Diffusive equilibrium properties of O2 in amorphous SiO2 nanoparticles probed via dependence of concentration on size and pressure

An experimental study on the diffusive equilibrium value of interstitial O2 in silica nanoparticles was carried out on samples with average particles diameter 40, 14, and 7 nm. The investigation was performed by measuring the concentration of interstitial O2 by Raman and photoluminescence techniques. The dependence of diffusive equilibrium concentration on pressure and temperature was investigated in the pressure range from 0.2 to 76 bar and in the temperature range from 98 to 244 °C. The equilibrium concentration of interstitial O2 follows Henry’s law at pressures below 13 bar whereas a departure from this model is observed at higher pressures. In particular, O2 concentration saturates abo…

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…

Modification of Ce oxidation state by thermal treatments in controlled atmosphere of Ce-Ti-Eu doped SiO2 glasses

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 …

Effects of thermal treatments in controlled atmosphere on the Ce oxidation state in Ce-Ti-Eu doped SiO2 sol-gel glasses

We report an experimental study by optical absorption, photoluminescence and Raman spectroscopies of the modifications induced on Ce–Ti-Eu doped SiO2 glasses by thermal treatments in controlled atmosphere. Samples with Ce content varying up to 5,000 part per million by weight (ppm) and with Ti and Eu content fixed at 40 and 300 ppm respectively, have been investigated. The treatments were done in inert atmosphere of He and in O2 atmosphere at 390 C and 100 bar. Our experiments show that only Ce4? ions are affected by He treatments, whereas both Ce4? and Ce3? ions are affected by O2 treatments. The obtained results are interpreted on the basis of microstructural changes induced by the therma…

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…

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.

Experimental evidence for two different precursors of Eγ′ centers in silica

Abstract Electron paramagnetic resonance measurements of concentration and line shape of E γ ′ centers induced by γ ray irradiation are presented for natural and synthetic commercial silica with different OH contents. Synthetic materials with OH content >200 ppm by weight show one line shape for all investigated doses. In contrast, the other materials show a different line shape at low irradiation doses. Differences are also observed in the concentration growth of the E γ ′ centers in synthetic wet materials and in the other materials. The results are interpreted as evidence of two E γ ′ centers distinguishable by their line shape and having different precursors.

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

Modifications of optical absorption band of E'gamma center in silica

We report a study by electron paramagnetic resonance on the E0 point defect in amorphous silicon dioxide (a-SiO2). Our experiments were performed on -ray irradiated oxygen-deficient materials and pointed out that the 29Si hyperfine structure of the E0 consists of a pair of lines split by 49 mT. On the basis of the experimental results, a microscopic model is proposed for the E0 center, consisting of a hole trapped in an oxygen vacancy with the unpaired electron sp3 orbital pointing away from the vacancy in a back-projected configuration and interacting with an extra oxygen atom of the a-SiO2 matrix.

Double-quantum nutations in a two-level spin system

The transient oscillatory behavior of the nonlinear response of a two-level electron-spin system is experimentally investigated in a sample of glassy silica with ${E}_{1}^{\mathcal{'}}$ centers (S=(1/2)) at microwave frequency at T=4.2 K. The transient regime, excited by an intense step-modulated radiation tuned to double-quantum (DQ) resonance, is monitored by revealing the second-harmonic (SH) wave radiated by the spins undergoing DQ transitions. Time- and frequency-domain results show that the emitted SH wave has two components: the former, which vanishes at the DQ resonance, exhibits an overdamped transient regime, the latter consists of damped oscillations at a frequency which depends …

Annealing of radiation induced oxygen deficient point defects in amorphous silicon dioxide: evidence for a distribution of the reaction activation energies

The selective annealing of point defects with different activation energies is studied, by performing sequences of thermal treatments on gamma irradiated silica samples in the temperature range 300-450 °C. Our experiments show that the dependence on time of the concentration of two irradiation induced point defects in silica, named ODC(II) (standing for oxygen deficient centre II) and the E(γ)(') centre, at a given temperature depends on the thermal history of the sample for both of the centres studied; moreover in the long time limit this concentration reaches an asymptotic value that depends on the treatment temperature alone. These results suggest the existence of a distribution of the a…

INTRINSIC PARAMAGNETIC CENTERS INDUCED IN GAMMA RAY IRRADIATED OXYGEN-DEFICIENT SILICA

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.

