-resolved luminescence of non-bridging oxygen hole centre in silica: Bulk and surface properties

Optical properties of oxygen-deficiency related centers in amorphous SiO 2 investigated by synchrotron radiation

We report an investigation of the photoluminescence activity at 4.4 v eV in g -irradiated silica under UV and vacuum-UV excitation by synchrotron radiation. Our results evidence two iso-energetic contributions which can be related to two oxygen-deficient centers variants: ODC(I) and ODC(II). The first, excited within the 7.6 v eV absorption, is detected only at low temperature and has a lifetime of about 2 v ns. The second exhibits two excitation maxima peaked at 5.0 and 6.8 v eV, its amplitude decreases by a factor 2 on increasing the temperature whereas its lifetime has a value of about 4 v ns. These features give new insights on the excitation pathway of the 4.4 v eV emission involving t…

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800 °C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2–3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with r…

Solvatochromism Unravels the Emission Mechanism of Carbon Nanodots

High quantum yield, photoluminescence tunability, and sensitivity to the environment are hallmarks that make carbon nanodots interesting for fundamental research and applications. Yet, the underlying electronic transitions behind their bright photoluminescence are strongly debated. Despite carbon-dot interactions with their environment should provide valuable insight into the emitting transitions, they have hardly been studied. Here, we investigate these interactions in a wide range of solvents to elucidate the nature of the electronic transitions. We find remarkable and systematic dependence of the emission energy and kinetics on the characteristics of the solvent, with strong response of …

Graphene p-Type Doping and Stability by Thermal Treatments in Molecular Oxygen Controlled Atmosphere

Doping and stability of monolayer low defect content graphene transferred on a silicon dioxide substrate on silicon are investigated by micro-Raman spectroscopy and atomic force microscopy (AFM) during thermal treatments in oxygen and vacuum controlled atmosphere. The exposure to molecular oxygen induces graphene changes as evidenced by a blue-shift of the G and 2D Raman bands, together with the decrease of I2D/IG intensity ratio, which are consistent with a high p-type doping (∼1013 cm-2) of graphene. The successive thermal treatment in vacuum does not affect the induced doping showing this latter stability. By investigating the temperature range 140-350 °C and the process time evolution, …

Competitive relaxation processes of oxygen deficient centers in silica

Physical review / B 67, 033202 (2003). doi:10.1103/PhysRevB.67.033202

Insight into the defect-molecule interaction through the molecular-like photoluminescence of SiO2 nanoparticles

Luminescence properties due to surface defects in SiO2 are the main keystone with particles that have nanoscale dimensions, thus motivating their investigation for many emission related applications in the last few decades. A critical issue is the role played by the atmosphere that, by quenching mechanisms, weakens both the efficiency and stability of the defects. A deep knowledge of these factors is mandatory in order to properly limit any detrimental effects and, ultimately, to offer new advantageous possibilities for their exploitation. Up to now, quenching effects have been interpreted as general defect conversion processes due to the difficulty in disentangling the emission kinetics by…

Photo-conversion of oxygen-deficient related centers in natural silica

Dynamic modification of Fermi energy in single-layer graphene by photoinduced electron transfer from carbon dots

Graphene (Gr)&mdash

Emissive titanium dioxide nanoparticles synthesized py pulsed laser ablation in liquid phase

The remarkable applications of TiO2 nanomaterials, including, e.g. photocatalysis and dye-sensitized solar cells, have inspired in the last two decades an extensive amount of research aimed at understanding the properties of these materials. Photoluminescence is scarcely used to probe the electronic properties of TiO2, because neither bulk or nanosized TiO2 commonly display room-temperature emission. In particular, the fundamental luminescence due to the recombination of the self-trapped exciton in anatase TiO2 is typically observed only at low temperatures. We report the synthesis of luminescent titanium dioxide nanoparticles (NPs) by pulsed laser ablation of titanium in aqueous solution. …

A Comparative Study of Top-Down and Bottom-Up Carbon Nanodots and Their Interaction with Mercury Ions

We report a study of carbon dots produced via bottom-up and top-down routes, carried out through a multi-technique approach based on steady-state fluorescence and absorption, time-resolved fluorescence spectroscopy, Raman spectroscopy, infrared spectroscopy, and atomic force microscopy. Our study focuses on a side-to-side comparison of the fundamental structural and optical properties of the two families of fluorescent nanoparticles, and on their interaction pathways with mercury ions, which we use as a probe of surface emissive chromophores. Comparison between the two families of carbon dots, and between carbon dots subjected to different functionalization procedures, readily identifies a …

UV-Visible down conversion based on nanosized silica promising for CPV applications

Room Temperature Instability of E′γ Centers Induced by γ Irradiation in Amorphous SiO2

We study by optical absorption measurements the stability of E'(gamma) centers induced in amorphous silica at room temperature by gamma irradiation up to 79 kGy. A significant portion of the defects spontaneously decay after the end of irradiation, thus allowing the partial recovery of the transparency loss initially induced by irradiation. The decay kinetics observed after gamma irradiation with a 0.6 kGy dose closely resembles that measured after exposure to 2000 pulses of pulsed ultraviolet (4.7 eV) laser light of 40 mJ/cm(2) energy density per pulse. In this regime, annealing is ascribed to the reaction of the induced E'(gamma) centers with diffusing H(2) of radiolytic origin. At higher…

Bright Visible Luminescence in Silica Nanoparticles

International audience; We demonstrate that a porous film of silica nanoparticles emits a bright visible luminescence associated with defects stabilized by oxygen chemisorption at oxygen deficient center sites. Time-resolved spectra excited by a tunable laser allow us to distinguish the luminescence at 1.99 eV, characteristic of the nonbridging oxygen hole center (NBOHC) (Si-O)3 Si-O*, and a fast and a slow emission: the first (lifetime τ ≈ 25 ns) is peaked at 2.27 eV with an excitation spectrum centered at 5.5 eV; the second (τ ≈ 7.5 μs) is peaked at 2.41 eV and is excited around 3.2 and 5.2 eV. Reaction in an air atmosphere leads to the disappearance of the NBOHC luminescence and of the …

Luminescence features of nonbridging oxygen hole centres in silica probed by site-selective excitation with tunable laser

Time-resolved photoluminescence at 1.9 eV associated with the nonbridging oxygen hole centre (NBOHC) in silica was investigated under excitation with a ns pulsed laser system, tunable in the visible range. Mapping of the excitation/emission pattern evidences the site-selective excitation of the resonant zero phonon line (ZPL) transition due to its weak coupling with the stretching mode of dangling oxygen. Decay of ZPL follows an exponential law with lifetime of 15.3 μs, which provides a precise measure of the electronic transition probability of a single NBOHC.

