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 the structural disorder typical of amorphous solids. Specifically, the observations on ODC(II) are interpreted by introducing a gaussian statistical distribution of the zero phonon line energy position. Comparison with the results obtained on F+ 3 crystalline defects strongly confirms the validity of the model. By analyzing experimental data within this frame, we obtain separate estimations of the homogenous and inhomogeneous contributions to the measured total linewidth of ODC(II), which results to be mostly inhomogeneous.Comment: 8 pages, 4 figure

Photoluminescence dispersion as a probe of structural inhomogeneity in silica

We report time-resolved photoluminescence spectra of point defects in amorphous silicon dioxide (silica), in particular the decay kinetics of the emission signals of extrinsic Oxygen Deficient Centres of the second type from singlet and directly-excited triplet states are measured and used 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, we observe a variation of the decay lifetimes with emission energy and a time dependence of the first moment of the emission bands. These features are analyzed within a theoretical model with explicit hypothesis about the effect introduced by the disorder of vitreous systems. Separate estimations of the homogenous and inhomogeneous contributions to the measured emission linewidth are obtained: it is found that inhomogeneous effects strongly condition both the triplet and singlet luminescence activities of oxygen deficient centres in silica, although the degree of inhomogeneity of the triplet emission turns out to be lower than that of the singlet emission. Inhomogeneous effects appear to be negligible in sapphire

Twofold co-ordinated Ge defects induced by gamma-ray irradiation in Ge-doped SiO2.

We report an experimental study by photoluminescence, optical absorption and Electron Paramagnetic Resonance measurements on the effects of exposure of Ge-doped amorphous SiO2 to gamma ray radiation at room temperature. We have evidenced that irradiation at doses of the order of 1 MGy is able to generate Ge-related defects, recognizable from their optical properties as twofold coordinated Ge centers. Until now, such centers, responsible for photosensitivity of Ge-doped SiO2, have been induced only in synthesis procedures of materials. The found result evidences a role played by gamma radiation in generating photosensitive defects and could furnish a novel basis for photosensitive pattern writing through ionizing radiation

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, correctly reproduce the general trends of experimental results. This calculation tool has been used to study the influence of the amplifier design on its radiation response. The fiber length used to ensure the optimal amplification before irradiation may be rather defined and adjusted to optimize the amplifier performance over the whole space mission profile rather than before integration in the harsh environments. Both forward and backward pumping schemes lead to the same kind of degradation with our active fibers. By using this promising coupled approach, radiation-hardened amplifiers nearly insensitive to radiations may be designed in the future

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

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 influence of some amplifier design parameters on its sensitivity to radiations. Simulations show that the RE-doped fiber length used in the amplifier needs to be adjusted to optimize the amplifier performance over the whole space mission profile rather than to obtain the maximal amplification efficiency before its integration in the harsh environment. By combining this coupled approach with the newly-developed RH RE-doped fibers, fiber-based amplifiers nearly insensitive to space environment may be designed in the future

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

We report an experimental investigation on the effects of γ-ray irradiation in several types of silica nanoparticles previously loaded with O2 molecules. They differ in specific surface and average diameter. By electron paramagnetic resonance (EPR) measurements we observe the generation of about 1018 HO2•/cm3 interstitial radicals. These radicals are induced by reaction of interstitial O2 molecules with radiolytic H atoms, as previously suggested for O2-loaded bulk a-SiO2 samples. However, at variance with respect to bulk materials, our experimental evidences suggest a different generation process of HO2• radical. In fact, by a detailed study of samples exposed to D2O, our results prove that radiolytic hydrogen atoms reacting with O2 to produce HO2• mainly arise from a radiation induced breaking of H2O molecules in the layers surrounding the nanoparticles or in the interstices. Also, by the correlation of HO2• paramagnetic centers concentration, determined by EPR measurements, and O2 Raman/PL signal we further considered the issue of the direct estimation of the O2 concentration in silica nanoparticles from Raman/PL spectra giving an independent conversion factor (the ratio between these latter two quantities), which is in good agreement with those previously proposed by other authors basing on optical measurements

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 opticalfibers 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 Center

Intrinsic generation of OH groups in dry silicon dioxide upon thermal treatments

We show the existence of an intrinsic generation mechanism of OH groups in synthetic dry silica upon thermal treatments. Samples are treated for ~160 h at 390 °C in He at 2.7 or 180 bar, and the growth of the OH IR absorption band at 3670 cm−1 is observed. An OH concentration of ~10^18 cm^−3 is estimated. Possible contributions of reactions with molecules absorbed from the atmosphere are excluded. Reactions with H2O already contained in the samples are rejected by IR measurements. The observed OH generation is attributed to the reaction of network sites with H2 already present in the material. Possible reaction paths are examine