Effects of Pressure, Temperature, and Particles Size on O2 Diffusion Dynamics in Silica Nanoparticles

The O2 diffusion process in silica nanoparticles is experimentally studied in samples of average radius of primary particles ranging from 3.5 to 20 nm and specific surface ranging from 50 to 380 (m2/g). The investigation is done in the temperature range from 98 to 177 °C at O2 pressure ranging from 0.2 to 66 bar by measuring the interstitial O2 concentration by Raman and photoluminescence techniques. The kinetics of diffusion can be described by the Fick’s equation with an effective diffusion coefficient depending on the temperature, O2 pressure, and particles size. In particular, the dependence of the diffusion coefficient on the pressure and nanoparticles size is more pronounced at lower …

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…

Instantaneous diffusion in spin-echo dynamics: A frequency-domain experimental investigation.

We report an experimental investigation on the spectral content of the echo radiation emitted by an electron spin system excited by a two-pulse sequence. The measurements are carried out at liquid-helium temperature in a sample of quartz containing a very low concentration of [${\mathrm{AlO}}_{4}$${]}^{0}$ centers, in which instantaneous diffusion mechanism makes the main contribution to the phase relaxation. The experimental spectral shapes reproduce the theoretical ones, as calculated for an ideal system of noninteracting spins. However, the agreement is only qualitative, as the experimental spectral widths are found to be less than expected by a factor that depends on the exciting sequen…

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…

Bright blue emission of synthesized silica nanoparticles conferred by surface defects

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 …

Non-Bloch decay of transient nutations in S=1/2 systems: An experimental investigation.

The decay of transient nutations has been experimentally investigated in S=1/2 spin systems at microwave frequency: E' centers in silica and [${\mathrm{AlO}}_{4}$${]}^{0}$ centers in quartz have been studied. We have found that the damping is well described by a single exponential decay function, as expected from a ${\mathit{T}}_{1}$-${\mathit{T}}_{2}$ model (Bloch model). However, the agreement is only qualitative. In fact the measured decay rate \ensuremath{\Gamma} is faster than expected and depends on the driving-field amplitude: it tends to the Bloch value ${\mathrm{\ensuremath{\Gamma}}}_{\mathit{B}}$=1/2${\mathit{T}}_{2}$ in the low-power limit and becomes faster and faster on increas…

Sturctural disorder and silanol groups content in amorphous SiO2

We present a study on the features of the Urbach edge in amorphous silicon dioxide a-SiO2 . The effects of temperature on the absorption edge in the range from 4 to 300 K were studied in both materials having negligible dry, 1017 cm−3 and significant wet, 1019 cm−3 silanol groups contents. Remarkable differences in the values and in the temperature dependence of the Urbach energy in the dry and wet samples were observed. These differences are interpreted as a consequence of a drastic reduction in the degree of disorder in wet materials, which turn out to be characterized by an electronic structure more similar to that of crystalline quartz. Furthermore, our results indicate that silanol gro…

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.

O2 Diffusion in Amorphous SiO2 Nanoparticles Probed by Outgassing

An experimental study of the O2 diffusion process in nanoparticles of amorphous SiO2 in the temperature range from 98 to 157 °C was carried out by Raman and photoluminescence techniques. We studied O2 diffusion in high purity silica nanoparticles with a mean diameter of 14, 20, and 40 nm detecting the outgassing of molecules trapped during the manufacturing. The kinetics of diffusion is well described for all the investigated nanoparticles by the Fick’s equation proving its applicability to nanoscale systems. The diffusion coefficient features an Arrhenius law temperature dependence in the explored temperature range, and the diffusion coefficient values are in good agreement with extrapolat…