UV photobleaching of carbon nanodots investigated by in situ optical methods.

Carbon dots are a family of optically-active nanoparticles displaying a combination of useful properties that make them attractive for many applications in photonics and photochemistry. Despite the initial claims of high photostability of carbon dots even under prolonged illuminations, several recent studies have evidenced their photobleaching (PB) under UV light, detrimental for some applications. A study of the mechanism and dynamics of carbon dot PB can be considered a useful route to gather relevant information on the underlying photophysics of these nanoparticles, which is still widely debated. Here we report a study of the PB of carbon dots under UV light, conducted through optical ex…

Phase change and O2 loading in mesoporous silica MCM41, MSU-H and MSU-F

Radiation effects on silica-based preforms and optical fibers-II: Coupling ab initio simulations and experiments

International audience; Abstract—Experimental characterization through electron paramagnetic resonance (EPR) and confocal luminescence microscopy (CML) of a Ge-doped glass (preform and fiber) reveals the generation of several point defects by 10 keV X-ray radiation-induced attenuation: GeE', Ge(1), Ge(2), and Ge-ODC. The generation mechanisms of Ge-ODC and charged defects like GeE' centers are studied through ab initio simulation. Our calculations used a 108 atom supercell with a glass composition comparable to the Ge-doped core or to the pure-silica cladding of the canonical sample. The large size of our cell allows us to study the influence of the local environment surrounding the X-ODC d…

Near‐IR Radiation‐Induced Attenuation of Aluminosilicate Optical Fibers

The X-ray radiation-induced attenuation (RIA) growth kinetics are studied online in different single-mode aluminosilicate optical fibers in the near-IR (NIR) domain to evaluate their potential in terms of dosimetry. The optical fibers differ by Al contents, core sizes, drawing parameters, and also by a preform deposition process. The data show no dependence of the RIA on all these parameters, a positive result for the design of point or distributed radiation detectors exploiting RIA to monitor the dose. The RIA growth rate is unchanged for dose rates changing from 0.073 to 6.25 Gy(SiO2) s−1, and the RIA linearly increases with the dose up to 2 kGy(SiO2). Small but noticeable RIA changes are…

β-C3N4 Nanocrystals: Carbon Dots with Extraordinary Morphological, Structural, and Optical Homogeneity

Carbon nanodots are known for their appealing optical properties, especially their intense fluorescence tunable in the visible range. However, they are often affected by considerable issues of optical and structural heterogeneity, which limit their optical performance and limit the practical possibility of applying these nanoparticles in several fields. Here we developed a synthesis method capable of producing a unique variety of carbon nanodots displaying an extremely high visible absorption strength (ε &gt; 3 × 106 M(dot)−1 cm−1) and a high fluorescence quantum yield (73%). The high homogeneity of these dots reflects in many domains: morphological (narrow size distribution), structural (q…

Effects induced by UV laser irradiation on pure silica core multimode optical fibers investigated by in situ optical absorption measurements

Overview of radiation induced point defects in silica-based optical fibers

International audience; Silica-based optical fibers, fiber-based devices and optical fiber sensors are today integrated in a variety of harsh environments associated with radiation constraints. Under irradiation, the macroscopic properties of the optical fibers are modified through three main basic mechanisms: the radiation induced attenuation, the radiation induced emission and the radiation induced refractive index change. Depending on the fiber profile of use, these phenomena differently contribute to the degradation of the fiber performances and then have to be either mitigated for radiation tolerant systems or exploited to design radiation detectors and dosimeters. Considering the stro…

Thermally induced structural modifications and O2 trapping in highly porous silica nanoparticles

Abstract In this work we investigate by Raman spectroscopy the effect of isochronal (2 h) thermal treatments in air in the temperature range 200–1000 °C of amorphous silicon dioxide porous nanoparticles with diameters ranging from 5 up to 15 nm and specific surface 590–690 m2/g. Our results indicate that the amorphous structure changes similarly to other porous systems previously investigated, in fact superficial SiOH groups are removed, Si–O–Si linkages are created and the ring statistic is modified, furthermore these data evidence that the three membered rings do not contribute significantly to the Raman signal detected at about 495 cm−1. In addition, after annealing at 900 and 1000 °C we…

Absorption band at 7.6 eV induced by γ-irradiation in silica glasses

Optical absorption of defects induced by γ-irradiation in both natural and synthetic silica is experimentally investigated in the vacuum-ultraviolet (UV) range. Our results show that γ-rays, in a dose range of 1000 Mrad, induce an absorption band centered at 7.6 eV, the so-called E band, whose growth kinetics is not related to γ-activated precursors but to defects of the glassy matrix directly induced via the breaking of Si–O bonds occurring under γ-irradiation. Moreover, we observe that γ-rays do not bleach the E band present in some silica samples before irradiation, so ruling out that the associated defects can be precursors of the paramagnetic E′ centers, also induced by γ-irradiation.

Environment assisted photoconversion of luminescent surface defects in SiO 2 nanoparticles

Abstract Time-resolved photoluminescence investigation on SiO 2 nanoparticles was carried out in controlled atmosphere, with the aim to discern the effects induced on the typical blue luminescence band by high power UV Nd:YAG laser photons (4.66 eV) and by some selected molecular species of the air (O 2 , N 2 , CO 2 , H 2 O). These factors ultimately determine both the brightness and photostability of the emitting defect, so as to limit the unique and attracting potentialities offered by this system in many applicative fields. Here it is highlighted that the effects due to photons and molecules, singularly considered, are not additive, the radiation being more dramatic in reducing the emiss…

Radiation Response of OFDR Distributed Sensors Based on Microstructured Pure Silica Optical Fibers

International audience; Temperature sensors based on microstructured pure silica optical fibers are investigated by OFDR and RIA performed during X-ray irradiation up to 50kGy dose. The results evidence that the temperature measures are poorly influenced by irradiation (the error being less than 0.3°C). Such a radiation tolerance is relevant for the use of these Rayleigh based sensors in harsh environments.

