Lavinia Vaccaro

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

We studied the inhomogeneous distribution of the luminescence band associated with the nonbridging oxygen hole centre in silica through site selective excitation/detection of the zero phonon line by a tunable laser source. Defects induced in the bulk of synthetic samples by γ and β exposure exhibit an increase of the inhomogeneous width from 0.071 to 0.086 eV on increasing the irradiation dose from 2 × 10(6) to 5 × 10(9) Gy. We also investigated two defect variants stabilized at the surface of the silica nanoparticles, (≡ Si-O)3 Si–O* and (≡ Si-O)2(H-O)Si-O*, whose inhomogeneous width was measured to be 0.042 eV and 0.060 eV, respectively. These results can be accounted for by the structural disorder around the defect, and specific causes of its variation can be pointed out, such as the network modification induced by irradiation or the structural alteration near the SiO(4) coordination sphere.

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 γ 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.

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

{\rm Ce}^{3+}

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

Codoping on the Photoluminescence Excitation Channels of Phosphosilicate Yb/Er-Doped Glasses

We studied the photoluminescence properties of a sample of SiO2-clathrate Melanophlogite, a crystalline microporous material which is found in nature as a rare mineral. Upon β irradiation, the material displays an intense light emission under near-UV illumination. We studied in detail this optical activity by steady-state and time-resolved photoluminescence measurements as a function of temperature. The spectroscopic properties we find can be ascribed to a population of quasi-free molecules trapped within each of the two different types of cage available in the structure of this clathrate, although the spectroscopic properties of the guest molecules are affected by their interactions with the host matrix. Based on the available data, we attribute the observed photoluminescence to trapped S2 molecules, emitting from their excited 3Σu− or 3Πu electronic states, depending on the cage they are trapped in and on temperature. Our results have an impact on the fundamental understanding of host–guest interactions characteristic of microporous systems such as clathrates. Indeed, the data highlight that even a relatively weak coupling between quasi-free S2 molecules and the two types of cages provided by the Melanophlogite host has a surprisingly complex influence on the optical properties of the guest.

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

Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO2 and amorphous fully oxidized SiO2, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescence bands agrees with the two structural typologies: Si nanocrystals emit a μs-decaying red band; defects of SiO2 give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.

Photoluminescence properties of S2 molecule trapped in Melanophlogite

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 Fluorine-doped 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 assign the asymmetric absorption around 2 eV to an unique defect, the NBOHC, instead of a set of various defects.

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

A structured emission/excitation pattern, proper of isolated defects, arises in a vacuum from silica nanoparticles. The luminescence, centered around 3.0-3.5 eV, is characterised by a vibronic progression due to the phonon coupling with two localised modes of frequency  ∼1370 cm(-1) and  ∼360 cm(-1), and decays in about 300 ns at 10 K. On increasing the temperature, the intensity and the lifetime decrease due to the activation of a non-radiative rate from the excited state. Concurrently, the temperature dependence of the lineshape evidences the low coupling with non-localised modes of the matrix (Huang-Rhys factor S ~ 0.2) and the poor influence of the inhomogeneous broadening. These findings outline an uncommon behaviour in the field of the optical properties of defects in amorphous solids, evidencing that the silica surface can allocate luminescent defects almost disentangled from the basal network.

Origin of the visible absorption in radiation-resistant optical fibers

Luminescence properties due to surface defects in SiO2 are the main keystone with particles that have nanoscale dimensions, thus motivating their investigation for many emission related applications in the last few decades. A critical issue is the role played by the atmosphere that, by quenching mechanisms, weakens both the efficiency and stability of the defects. A deep knowledge of these factors is mandatory in order to properly limit any detrimental effects and, ultimately, to offer new advantageous possibilities for their exploitation. Up to now, quenching effects have been interpreted as general defect conversion processes due to the difficulty in disentangling the emission kinetics by the action of the specific quenchers. To overcome this limit, we report a time-resolved investigation of the effects induced in specific controlled molecular environments (N2, O2, CO2 and H2O) on the exceptional molecular-like luminescence that is observed around 3.0–3.4 eV in SiO2 nanoparticles. A comparison with the effects under vacuum indicates changes of the luminescence intensity and lifetime that agree with two quenching mechanisms, static and dynamic. The peculiarity of the spectral features, together with a powerful investigation approach, makes this the system of choice to probe inside the dynamics of the molecule–defect interactions and to reveal promising characteristics for molecular-sensing purposes.

Luminescence from nearly isolated surface defects in silica nanoparticles

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••.