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…

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…

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

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

Optical absorption and electron paramagnetic resonance of the E’_alfa center in amorphous silicon dioxide

We report a combined study by optical absorption OA and electron paramagnetic resonance EPR spectroscopy on the E point defect in amorphous silicon dioxide a-SiO2. This defect has been studied in -ray irradiated and thermally treated oxygen-deficient a-SiO2 materials. Our results have pointed out that the E center is responsible for an OA Gaussian band peaked at 5.8 eV and having a full width at half maximum of 0.6 eV. The estimated oscillator strength of the related electronic transition is 0.14. Furthermore, we have found that this OA band is quite similar to that of the E center induced in the same materials, indicating that the related electronic transitions involve states highly locali…

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…

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.

Optical absorption band at 5.8 eV associated with the E’_gamma centers in amorphous silicon dioxide: Optical absorption and EPR measurements

Line shape modifications induced by thermal treatment in the optical absorption and electron paramagnetic resonance EPR signals associated with the E center are experimentally investigated in various types of -irradiated amorphous silicon dioxide a-SiO2. The g values of the EPR main resonance line of the E center show a shift correlated with the peak energy variation of the absorption band at about 5.8 eV associated with this defect. These spectroscopic changes are proposed to originate from structural modifications of the defect environment. The correlation is theoretically explained considering that the spin-orbit interaction couples the g-tensor’s elements and the electronic energy level…

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.

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

Generation of oxygen deficient point defects in silica by γ and β irradiation

We report an experimental study of the effects of y and β irradiation on the generation of a point defect known as ODC(II) in various types of commercial silica (a-SiO 2 ). The ODC(II) has been detected by means of photoluminescence (PL) spectroscopy measuring the PL band centered at 4.4 eV and excited at 5.0 eV associated to this defect. Our experiments show that ODC(II) are induced in all the investigated materials after irradiation at doses higher than 5 x 10 2 kGy. A good agreement is observed between the efficiencies of generation of ODC(II) under y and β irradiation, enabling a comprehensive study up to the dose of 5 x 10 6 kGy. Two different growth rates, one in the low and one in th…

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.

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.

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…

Transputer-based parallel system for acquisition and on-line analysis of single-fiber electromyographic signals.

Abstract We describe a transputer-based system suitable for accurate measurements of single-fiber electromyographic jitter. It consists of a conventional electromyograph, a home-made interface and a commercially available transputer-based board installed within a PC/AT compatible. Taking advantage of the concurrent operation of two transputer modules, the system features simultaneous data acquisition and statistical signal processing: while data are acquired and analyzed, a real-time visualization of the signal latency and its variability is provided. In the present configuration, the system can acquire and analyze up to 40,000 consecutive action potentials, which can be grouped into up to …

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

Absorption edge in silica glass

Measurements of optical absorption in the v-UV range in a variety of silica glass are used to determine the width of the absorption edge (Urbach energy). Measured values range from 60 meV up to 180 meV. So high a variability over silica types is tentatively ascribed to the different disorder degree, which characterizes different materials.

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…

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…

Optical properties and photosensitivity of vacuum synthesized Ge-doped sol-gel amorphous SiO/sub 2/

We report optical and electron paramagnetic resonance investigations of gamma ray irradiation effects in sol-gel Ge-doped amorphous SiO/sub 2/. The studied materials have Ge-doping levels up to 10/sup 4/ molar part per million and were densified by two routes differing for the atmosphere: O/sub 2/+N/sub 2/ or vacuum. The obtained results evidence that irradiation affects matrix sites inducing paramagnetic defects. Furthermore, the comparison between the two densification procedures shows that vacuum atmosphere induces higher radiation sensitivity.