Instantaneous diffusion effect on spin-echo decay: Experimental investigation by spectral selective excitation

The influence of the instantaneous diffusion process on spin-echo decay of ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ centers in gamma irradiated silica is experimentally probed by spectral selective excitation within their inhomogeneous resonance line. Our results evidence the different effectiveness of this dephasing mechanism on varying the resonance field, manifesting itself by a faster decay of the echo signal when generated by spin packets located in the central part of the spectrum. It is shown that the dependence of the instantaneous diffusion rate on the spectral position of echo-active spins reproduces the shape of the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ centers resonan…

On-Line Characterization of Gamma Radiation Effects on Single-Ended Raman Based Distributed Fiber Optic Sensor

We report distributed temperature measurements based on Raman scattering performed during steady state $\gamma $ -ray irradiation at a dose rate of 1 kGy( ${\rm SiO}_{2}$ )/h and up to a total ionizing dose (TID) of $\sim 0.1\ \hbox{MGy}$ . We characterize on-line the evolution of the performances of a single-ended Raman distributed temperature sensor (RDTS) during the $\gamma $ -ray exposure of different classes of commercial multimode fibers (MMFs) acting as the sensing element. RDTS is influenced by the radiation-induced attenuation (RIA) phenomena leading to both large errors in the temperature measurements and a diminution of the useful sensing length. The amplitude of the radiation-in…

Multiband light emission and nanoscale chemical analyses of carbonized fumed silica

Fumed silica with a specific area of 295 m2/g was carbonized by successive phenyltrimethoxysilane treatments followed by annealing in inert atmosphere up to 650 °C. Emission, excitation, kinetics, and photo-induced bleaching effects were investigated by steady state and time-resolved photoluminescence spectroscopies. The local chemistry was also studied by infrared transmission spectroscopy. Strong ultraviolet and visible photoluminescence was observed in the samples after the chemical treatments/modifications and thermal annealing. It has been shown that ultraviolet photoluminescence in chemically modified fumed silica is associated with phenyl groups, while near ultraviolet and visible em…

Self-limiting and complete oxidation of silicon nanostructures produced by laser ablation in water

Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO2 and amorphous fully oxidized SiO2, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescen…

Ultraviolet-visible light-induced solarisation in silica-based optical fibres for indoor solar applications

Abstract The transmission performances of pure- and doped-silica (a-SiO2) optical fibres are compared during the exposure to a high-power broadband light source approximating the solar spectrum. From the Gaussian decomposition of the attenuation spectra, we found that Al- and P-doped fibres show a fast solarisation effect which leads to transmission degradation in the ultraviolet-visible range. Similarly, Ge-doped fibres undergo photoinduced colour-centre formation which, however, does not prevent visible-light propagation. One of the two tested pure-silica fibres results completely unaffected by light exposure whereas the other shows an absorption band probably due to the presence of chlor…

Evidence of delocalized excitons in amorphous solids

We studied the temperature dependence of the absorption coefficient of amorphous ${\mathrm{SiO}}_{2}$ in the range from 8 to 17.5 eV obtained by Kramers-Kronig dispersion analysis of reflectivity spectra. We demonstrate the main excitonic resonance at 10.4 eV to feature a close Lorentzian shape redshifting with increasing temperature. This provides a strong evidence of excitons being delocalized notwithstanding the structural disorder intrinsic to amorphous ${\mathrm{SiO}}_{2}$. Excitons turn out to be coupled to an average phonon mode of 83 meV energy.

Stimulated nutation echo: application to the driven decoherence study

We study experimentally the dynamical and decay properties of the stimulated nutation echo (SNE) in a two-level spin system, the signal of which allows the observation timescale of the driven coherence relaxation to be extended. This signal appears in the transient response of the system to the second pulse at time τ1 from its start and coinciding with the duration of the first pulse. The information about the first pulse duration is imprinted into the population difference of the inhomogeneously broadened ensemble of the two-level absorbers. The decay of the SNE signal has two contributions. One originates from the population decay during the time τ between the two pulses. Another is cause…

Optical absorption, luminescence, and ESR spectral properties of point defects in silica

Publisher Summary This chapter is divided into two parts: (1) In the introductory part, it describes the problems of point defects in a-SiO2, and (2) in the second part it discusses the experimental results. This chapter focuses on the Oxygen-Deficient Centers (ODCs) species in silica. This chapter investigates the ODC defects in a-SiO2 through their optical absorption, photoluminescence, and electron spin resonance activities. The effects of γ-ray irradiation are also investigated to evidence their ability to generate or transform structural defects. The aim of this chapter is to understand the optical activity of such defects to help in the characterization of their structure. The propert…

Influence of Ce codoping and H2 pre-loading on Er/Yb-doped fiber: Radiation response characterized by Confocal Micro-Luminescence

International audience; Confocal microscopy luminescence measurements were applied to study the X-ray radiation response of Er/Yb-doped optical fibers in connection with H2 pre-loading and with the addition of another lanthanide element (Cerium) in the core composition. Laser excitations at 488 nm and 325 nm allow deriving the emission and absorption pattern of Er3+, the latter derived from the dips appearing in a wide luminescence band related to defects in silica. We found that the luminescence spectrum of the X-irradiated Er/Yb-doped core fiber evidences an increase in the emission intensity around 520 and 660 nm; in contrast, no changes are induced by radiation neither after H2 pre-load…

Vibrational properties of the surface-nonbridging oxygen in silica nanoparticles

By studying the site-selective luminescence spectra of oxidized silica nanoparticles we identify the electronic and the vibrational lines associated with the surface nonbridging oxygen, $\ensuremath{\equiv}{\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$. This defect emits a zero-phonon line inhomogeneously distributed around 2.0 eV with full width at half maximum of 0.04 eV, weakly coupled with the local ${\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$ stretching mode whose frequency is measured to be $920\text{ }{\text{cm}}^{\ensuremath{-}1}$. These findings are different from those of the well-characterized defect in the bulk silica thus evidencing structural peculiarities of …

Structural inhomogeneity of Ge-doped amorphous SiO2 probed by photoluminescence lifetime measurements under synchrotron radiation.

