Marco Cannas

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 the γ-induced absorption band at 5.8 eV. Finally, exposure to γ rays generates in all the samples a photoluminescence band at 4.4 eV, whose excitation spectrum has a maximum at 4.95 eV. This band exhibits a sublinear growth kinetics in all the investigated samples.

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 the photoexcited dots to hydrogen bonding. These findings suggest that the fluorescence originates from the radiative recombination of a photoexcited electron migrated to surface groups with holes left in the valence band of the crystalline core. Furthermore, the results demonstrate the fluorescence tunability to inherently derive from dot-to-dot polydispersity, independent of solvent interactions.

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

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

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

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 complex response of the tested fibers in such mixed environments. Increasing the temperature of irradiation increases or decreases the RIA values measured at 25 °C or sometimes has no impact at all. Furthermore, R&T effects are time dependent giving an impact of the temperature on RIA that evolves with the time of irradiation. The two observed transient and stationary regimes of temperature influence will make it very difficult to evaluate sensor vulnerability or the efficiency of hardening approaches without extensive test campaigns.

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 afterglows in about 100 s at the end of steady-state excitation. The origin of the observed luminescence bands and the comparison with optical features of oxygen-deficient centres in silica glass are discussed in the framework of different models proposed in the literature.

Experimental evidence of the composite nature of the 3.1 eV luminescence in natural silica

Abstract The 3.1 eV photoluminescence of silica has been investigated on several samples of commercial origin, by measuring both time-resolved and stationary spectra. This structure, known as the β band, displayed the well known peculiarities: 3.1 eV energy position, 0.4 eV full width at half maximum, excitation peak at 5.1 eV and 100 μs decay time. However, an accurate analysis of the experimental data has shown the double nature of the β band in all natural silica samples here studied. The characteristic values of the two components β1 and β2 are: peak energy 3.04 and 3.20 eV, full width at half maximum of 0.44 and 0.35 eV and decay time of 115 and 97 μs respectively. In addition the intensity ratio between the luminescent emissions at 3.1 and 4.2 eV was found to be constant in the whole set of samples. The occurrence of two β components with so close spectral and time peculiarities might be ascribed to fluorescence processes involving the same oxygen deficient centers surrounded by two slightly different environments.

Chapter 1 – 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 properties of point defects in a wide variety of both natural and synthetic silica types of commercial origin are investigated in the chapter. This chapter outlines the role of structural and dynamic properties of the vitreous matrix in determining the observed spectral properties of different centers. It deals with the theoretical aspects of the mechanism that are able to influence the fine structure of the spectral band profiles of point defects in interaction with the glassy matrix.

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

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

Sol-Gel GeO2-Doped SiO2 Glasses for Optical Applications

Optical and structural properties of silica materials with controlled Ge-content were investigated in aerogels samples with Ge concentration up to 100000 molar ppm prepared by a sol-gel method and densified at 1150°C. An optical absorption band centered at 242 nm, commonly ascribed to an under-coordinated germanium point defect, was observed in all doped samples, and its amplitude was found to be almost linearly correlated with the Ge-content. This feature may be ascribed to the new preparation technique so that this is potentially useful to produce materials with controlled defect content for specific optical applications.

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 Cigéo. Both γ-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 γ-rays or combined radiations and H2 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, (αAS - αS) causes a temperature errors, up to 30° C with standard multimode fibers (100 m) irradiated at 10 MGy dose. This degradation mechanism that is more detrimental than the radiation induced attenuation (RIA) limiting only the sensing range. The attenuation in the [800-1600 nm] spectral range at room temperature is explored for the three fibers γ-irradiated and/or hydrogen loaded to understand the origin of the differential RIA. We show that by adapting the characteristics of the used fiber for the sensing, we could limit its degradation but that additional hardening by system procedure is necessary to correct the T error in view of the integration of our RDTS technology in Cigéo. The current version of our correction technique allows today to limit the temperature error to ~ 2° C for 10 MGy irradiated samples.