Effect of oxygen deficiency on the radiation sensitivity of sol-gel Ge-doped amorphous SiO2

We report experimental investigation by electron paramagnetic resonance (EPR) measurements of room temperature γ-ray irradiation effects in sol-gel Ge doped amorphous SiO2. We used materials with Ge content from 10 up to 104 part per million (ppm) mol obtained with different preparations. These latter gave rise to samples characterized by different extents of oxygen deficiency, estimated from the absorption band at ~5.15 eV of the Ge oxygen deficient centers (GeODC(II)). The irradiation at doses up to ~400 kGy induces the E'-Ge, Ge(1) and Ge(2) paramagnetic centers around g ~ 2 with concentrations depending on Ge and on GeODC(II) content. We found correlation between Ge(2) and GeODC(II) con…

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.

Thermal evolution of the OH-related infrared absorption lineshape in synthetic wet silica

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…

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 …

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…

Temperature effects on the IR absorption bands of hydroxyl and deuteroxyl groups in silica glass

Abstract In this report we will show the changes of the band shape of the hydroxyl group (SiOH) infrared (IR) absorption band (∼3670 cm −1 ) in silica glass induced by lowering temperature in the range from 290 to 20 K. This band is considered as the overlap of several spectral components associated to the vibrational activity of hydroxyl groups in different bond configurations. By a suitable analysis of the experimental band profile in terms of different sub-bands, we studied the thermal evolution of each component and we reconsidered their assignations. For comparison we examined the SiOD absorption band (∼2710 cm −1 ) as a function of temperature as well. Our data can be interpreted as a…

Effects of high pressure thermal treatments in oxygen and helium atmospheres on amorphous silicon dioxide and its radiation hardness

The effects of thermal treatments at similar to 400 degrees C in oxygen or helium atmospheres at similar to 180 baron the radiation hardness of amorphous SiO(2) are studied. The generation efficiency of several point defects under gamma irradiation is compared to that of the untreated material. All the effects on point defects generation here observed can be explained in terms of changes in the precursor sites. In particular it has been observed that the thermal treatments can change the precursors sites of point defects both through temperature and pressure related processes, not depending on the atmosphere, and through oxygen related processes creating oxygen excess sites. The presence of…

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

Vacuum-ultraviolet absorption of amorphous SiO2: intrinsic disorder and role of silanol groups

We present a study on the vacuum-ultraviolet VUV absorption properties of amorphous SiO2 a-SiO2 with high concentrations of silanol groups Si-OH . We found that the absorption spectra are made up of a couple of exponential profiles. The first, in the range from 7.5 to 8.1 eV, was attributed to Si-OH group absorption, while the second, in the range from 8.1 to 8.25 eV, was ascribed to the intrinsic absorption. The VUV absorption cross section of Si-OH groups in a-SiO2 was determined as well. The intrinsic absorption was found to be affected by the Si-OH concentration: high silanol group contents allow lower values of the Urbach energy. This result is interpreted in terms of a reduction in th…

Isolation of the CH3˙ rotor in a thermally stable inert matrix: first characterization of the gradual transition from classical to quantum behaviour at low temperatures

International audience; Matrix isolation is a method which plays a key role in isolating and characterizing highly reactive molecularradicals. However, the isolation matrices, usually composed of noble gases or small diamagnetic molecules,are stable only at very low temperatures, as they begin to desegregate even above a few tens of Kelvin.Here we report on the successful isolation of CH3 radicals in the cages of a nearly inert clathrate–SiO2matrix. This host is found to exhibit a comparable inertness with respect to that of most conventionalnoble gas matrices but it is characterized by a peculiar thermal stability. The latter property is related to thecovalent nature of the host material a…

Hydrogen-Related Paramagnetic Centers in Ge-Doped Sol-Gel Silica Induced by γ-Ray Irradiation

We have studied the generation mechanisms of H(II) paramagnetic centers in Ge-doped silica by investigating up to 104 mol ppm sol-gel Ge-doped silica materials. We have considered materials with the same concentrations of Ge but that are produced by two different densification routes that give rise to different concentrations of Ge-related oxygen deficient centers (GeODC(II)). These centers are characterized by an optical absorption band at ∼5.2 eV (B2 β band) and two related emissions at ∼3.2 eV and ∼4.3 eV. The GeODC(II) content was estimated by absorption and emission measurements. The H(II) centers were induced by room temperature γ-ray irradiation and their concentration was determined…