We report a study of the photoluminescence (PL) time decay of the B-type center, characterized by an optical absorption band peaked at similar to 5.2 eV and two related PL bands peaked at similar to 3.2 eV and similar to 4.3 eV, in sol-gel Ge-doped a- SiO2 under excitation by synchrotron radiation. Measurements were carried out by excitation in UV and in vacuum-UV (VUV), and were performed in the temperature range from 8 K up to 300 K in order to isolate the effects of the intersystem-crossing process, proposed to link the two emission bands of the center. Repeating the time decay measurement at several emission energies falling inside the 4.3 eV band, we have observed a variation of the PL…

Spectroscopic parameters related to non bridging oxygen hole centers in amorphous-SiO2

The relationship between the luminescence at 1.9 eV and the absorption bands at 2.0 eV and at 4.8 eV were investigated in a wide variety of synthetic silica samples exposed to different gamma- and beta-ray irradiation doses. We found that the intensities of these optical bands are linearly correlated in agreement with the model in which they are assigned to a single defect. This finding allows to determine spectroscopic parameters related to optical transitions efficiency: the oscillator strength of the 4.8 eV results ~200 times higher than that of the 2.0 eV; the 1.9 eV luminescence quantum yield under 4.8 eV excitation is lower (by a factor ~3) than that under 2.0 eV excitation. These res…

'School adopts an experiment': the photoluminescence in extra-virgin olive oil and in tonic water

We report a laboratory activity, carried out along with high- and secondary-school students, that can be done to increase the interest of the young in scientific studies. Groups of selected students ‘adopted’ experiments at physics research laboratories, under the guidance of university researchers. Subsequently, the students demonstrated the experiments to the public at large during the annual science festival organized in Palermo by the association PalermoScienza, in collaboration with the University of Palermo. Experiments on the magnetic levitation of superconductors and on the photoluminescence of several substances were proposed. We discuss the experiment on photoluminescence as a cas…

Radiation hardening of Rare-Earth doped fiber amplifiers

We investigated the radiation hardening of optical fiber amplifiers operating in space environments. Through a real-time analysis in active configuration, we evaluated the role of Ce in the improvement of the amplifier performance against ionizing radiations. Ce-codoping is an efficient hardening solution, acting both in the limitation of defects in the host glass matrix of RE-doped optical fibers and in the stabilization of lasing properties of the Er3+-ions. On the one hand, in the nearinfrared region, radiation induced attenuation measurements show the absence of radiation induced P-related defect species in host glass matrix of the Ce-codoped active fibers; on the other hand, in the Ce-…

Visible luminescence peculiar to sintered silica nanoparticles: Spectral and decay properties

We report that the sintering at 1000 degrees C of silica nanoparticles (an average diameter of 14 nm) produces a transparent sample that exhibits a bright visible emission under UV excitation. The use of time resolved luminescence spectroscopy and a tunable laser source allows us to single out three contributions centered at 1.96 eV, 2.41 eV and 3.43 eV. The excitation spectra of these emissions evidence bell shaped bands consistent with transitions between localized defects' states. For each emission we study the intensity and the lifetime in the temperature range from 300 K down to 10 K, thus evidencing the competition between radiative and non-radiative processes in the optical cycle of …

Decagram-Scale Synthesis of Multicolor Carbon Nanodots: Self-Tracking Nanoheaters with Inherent and Selective Anticancer Properties

Carbon nanodots (CDs) are a new class of carbon-based nanoparticles endowed with photoluminescence, high specific surface area, and good photothermal conversion, which have spearheaded many breakthroughs in medicine, especially in drug delivery and cancer theranostics. However, the tight control of their structural, optical, and biological properties and the synthesis scale-up have been very difficult so far. Here, we report for the first time an efficient protocol for the one-step synthesis of decagram-scale quantities of N,S-doped CDs with a narrow size distribution, along with a single nanostructure multicolor emission, high near-infrared (NIR) photothermal conversion efficiency, and sel…

Inhomogeneous properties of defects in amorphous silica probed by time-resolved luminescence

Effect of irradiation temperature on the radiation induced attenuation of Ge-doped fibers

International audience; The UV-visible radiation induced attenuation (RIA) was studied in Ge-doped optical fibers, during X-ray (10 keV) irradiations at different temperatures. By comparing the spectra recorded in dissimilarly irradiated samples we evidenced the impact of the irradiation temperature. In details, we highlighted that, from a certain dose, increasing the temperature the RIA decreases for wavelengths lower than 470 nm, whereas at higher wavelengths the RIA depends only on the dose. Such findings suggest that it is possible to distinguish the irradiation temperature by comparing the signal at two different wavelengths. From the microscopic point of view, it appears that the RIA …

Wide range excitation of visible luminescence in nanosilica

The visible luminescence of nanometer-sized silica particles (7 nm mean diameter) was investigated using time resolved spectroscopy. This luminescence is characterized by a wide excitation in the visible and ultraviolet range. The emission spectrum is centred at 2.72 eV with a full width at half maximum of 0.70 eV when excited above 3.5 eV, whereas it progressively empties on the high energy side when excited below 3.5 eV. Moreover, the lifetime falls in the ns timescale and decreases on increasing the emission energy. These features are due to the exceptionally broad inhomogeneous distribution of the emitting centres peculiar to the silica nanoparticles. © 2010 Elsevier B.V. All rights res…

X-ray irradiation effects on a specific multistep Ge-doped fiber

International audience; The study of point defects generation in optical fibers plays an important role with regards to their use and application in different domains. Their design and elaboration processes (dopants type, concentration, refractive index profile, drawing conditions...) govern their responses and more generally their radiation hardness [1]. In this work we investigated, the influence of 10 keV X-ray irradiations on a set of specific germanosilicate optical fibers elaborated from the same preform at different drawing conditions. The germanium doping levels along the fiber core diameter was specifically designed to follow a two-step distribution in order to highlight the Ge-con…

Fluorescent nitrogen-rich carbon nanodots with an unexpected β-C3N4nanocrystalline structure

Carbon nanodots are a class of nanoparticles with variable structures and compositions which exhibit a range of useful optical and photochemical properties. Since nitrogen doping is commonly used to enhance the fluorescence properties of carbon nanodots, understanding how nitrogen affects their structure, electronic properties and fluorescence mechanism is important to fully unravel their potential. Here we use a multi-technique approach to study heavily nitrogen-doped carbon dots synthesized by a simple bottom-up approach and capable of bright and color-tunable fluorescence in the visible region. These experiments reveal a new variant of optically active carbonaceous dots, that is a nanocr…

Evaluation of Distributed OFDR-Based Sensing Performance in Mixed Neutron/Gamma Radiation Environments

We report the study of a radiation resistant single mode optical fiber doped with fluorine exposed to mixed neutron and $\gamma $ -radiation up to $10^{17}$ n/cm2 fluence and >2 MGy dose to evaluate its performances when used as the sensing element of a distributed Optical Frequency Domain Reflectometry (OFDR). The use of complementary spectroscopic techniques highlights some differences between the responses of solely $\gamma $ -radiation (10 MGy) or mixed neutron and $\gamma $ ( $10^{17}$ n/cm $^{2}+>2$ MGy) irradiated samples. Those differences are linked to the defect generation rather than to structural changes of the ${a}$ -SiO2 host matrix. We show that a modification of the refracti…

Alpha and deuteron irradiation effects on silica nanoparticles

We present an experimental investigation focused on the effects of alpha and deuteron irradiation on different silica nanoparticles. The study has been devoted also to characterize the induced point defects and the eventual structural modifications to evaluate the effects of the different irradiation source in comparison with the bulk materials. After irradiation up to about 10^16 ions cm^-2, we performed electron paramagnetic resonance (EPR), photoluminescence (PL), infrared (IR) absorption, Raman, and atomic force microscopy (AFM) measurements. We found that the two types of irradiation qualitatively induce comparable effects. Furthermore, irradiation generates the socalled twofold coordi…

Radiation Effects on Silica-Based Preforms and Optical Fibers - I: Experimental Study with Canonical Samples

International audience; The influence of the F- and Ge-doping on the fiber radiation responses is investigated through online measurements of the UV-visible induced attenuation and spectroscopic studies (ESR, confocal microscopy of luminescence) on prototype samples

ESR and PL centers induced by gamma rays in silica

We have studied the point defects created by γ irradiation in various types of commercial silica glasses, including both natural and synthetic samples, with different OH content, in the low dose regime (0.05–100 Mrad). We found that the growth rate of E′ centers depends strongly on the silica type, ranging from 2 × 1015 cm−3 Mrad−1 to 6 × 1017 cm−3 Mrad−1. Samples of natural silica are rather susceptible to γ ray exposure, as E′ concentration saturates (typically 5 × 1017 cm−3) for doses as low as a few Mrads. For both synthetic and natural samples, the radiation hardness is higher in wet than in dry silica. Moreover, we found a strict correlation between the concentration of E′ centers and…

Fluorescence of carbon dots embedded in a SiO2 host matrix

Carbon dots (CD) are an emerging class of recently discovered carbonaceous nanomaterials, which have attracted a large interest because of their bright and characteristically “tunable” fluorescence, and their potential for suggestive applications. Despite quite an intense research, the fundamental properties of these systems are poorly understood and still lively debated. Here we report on a series of experiments on N-doped CDs prepared by thermal decomposition of citric acid and urea. We studied these CDs by steady-state and nanosecond time-resolved photoluminescence, optical absorption, infrared absorption and atomic force microscopy. CDs (3 nanometers-sized) are found to emit two co-exis…

Radiation-induced effects in silica based glasses: experimental and theoretical results

Monolayer graphene doping and strain dynamics induced by thermal treatments in controlled atmosphere

Time dynamics of doping and strain induced in single layer graphene by thermal treatments up to 300 degrees C in vacuum, nitrogen, carbon dioxide and oxygen controlled atmosphere are deeply studied by Raman spectroscopy and they are compared with its morphological evolution investigated by Atomic Force Microscopy. The reaction dynamics in oxygen treatments is determined down to a time scale of few minutes as well as that of dedoping process made by water vapor treatment. The interplay of strain modification and doping effects is separated. The strain is clarified to be strongly influenced by the cooling time. The doping removal is dominated by the water vapor, showing that the concentration…

Highly Homogeneous Biotinylated Carbon Nanodots: Red-Emitting Nanoheaters as Theranostic Agents toward Precision Cancer Medicine

Very recent red-emissive carbon nanodots (CDs) have shown potential as near-infrared converting tools to produce local heat useful in cancer theranostics. Besides, CDs seem very appealing for clinical applications combining hyperthermia, imaging, and drug delivery in a single platform capable of selectively targeting cancer cells. However, CDs still suffer from dramatic dot-to-dot variability issues such that a rational design of their structural, optical, and chemical characteristics for medical applications has been impossible so far. Herein, we report for the first time a simple and highly controllable layer-by-layer synthesis of biotin-decorated CDs with monodisperse size distribution, …

Role of diffusing molecular hydrogen on relaxation processes in Ge-doped glass

Temperature dependencies of steady-state and time-resolved photoluminescence (PL) from triplet state at 3.1 eV and singlet state at 4.2 eV ascribed to the twofold-coordinated Ge have been measured in unloaded and H2-loaded Ge-doped silica samples under 5.0 eV excitation in the 10–310 K range. Experimental evidences indicate that diffusing molecular hydrogen (H2) depopulates by a collisional mechanism the triplet state, decreasing both its lifetime of about 14% and the associated triplet PL intensity, whereas those of the singlet are insensitive to the presence of H2.

Design of Radiation-Hardened Rare-Earth Doped Amplifiers through a Coupled Experiment/Simulation Approach

International audience; We present an approach coupling a limited experimental number of tests with numerical simulations regarding the design of radiation-hardened (RH) rare earth (RE)-doped fiber amplifiers. Radiation tests are done on RE-doped fiber samples in order to measure and assess the values of the principal input parameters requested by the simulation tool based on particle swarm optimization (PSO) approach. The proposed simulation procedure is validated by comparing the calculation results with the measured degradations of two amplifiers made with standard and RH RE-doped optical fibers, respectively. After validation, the numerical code is used to theoretically investigate the …

Combined heat and power generation with a HCPV system at 2000 suns

In the framework of the FAE “Fotovoltaico ad Alta Efficienza” (“High Efficiency Photovoltaic”) Research Project funded by the Sicilian Region under the program PO FESR Sicilia 2007/2013 4.1.1.1, we have developed an innovative solar CHP system for the combined production of heat and power at the high concentration level of 2000 suns [1]. This work shows the experimental results obtained on FAE-HCPV modules and analyses the behaviour of the system. The solar radiation is concentrated on commercial InGaP/InGaAs/Ge triple-junction solar cells designed for intensive work. The primary optics is a rectangular off-axis parabolic mirror (with a size of 46x46 = 2116 cm2 in a projection normal to the…

Luminescence properties induced by sintering of silica nanoparticles

The effect of sintering on the optical properties of silica nanoparticles, a mean diameter of ~14 nm, are investigated by absorption and luminescence experiments. The sintering is induced by a thermal treatment of 1000 °C for 272 hours; after that the sample is transparent, and emits a bright luminescence under UV excitation. Time resolved photoluminescence spectra excited by a tunable laser source allows to evidence four bands around 2.0 eV, 2.4 eV, 2.7 eV and 3.4 eV, peculiar to defects induced by the sintering.