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)

Anomalous time decay of transient nutations in S = 1/2 spin systems

La decroissance temporelle des signaux de nutation transitoire a ete etudiee experimentalement a la frequence micro-onde sur des systemes de spin 1/2 (centres E' dans la silice and [AlO 4 ] o dans le quartz). Ces signaux decroissent exponentiellement mais avec une vitesse plus grande que la valeur habituellement donnee par les equations de Bloch. On trouve une dependence lineaire de cette vitesse avec la frequence de Rabi. Aucun interpretation pour le moment n'explique veritablement ce comportement anormal

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 examined

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.

Spectral investigation of spin echo emission

Abstract The spectral content of the echo radiation emitted after a two-pulse sequence is measured in a two-level spin system. The spectral profiles exhibit maxima and zeroes of spectral density depending on the exciting sequence parameters. A calculation based on a vectorial model relates the zeroes to those packets that happen to be transparent to the second (refocusing) pulse. Moreover we report on a new spectral narrowing effect which we tentatively ascribe to the instantaneous diffusion.

EPR investigation on the polyamorphic transformation induced by electron irradiation in SiO2 glass

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…

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…

Irradiation effects on the absorption edge of silica glass

Abstract Vacuum ultraviolet absorption experiments were carried out on a variety of specimens of amorphous silica β-irradiated at different doses from ∼103 to 5 × 106 kGy. Changes in the width of the absorption (Urbach) edge were investigated. These changes strongly depend on the kind of silica considered: in particular the Urbach energy of silica of industrial manufacture increases in the irradiated samples, whereas in sol–gel silica it is poorly influenced by the irradiation. The fictive temperature of the different materials before and after irradiation was also monitored. The changes of the Urbach energy and of the fictive temperature are tentatively discussed considering the disorder d…

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

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

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…

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

The role of impurities in the irradiation induced densification of amorphous SiO(2).

In a recent work (Buscarino et al 2009 Phys. Rev. B 80 094202), by studying the properties of the (29)Si hyperfine structure of the E'(γ) point defect, we have proposed a model able to describe quantitatively the densification process taking place upon electron irradiation in amorphous SiO(2) (a-SiO(2)). In particular, we have shown that it proceeds heterogeneously, through the nucleation of confined densified regions statistically dispersed into the whole volume of the material. In the present experimental investigation, by using a similar approach on a wider set of materials, we explore how this process is influenced by impurities, such as OH and Cl, typically involved in relevant concent…

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.

Luminescence and absorption spectroscopy of Sn-related impurity centers in silica

We report an experimental study on the absorption and luminescence spectra of oxygen deficient point defects in Sn-doped silica. The absorption band at 4.9 eV (B2β band) and the two related photoluminescence bands at ∼4.2 eV (singlet-singlet emission, S1 → S0) and at ∼3.2 eV (triplet-singlet emission, T1 → S0), linked by a thermally activated T1 → S1 inter-system crossing process (ISC), are studied as a function of temperature from 300 to 20 K. This approach allows us to investigate the dynamics properties of the matrix in the surroundings of the point defects and the effects of local disorder on the two relaxation processes from S1: the radiative channel to S0 and the ISC process to T1. We…

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…

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. …

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.

Structural organization of silanol and silicon hydride groups in the amorphous silicon dioxide network

We present a study on the effects of an isothermal annealing treatment on a-SiO 2 having a significant content of silanol hydride groups (Si-H). We examined the properties of the IR absorption bands of silanol (Si-OH) and silicon hydride groups as a function of the duration of the thermal treatment. We showed that the Si-OH and Si-H groups contents decrease in a linearly correlated way. The annealing dynamics suggest that the two species are close to each other in the amorphous network. We showed that the profile of the silanol groups absorption band is the same as that observed in other commercial a-SiO 2 materials, irrespectively of the concomitant presence of nearby Si-H groups, and, mor…

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…

A two-component model for the 2260cm−1 infrared absorption band in electron irradiated amorphous SiO2