Effects induced by UV laser radiation on the blue luminescence of silica nanoparticles

The effects induced on the blue luminescence centered around 2.8 eV, characteristic of silica nanoparticles, were investigated by monitoring its intensity during and after exposure to the third and the fourth harmonic of a Nd:YAG pulsed laser. The luminescence trend is found to be dependent on the UV photon energy: 3.50 eV photons induce a partial bleaching followed by a recovery in the post-irradiation stage; 4.66 eV photons cause a total bleaching permanent after the irradiation. These results are interpreted as the conversion of luminescent defects towards stable and metastable configurations.

Approche couplée pour le développement de matériaux optiques résistants aux radiations

National audience; De très nombreuses applications sont aujourd'hui envisagées pour les matériaux optiques en environnement radiatif. Ce regain d'intérêt pour l'usage de verres ou fibres optiques dans des environnements hostiles s'explique par leurs avantages inhérents en particulier leur immunité électromagnétique. En revanche, il est également bien établi que les radiations entrainent la génération de défauts ponctuels dans verres amorphes. Ces défauts vont, au niveau macroscopique, entrainer une altération des propriétés optiques du matériau, le plus souvent de la silice amorphe pure ou dopée. Ainsi, les fibres optiques vont, sous irradiation, voir leur atténuation linéique augmenter, po…

Durcissement de matériaux pour l’optique et la photonique destinés à l’utilisation dans un environnement énergétique

Metal thin-film temperature sensor embedded in heat-sink for CPV cells characterization

The efficiency of a photovoltaic cell is dependent on its temperature, for this reason an accurate measurement of this parameter is important to fully characterize the device and to optimize its performance. For CPV applications a significant heat flux is needed to remove excess heat from the cell towards a heat sink, making it difficult to derive the cell temperature. In fact, measurements performed directly between the cell and the heat-sink, by use of commercial bulk sensors, would produce a significant disturbance in the heat flow; on the other hand, a measurement performed out of the cell / heat sink axis would be subject to large uncertainties, due to the high radial temperature gradi…

Paramagnetic germanium-related centers induced by energetic radiation in silica based devices

Zero phonon line associated with Non Bridging Oxygen Hole Center in silica: comparison between bulk and surface properties

Development of a Temperature Distributed Monitoring System Based On Raman Scattering in Harsh Environment

Raman Distributed Temperature Sensors (RDTSs) offer exceptional advantages to monitor the envisioned French deep geological repository for nuclear wastes, called Cigeo. Both $\gamma $ -ray and hydrogen release from nuclear wastes can strongly affect the temperature measurements made with RDTS. We present experimental studies on how the performances of RDTS evolve in harsh environments like those associated with $\gamma $ -rays or combined radiations and ${{\rm H}_2}$ release. The response of two standard and one radiation tolerant multimode fibers (MMFs) are investigated. In all fibers the differential induced attenuation between Stokes and anti-Stokes signal, ${({{\alpha _{\rm AS}} - {\alp…

Coupled theoretical and experimental studies for the radiation hardening of silica-based optical fibers

International audience; We applied theoretical and experimental spectroscopy tools to ad hoc silica-based "canonical" samples to characterize the influence of several dopants and of some drawing process parameters on their radiation sensitivities. We present in this paper, the recent advances and results occurring from our coupled approach. On the experimental side, we studied the doping influence on the response of optical fibers and showed that changing the drawing parameters has a negligible influence on the fiber response in the case of specialty fibers. We focus mainly on the ${rm SiE}^prime$ defect that is observed through Electron Paramagnetic Resonance (EPR) measurements in all cano…

Irradiation temperature influence on the in-situ measured radiation induced attenuation of Ge-doped fibers

International audience; We report an experimental investigation on the radiation induced attenuation (RIA) in the ultraviolet-visible domain for Ge-doped optical fibers, during X-rays (10 keV) exposure at different temperatures. The objective is to characterize the impact of the irradiation temperature on the RIA levels and kinetics. Our data highlight that for dose exceeding 1 kGy(SiO2) the RIA spectrum changes with the irradiation temperature. In particular, for wavelengths below 470 nm the RIA depends both on the dose and on the irradiation temperature, whereas at higher wavelengths the RIA depends only on the dose. From the microscopic point of view the origin of this behavior is explai…

Synthesis of luminescent glass monoliths embedding water-soluble Carbon dots

Carbon dots (CD) are an emerging class of nanomaterials, currently motivating an intense scientific interest because of their bright and characteristically tunable fluorescence, and their possible applications such as sensors, lasers, imaging agents, white light emitting devices [1]. While most studies focused on CDs in liquid phase, a strong effort is being recently devoted to produce fluorescent solids embedding highly dispersed CDs. Many of these procedures are elaborate and require pre-functionalization of the dots [2]. Here we report a novel and very facile route to prepare glass monoliths containing CDs with no need of pre-functionalization of the dots. Our low-cost synthesis method p…

Near-IR- and UV-femtosecond laser waveguide inscription in silica glasses

The influence of laser parameters on silica based waveguide inscription is investigated by using femtosecond laser pulses at 1030 nm (near-IR) and at 343 nm (UV). Negative phase contrast microscopy technique is used to measure the refractive index contrast for different photo-inscribed waveguides and shows the effects of both laser wavelength and scanning speed. In particular, UV photons have a higher efficiency in the waveguide production process as also confirmed by the lower optical losses at 1550 nm in these waveguides. These measurements are combined with micro-Raman and photoluminescence techniques, highlighting that laser exposure induces both structural modification of the silica an…

Stability of E' centers induced by 4.7eV laser radiation in SiO2

The kinetics of E' centers (silicon dangling bonds) induced by 4.7eV pulsed laser irradiation in dry fused silica was investigated by in situ optical absorption spectroscopy. The stability of the defects, conditioned by reaction with mobile hydrogen of radiolytic origin, is discussed and compared to results of similar experiments performed on wet fused silica. A portion of E' and hydrogen are most likely generated by laser-induced breaking of Si-H precursors, while an additional fraction of the paramagnetic centers arise from another formation mechanism. Both typologies of E' participate to the reaction with H_2 leading to the post-irradiation decay of the defects. This annealing process is…

Generation of a 7.4 mT ESR doublet induced by γ rays in amorphous-SiO2

Abstract Paramagnetic defects induced by γ rays, in a dose range from 1 to 1000 Mrad, have been investigated by electron spin resonance (ESR) spectroscopy in various types of natural and synthetic silica, having different OH content. A doublet with a field splitting of 7.4 mT, arising from the hyperfine interaction of an unpaired electron with a H nucleus associated with the H(I) center, was detected in all the investigated samples. This ESR structure exhibits a sublinear growth with the γ dose linearly correlated with the γ-induced photoluminescence band at 4.4 eV. The intensity ratio of these two signals depends on the OH content of the sample. Our results agree with a model in which the …

Radiation and Hydrogen-Loading effects on Raman fiber-based temperature sensors

We present experimental studies on how Raman based temperature sensors undergone two different treatments: gamma-radiation and H-loading. Unfortunately, gamma radiation and hydrogen release in harsh nuclear environment can affect the temperature measurements based on this technology of sensor, limiting the sensor performances. Moreover, the Raman device response in both cases changes with the different classes of multimode fibers that are used by the engineers.

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

International audience; 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 degrees 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 degrees 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 t…

Post UV irradiation annealing of E’ centers in silica controlled by H2 diffusion

Abstract We investigate the isothermal annealing of E′ centers generated by UV photons (266 nm) of a pulsed Nd:YAG laser in two natural silica types differing for their OH content. Electron spin resonance and absorption spectra recorded at room temperature at different delays from the laser exposure evidenced a partial reduction of E′ centers, more pronounced in the wet silica. These post irradiation kinetics complete within 10 5 s, regardless the silica type, and they are consistent with a diffusion limited reaction between the E′ centers and the molecular hydrogen H 2 . Analysis of our data is done by theoretical fits using the Waite's equation and compared with the H 2 diffusion paramete…

Luminescence from nearly isolated surface defects in silica nanoparticles

A structured emission/excitation pattern, proper of isolated defects, arises in a vacuum from silica nanoparticles. The luminescence, centered around 3.0-3.5 eV, is characterised by a vibronic progression due to the phonon coupling with two localised modes of frequency  ∼1370 cm(-1) and  ∼360 cm(-1), and decays in about 300 ns at 10 K. On increasing the temperature, the intensity and the lifetime decrease due to the activation of a non-radiative rate from the excited state. Concurrently, the temperature dependence of the lineshape evidences the low coupling with non-localised modes of the matrix (Huang-Rhys factor S ~ 0.2) and the poor influence of the inhomogeneous broadening. These findin…

Resonance Raman of oxygen dangling bonds in amorphous silicon dioxide

We investigate the origin of a resonance Raman band induced by ionizing radiation in amorphous silicon dioxide (silica glass), which can be detected under ultraviolet laser excitation. A silica sample, rich of oxygen-excess related defects, was prepared by treating some length of a pure-silica-core multimode fiber in an O2 atmosphere (at high temperature and pressure) and by irradiating it with X-rays at 10 MGy(SiO2) dose. A micro-Raman study revealed a gaussian band peaking at 896 cm−1 with a full width at half maximum of 32 cm−1, which could be detected by exciting the sample with the 325-nm line of a HeCd laser. This spectral feature is absent in the Raman spectra performed with the 442-…

Effect of Hydration Procedure of Fumed Silica Precursor on the Formation of Luminescent Carbon Centers in SiO 2 :C Nanocomposites

The effect of hydration procedure of fumed silica precursor on photoluminescent properties of carbonized silica (SiO2:C) nanocomposite after chemo/thermal treatments is studied. Main structural effect is the formation of chemical bonding of phenyl groups to silica surface via multiple CSiO bonding bridges. Synthesized samples demonstrate very broad photoluminescence (PL) bands in near ultraviolet and visible ranges with maximum intensity dependent on temperature of thermal annealing. Two main trends in luminescence properties are: 1) hydration-induced blue shift of PL in comparison with PL of unhydrated series; 2) red shift of PL bands with increasing synthesis temperature regardless hydr…

Silica-Based NIR Nano-Emitters for Applications in Vivo and Process for Production Thereof

Production of paramagnetic and phosphorescent nanoprobes, obtainable starting from nanometric silica particles by methods of synthesis and enrichment with O2 following suitable thermal treatments in a controlled environment. The nanoprobes thus obtained display emission in the near infrared (NIR), are excitable in the visible and in the NIR, and are characterized by a lifetime of the order of one second. These nanoprobes have considerable scientific and commercial potential in the market of the confocal spectroscopy for bio-imaging and in the market of the medical pharmaceutical applications of drug labelling and drug delivery.

Influence of Drawing Conditions on the Properties and Radiation Sensitivities of Pure-Silica-Core Optical Fibers

International audience; The structure and radiation sensitivities of three different pure-silica-core fluorine-doped-cladding optical fibers, made from the same original preform, were investigated by several experimental techniques. The fibers were obtained by changing the drawing speed and tension in the typical ranges of values used for the radiation-tolerant waveguides. The Raman spectroscopy revealed no significant difference among the fibers before irradiation. At variance, the comparison between the fibers and their associated preform highlighted an increase in the amplitude of the D2 band that is related to the concentration of 3 member rings. Moreover, in the zones where the D2 incr…

Radiation Effects on Silica-Based Preforms and Optical Fibers - II: Coupling Ab Initio Simulations and Experiments

International audience; Both experimental and theoretical approaches are combined to study the nature of precursor sites and radiation-induced point defects in pure and germanium-doped amorphous silica-based glasses.

Silica nanoparticle core structure examined by the E?Si? center 29Si strong hyperfine interaction

Abstract β-Ray irradiation up to 1.2 GGy was employed to induce E′Si γ defects and to study the structure of silica nanoparticles with diameters from 7 up to 20 nm. Defect concentration and their 29 Si strong hyperfine doublet were investigated through electron paramagnetic resonance measurements. Our data indicate that stable defects are located in the nanoparticle core. Furthermore, the E′Si γ hyperfine interaction evidences that the core structure is denser than bulk silica and independent from the particle size. Finally, we put in evidence that the core structure is stable and unaffected by the irradiation in the investigated dose range maintaining the specific features of nanoparticles.