Abstract We report an experimental study by infrared absorption (IR) measurements focused on the effects of electron irradiation in the dose range from 1.2 × 10 3  kGy to 5 × 10 6  kGy on the intrinsic band peaked at 2260 cm − 1 in amorphous silicon dioxide (a-SiO 2 ) materials. This IR band is particularly relevant as it is assigned to an overtone of the strong asymmetric stretching vibration of Si–O–Si bridges and consequently it is intimately related to the Si–O–Si bond angle distribution. In a recent work we have shown that structural modifications induced by irradiation take place through the nucleation of confined high-defective and densified regions statistically dispersed into the w…

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…

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 …

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…

Role ofH2Oin the thermal annealing of theEγ′center in amorphous silicon dioxide

The model for the annealing of a radiation-induced point defect in silica, the ${\text{E}}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center, is identified in the temperature range $(150--550)\ifmmode^\circ\else\textdegree\fi{}\text{C}$. Thermal treatments in controlled atmospheres of water vapor, oxygen, or helium of irradiated amorphous silicon dioxide are carried out. Direct experimental evidences that the annealing of the ${\text{E}}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center is caused by a reaction with diffusing water molecules are found. A rate equation system describing this annealing process is inferred, and its solutions are compared with experimental data to obtain quantitative …

Erratum to ‘Raman spectroscopy of β-irradiated silica glass’ by B. Boizot, S. Agnello, B. Reynard, R. Boscaino and G. Petite [J. Non-Cryst. Solids 325 (2003) 22–28]

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 …

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…

Polyamorphic transformation induced by electron irradiation ina-SiO2glass

We report a study by electron paramagnetic resonance of amorphous silicon dioxide $(a{\text{-SiO}}_{2})$ irradiated by 2.5 MeV electrons in the dose range from $1.2\ifmmode\times\else\texttimes\fi{}{10}^{3}$ to $5\ifmmode\times\else\texttimes\fi{}{10}^{6}\text{ }\text{kGy}$. By measuring the change in the splitting of the primary $^{29}\text{S}\text{i}$ hyperfine doublet of the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ centers we evidenced an irradiation induced local (around the defects) densification of $a{\text{-SiO}}_{2}$. Our data show that the local degree of densification of the materials is significantly higher than that obtained by mean density measurements, suggesting that the …

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…

Inhomogeneity Effects On Point Defects Studied By Photoluminescence Time Decay In SiO2.

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…

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…

Role of H2O in the thermal annealing of the E’_gamma center in amorphous silicon dioxide

Optical absorption and electron paramagnetic resonance of theEα′center in amorphous silicon dioxide

We report a combined study by optical absorption (OA) and electron paramagnetic resonance (EPR) spectroscopy on the E{sub {alpha}}{sup '} point defect in amorphous silicon dioxide (a-SiO{sub 2}). This defect has been studied in {beta}-ray irradiated and thermally treated oxygen-deficient a-SiO{sub 2} materials. Our results have pointed out that the E{sub {alpha}}{sup '} center is responsible for an OA Gaussian band peaked at {approx}5.8 eV and having a full width at half maximum of {approx}0.6 eV. The estimated oscillator strength of the related electronic transition is {approx}0.14. Furthermore, we have found that this OA band is quite similar to that of the E{sub {gamma}}{sup '} center in…

Competitive relaxation processes of oxygen deficient centers in silica

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

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

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

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.

Effects of Pressure, Temperature, and Particles Size on O2 Diffusion Dynamics in Silica Nanoparticles

The O2 diffusion process in silica nanoparticles is experimentally studied in samples of average radius of primary particles ranging from 3.5 to 20 nm and specific surface ranging from 50 to 380 (m2/g). The investigation is done in the temperature range from 98 to 177 °C at O2 pressure ranging from 0.2 to 66 bar by measuring the interstitial O2 concentration by Raman and photoluminescence techniques. The kinetics of diffusion can be described by the Fick’s equation with an effective diffusion coefficient depending on the temperature, O2 pressure, and particles size. In particular, the dependence of the diffusion coefficient on the pressure and nanoparticles size is more pronounced at lower …