Photoluminescence spectral dispersion as a probe of structural inhomogeneity in silica

We perform time-resolved photoluminescence measurements on point defects in amorphous silicon dioxide (silica). In particular, we report data on the decay kinetics of the emission signals of extrinsic oxygen deficient centres of the second type from singlet and directly excited triplet states, and we use them as a probe of structural inhomogeneity. Luminescence activity in sapphire (alpha-Al(2)O(3)) is studied as well and used as a model system to compare the optical properties of defects in silica with those of defects embedded in a crystalline matrix. Only for defects in silica did we observe a variation of the decay lifetimes with emission energy and a time dependence of the first moment…

10-keV X-ray irradiation effects on phosphorus doped fibers and preforms: electron spin resonance and optical studies

Ag nanoparticles agargel nanocomposites for SERS detection of cultural heritage interest pigments

Agarose gel (agargel) composites with commercial and laboratory made silver nanoparticles were prepared by a wet solution method at room temperature. The gel composites were used for pigment extraction and detection by Raman spectroscopy. Red (alizarin) and violet (crystal violet) pigments deposited on paper were extracted by the composites and were investigated by micro-Raman spectroscopy. Evaluation was carried out of the surface-enhanced Raman spectroscopy (SERS) effect induced by the silver nanoparticles embedded in the gel. A kinetic approach as a function of time was used to determine the efficiency of pigments extraction by composites deposition. A non-invasive extraction process of …

Radiation Vulnerability of Fiber Bragg Gratings in Harsh Environments

International audience; The difficulties encountered in the implementation of a temperature or strain sensor based on fiber Bragg grating (FBG) in a harsh radiative environment are introduced. We present the choices made to select both a radiation-resistant fiber in terms of transmission and also the grating inscription conditions necessary to write radiation tolerant FBGs in such fibers with a femtosecond laser. The radiation response of these gratings was also studied under radiation at dose up to 1 MGy. The comparison between Ge-free and Ge-doped fibers was highlighted.

Time Resolved Photoluminescence Associated with Non Bridging Oxygen Hole Centers in Irradiated Silica

Radiation Characterization of Optical Frequency Domain Reflectometry Fiber-Based Distributed Sensors

International audience; We studied the responses of fiber-basedtemperature and strain sensors related to Optical FrequencyDomain Reflectometry (OFDR) and exposed to high γ-ray dosesup to 10 MGy. Three different commercial fiber classes areused to investigate the evolution of OFDR parameters withdose, thermal treatment and fiber core/cladding composition.We find that the fiber coating is affected by both thermal andradiation treatments and this modification results in anevolution of the internal stress distribution inside the fiber that influences its temperature and strain Rayleigh coefficients. These two environmental parameters introduce a relative error up to 5% on temperature and strain…

Transient and Steady-State Radiation Response of Phosphosilicate Optical Fibers: Influence of H2 Loading

The radiation response of a phosphorus-doped multimode optical fiber is investigated under both transient (pulsed X-rays) and steady-state ( $\gamma $ - and X-rays) irradiations. The influence of a H2 preloading on the fiber radiation-induced attenuation (RIA) in the 300–2000-nm wavelength range has been characterized. To better understand the impact of this treatment, online behaviors of fiber samples containing different amounts of gas are compared from glass saturation (100%) to less than 1%. In addition to these in situ experiments, additional postirradiation spectroscopic techniques have been performed such as electron paramagnetic resonance or luminescence measurements to identify the…

Preferential solvatation of TFE in lysozyme: a luminescence study

Radiation hardening of FBG in harsh environments

International audience; The difficulties encountered in the implementation of a temperature or strain sensor based on Fiber Bragg Grating in a harsh radiative environment are introduced. We present the choices made to select both a radiation-resistant fiber in terms of transmission and also the grating inscription conditions necessary to write radiation tolerant FBGs in such fibers with a femto-second laser. The response of different classes of gratings was also studied under radiation at high doses (>1MGy). The comparison between F- and Ge-doped fibers was highlighted.

Photoluminescence time decay of surface oxygen-deficient centers in pure and Ge-doped silica

Quantum confinement effects observed by the photoluminescence of SiOx/SiO2 multilayers

Spectral and decay features related to the red emission from Si nanocrystals were investigated by time-resolved photoluminescence spectra carried out on SiOx/SiO2 nanosized multilayers. On decreasing the SiOx thickness from 8.4 nm to 2.2 nm this luminescence band exhibits a blue-shift from 1.65 eV to 1.75 eV and its lifetime increases from 12μs to 17 μs. These results are discussed on the basis of previous models proposed in literature and agree with quantum confinement effects arising from differently sized Si nanocrystals in our samples.

Structure effects induced by high mechanical compaction of STAM-17-OEt MOF powders

Financial support by PJ-RIC-FFABR_2017 and the EPSRC grant EPSRC industrial CASE award (grant EP/N50936X/1) are acknowledged. The research programme Nanoporous materials (P1-0021) financially supported by Slovenian Research Agency (ARRS) is acknowledged as well. Metal-organic frameworks (MOFs) are promising materials for many potential applications, spacing from gas storage to catalysis. However, the powder form of which they are generally made is not suitable, mainly because of the low packing density. Powder compaction is therefore necessary, but also challenging because of their typical mechanical fragility. Indeed, generally, they undergo irreversibly damages upon densification processe…

Radiation induced generation of non-bridging oxygen hole center in silica: Intrinsic and extrinsic processes

Abstract The generation of non-bridging oxygen hole center ( Si–O ) was investigated in a wide variety of natural (fused quartz) and synthetic silica samples exposed to different γ- and β-irradiation doses by looking at its optical bands. We distinguish two different generation processes: intrinsic associated with the cleavage of Si–O bond and characterized by a sublinear law and extrinsic due to the conversion of OH precursor characterized by a growth curve with a saturating tendency. The interplay between the two processes and the role of H are discussed.

Luminescence decay excited by synchrotron radiation in gamma-irradiated alpha-quartz

CCDC 2237075: Experimental Crystal Structure Determination

Related Article: Juan P. Mora-Fuentes, Marcos D. Codesal, Marco Reale, Carlos M. Cruz, Vicente G. Jiménez, Alice Sciortino, Marco Cannas, Fabrizio Messina, Victor Blanco, Araceli G. Campaña|2023|Angew.Chem.,Int.Ed.|62||doi:10.1002/anie.202301356