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…

V Symposium SiO2 and Advanced Dielectrics

Modifications of optical absorption band of center in silica

Abstract We report an experimental study of the modifications induced by gamma ray irradiation and by thermal treatment of both the electron paramagnetic resonance (EPR) and the optical absorption spectra of the E γ ′ center in silica. Our data show that the main g-values of E γ ′ EPR signal change as a function of the irradiation dose together with a red shift of the peak position of the absorption band around 5.8 eV attributed to the same center. Changes in the opposite direction are observed in both signals after thermal treatments. The peak position change of the optical absorption band is in quantitative agreement with the g-values shift. This strict correlation is evidence for the exi…

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…

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…

Twofold coordinated 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 wr…

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

Optical absorption band at5.8eVassociated with theEγ′centers in amorphous silicon dioxide: Optical absorption and EPR measurements

Line shape modifications induced by thermal treatment in the optical absorption and electron paramagnetic resonance (EPR) signals associated with the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center are experimentally investigated in various types of $\ensuremath{\gamma}$-irradiated amorphous silicon dioxide $(a\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{2})$. The $g$ values of the EPR main resonance line of the ${E}_{\ensuremath{\gamma}}^{\ensuremath{'}}$ center show a shift correlated with the peak energy variation of the absorption band at about $5.8\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ associated with this defect. These spectroscopic changes are proposed to originate from structu…

Raman spectroscopy study of β-irradiated silica glass

International audience; Natural and synthetic silica glass samples with different OH content have been submitted to β-irradiation at different doses from 106 to 5 × 109 Gy in a Van de Graaff accelerator. Structural changes under irradiation have been analyzed by Raman spectroscopy. The main findings are: (i) a decrease of the Si–O–Si angular dispersion and the average Si–O–Si angle as a function of dose and (ii) an increase of number of three-membered SiO4 ring concentration during irradiation. These results show therefore that purely electronic excitation from β-irradiation induces in a-SiO2 small but significant structural changes of the SiO4 membered ring statistics (size and dispersion)…

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…

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

Experimental evidence for two different precursors of E’γ centers in silica

Electron paramagnetic resonance measurements of concentration and line shape of centers induced by γ ray irradiation are presented for natural and synthetic commercial silica with different OH contents. Synthetic materials with OH content >200 ppm by weight show one line shape for all investigated doses. In contrast, the other materials show a different line shape at low irradiation doses. Differences are also observed in the concentration growth of the centers in synthetic wet materials and in the other materials. The results are interpreted as evidence of two centers distinguishable by their line shape and having different precursors.

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 …

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.

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

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

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 effects on the OH-related infrared absorption band in synthetic wet silica.

The effects of b-irradiation on the OH-related infrared (IR) absorption band in synthetic wet silica samples have been investigated by Fourier transform infrared spectroscopy. Depending on the accumulated doses, b-irradiation affects different zones of the IR composite band at about 3670 cm 1 , assigned to the OH stretching modes of silanol groups. These modifications are independent of the original OH content. The results are discussed considering possible radiation-induced changes of the silanol bonding configuration and of the glass network. These are monitored by revealing the IR band a 2260 cm 1 , which is related to the distribution of Si–O–Si bond angle. We have identified the existence of…

Properties of methyl radical trapped in amorphous SiO2 and in natural SiO2-clathrate Melanophlogite

Abstract We report an experimental investigation by electron paramagnetic resonance (EPR) on methyl radical (CH3 ) observed in γ-ray irradiated high-purity amorphous silicon dioxide (a-SiO2) and in a polycrystalline sample of Melanophlogite, a rare natural form of SiO2-clathrate. From the analysis of the EPR spectra we estimate the correlation time of the hindered rotational motion of CH3 molecules at T = 77 K in the two different materials. This physical quantity gives a quantitative measure of the freedom of motion of CH3 molecules trapped in the two solid systems, putting forward relevant information on the properties of the cavities/interstices in which the radicals are confined. In par…

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 …

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…

Structural disorder and silanol groups content in amorphousSiO2

We present a study on the features of the Urbach edge in amorphous silicon dioxide $(a{\text{-SiO}}_{2})$. The effects of temperature on the absorption edge in the range from 4 to 300 K were studied in both materials having negligible (dry, $l{10}^{17}\text{ }{\text{cm}}^{\ensuremath{-}3}$) and significant (wet, $g{10}^{19}\text{ }{\text{cm}}^{\ensuremath{-}3}$) silanol groups contents. Remarkable differences in the values and in the temperature dependence of the Urbach energy in the dry and wet samples were observed. These differences are interpreted as a consequence of a drastic reduction in the degree of disorder in wet materials, which turn out to be characterized by an electronic struc…

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.

Luminescence and absorption of Sn-related impurity centers in silica.

ABSTRACT We report an experimental study on the absorption and luninescence spectra of oxygen deficient point defects in Sn-doped silica. The absorption band at 4.9 eV (B2b band) and the two related photoluminescence bands at -4.2 eV (singlet-singlet emission, S1 -> So) and at 3.2 eV (triplet-singlet emission, T1 -> So), linked by a thermally activated T1 -> S1 inter-system crossing process (ISC), are studied as a function oftemperature from 300 to 20 K. This approach allows us to investigate the dynamics properties of the matrix in the surroundings of the point defects and the efects of local disorder on the two relaxation processes from S1: the radiatiye channel to So and the ISC process …

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…

Temperature dependence of the absorption properties of silanol groups in amorphous SiO2: Are silanol groups organized in clusters?

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

Vacuum-ultraviolet absorption of amorphousSiO2: Intrinsic contribution and role of silanol groups

We present a study on the vacuum-ultraviolet (VUV) absorption properties of amorphous ${\text{SiO}}_{2}$ $(a{\text{-SiO}}_{2})$ with high concentrations of silanol groups (Si-OH). We found that the absorption spectra are made up of a couple of exponential profiles. The first, in the range from $\ensuremath{\sim}7.5$ to $\ensuremath{\sim}8.1\text{ }\text{eV}$, was attributed to Si-OH group absorption, while the second, in the range from $\ensuremath{\sim}8.1$ to $\ensuremath{\sim}8.25\text{ }\text{eV}$, was ascribed to the intrinsic absorption. The VUV absorption cross section of Si-OH groups in $a{\text{-SiO}}_{2}$ was determined as well. The intrinsic absorption was found to be affected by…

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

Ge-doping dependence of gamma-ray induced germanium lone pair centers in Ge-doped silica

We report an experimental study on the y irradiation effects in Ge-doped sol-gel silica samples doped with Ge from 10 2 up to 10 4 part per million molar. The samples were exposed to the radiation generated by a 60 Co source up to an accumulated dose value of 10 MGy. Our data evidence that the γ irradiation significantly increases the number of Germanium Lone Pair Centers (GLPC). Such defects are induced with a concentration that depends on the Ge content of the employed material in those samples where no optical activity related to -s GLPC was detected before irradiation. Furthermore an increase of the GLPC concentration was detected also in a sample that already contains this defect after…

Second-harmonic free-induction decay in a two-level spin system

Temperature dependence of the absorption properties of silanol groups in amorphous : Are silanol groups organized in clusters?

Abstract We present a study on the vacuum-ultraviolet (VUV) and infrared (IR) absorption of silanol groups in amorphous silicon dioxide ( a - SiO 2 ) in the range of temperature from 4 to 300 K. The observed temperature induced modifications of IR and VUV absorption spectra are interpreted as due to a process of conversion of free into H-bonded silanol groups. The changes of the amplitude of the VUV absorption spectra are shown to be linearly correlated to the changes of the IR absorption of free Si–OH groups. This point together with the evidence that the shape of the Si–OH VUV absorption does not depend on temperature demonstrates that the different silanol group sub-species have differen…

Infrared activity of hydroxyl groups embedded in silica glasses.

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