Excitation energy dependence of the photoluminescence band at 2.7 and 4.3 eV in silica glass at low temperature

In this paper, we report the excitation energy dependence of the 2.7 and 4.3 eV photoluminescence (PL) bands in oxygen deficient silica glass at low temperature (20 K). The increase or decrease of the PL intensity at low temperatures is different for different exciting light wavelengths. The PL intensity tended to decrease with low temperatures when the excitation was near the upper and lower end of the excited level. The peak energy of the excitation spectrum increases with cooling. These results indicate that the change in excitation level with cooling is associated with the low-temperature dependence of light emission. Thermal motion is suppressed, when the sample temperature is lowered, and the energy-width of the excited level decreases, i.e., the light emission probability decreases (the emission intensity decreases), when near the upper and lower end of the excitation level. These phenomena were observed in the low-temperature dependence of the 4.3 eV emission intensity.     

Vacuum ultraviolet excitation of the 2.7 eV emission band in neutron irradiated silica

The temperature dependence of the photoluminescence induced at 2.7 eV by ultraviolet (UV) and vacuum ultraviolet (VUV) excitation of neutron irradiated (10²¹ n/m² and 10²² n/m²) KU1 and KS-4V high purity silica, with different OH content, have been studied. Commercial silica Infrasil 301 has also been studied for comparison. At the highest neutron fluence and at the same temperature, the three irradiated silica grades show similar excitation spectra. Two close UV excitation bands, which show opposite temperature dependence, are observed at 4.8 and 5.1 eV. The 4.8 eV band, related to the triplet–singlet transition in SiODCs(II), decreases on decreasing temperature from 300 to 10 K and the band at 5.1 eV, probably related to SiODCs(I), is observed only at very low temperatures (～10 K). An important VUV excitation structure, observed at low temperature, could also be related to SiODCs(I). A shift of the irradiated bands is detected at low temperature.     

Conformational heterogeneity of the point defects in silica: The lifetime of the phosphorescence band at 2.7 eV

We have measured the excitation and emission energy dependence of the lifetimes of the 2.7 eV photoluminescence band associated to oxygen deficient centers in silica glasses. The non-exponential behavior of this time decay is consistent with intrinsic conformational heterogeneity of these point defects in the amorphous matrix. Accordingly, we have analyzed the data in terms of a radiative rates distribution. Moreover, both surface and bulk typologies of these point defects have been studied. The mean value of the lifetime distribution of the surface defects increases from 12 to 15 ms varying the excitation energy from 4.6 to 5.2 eV, and it increases from 14 to 15 ms in the emission energy interval between 2.6 and 3.0 eV. As well similar variations of the lifetime are observed for interior defects, when measured at different excitation and emission energies. We can also estimate the width of the lifetime distribution of this ensemble of point defects in silica glass.     

Origins of optical absorption between 4.8 and 4.9 eV in silica implanted with Si and with O ions

We have determined some of the sources of the optical absorption bands between 4.8 and 4.9 eV in Si and O-implanted silica using several ion energies to produce layers of implanted ions with constant concentrations. The concentrations of implanted ions in the implanted layers ranged from >0.015 at.% to <3 at.%. Optical absorption was measured from 2.0 to 6.5 eV. Electron paramagnetic resonance measurements were made at ∼20.3 and 33 GHz for sample temperatures ranging from 77 to 100 K for most measurements. The components identified in the spectra, based on comparison with reported parameters, were, in the Si case, due to E′ centers and peroxy radicals. In the O case they were due to E′ centers, non-bridging oxygen hole centers, peroxy radical centers, and a newly appearing state which we labeled the OS center. By comparing the changes in the absorption at 4.83 eV with the changes in the concentrations of the various electron paramagnetic resonance components and with the reports in the literature, we conclude that there are at least four oxygen related centers and one Si related center absorbing between 4.8 and 4.9 eV.     

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

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 an evidence of a conversion process of free into H(D)-bonded SiOH(D) groups. Moreover, we estimated the ratio between the molar extinction coefficients of the two main species involved in this process finding that this ratio is appreciably influenced by the isotopic exchange.     

Correlation between the photoluminescence and different types of Si nano-clusters in amorphous silicon

This paper presents the results of PL spectrum study for Si nano-clusters in amorphous silicon matrix. The hydrogenated amorphous Si layers were prepared by the hot-wire CVD method on glass substrates. The layers were deposited at different wafer temperatures 280, 360, 420 and 460 °C and at one filament temperature of 1650 °C. The joint analysis of PL and X-ray diffraction spectra in dependence on the technological conditions and on different sizes of Si nano-clusters has been done. The mechanisms of PL are discussed as well.     

Observation of a new photoluminescence band at 320 nm under 270 nm excitation in Ge-doped silica glass

We investigate the influence of temperature on photoluminescence (PL) in Ge-doped silica glass. Under 270 nm excitation, we observe only one PL band at 424 nm at room temperature (RT). This band shifts to 436 nm with cooling (4 K), and a new PL band is recorded at 320 nm. We assign these PL bands to triplet-to-singlet and singlet-to-singlet transitions of a same Ge-related defect, whose structure is still unknown. The shift of the PL band (from 424 nm at RT to 436 nm at 4 K) is explained by the decrease of the overlap between PLs from different centers.     

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

We investigated by in situ optical absorption measurements the effects induced by 4.7 eV UV laser irradiation on pure silica core optical fibers. Laser irradiation with 100 MW cm^? 2 laser intensity generates in the fiber E′ centers which partially decay after irradiation due to their reaction with diffusing H₂. An absorption band peaked at 5.3 eV is observed to grow in the post-irradiation stage with a kinetics anti-correlated to the decay of the 5.8 eV band of the E′ centers. The defect absorbing at 5.3 eV is proposed to be formed by trapping on pre-existing precursors of hydrogen atoms made available by breaking of H₂ on E′. We also show by repeated irradiation experiments that the 5.3 eV-absorbing center is photochemically destroyed by 4.7 eV laser light, and we estimate the cross section of this process. Possible structural models for this defect are discussed.     

Time resolved thermal lens measurements of the thermo-optical properties of Nd2O3-doped low silica calcium aluminosilicate glasses down to 4.3 K

In this work, the thermal lens spectrometry was applied to measure the thermo-optical properties of Nd₂O₃-doped low silica calcium aluminosilicate glasses as a function of temperature, between 4.3 and 300 K. The thermal relaxation calorimetry was used to determine the specific heat, c_p. The results showed a decrease of the thermal diffusivity of about one order of magnitude from 4.3 K up to 300 K, with a T^?1 dependence in the interval between 20 and 70 K and a T^?0.35 between 4.3 and 20 K. The fluorescence quantum efficiencies of the doped samples were calculated down to 50 K, showing a variation of the order of 12% and 25% for the samples with 0.6 and 1.04 mol% of Nd₂O₃, respectively. In addition, the temperature corresponding to the maximum in c_p/T³, the so-called boson peak, was observed at about 17 K for the undoped sample and at lower temperatures for the doped glasses. In conclusion, our results showed the ability of the time resolved thermal lens to determine the thermo-optical properties of glasses at temperatures lower than 300 K, bringing new possibilities for experiments in a wide range of optical materials.     

Correlation between the luminescence properties and the surface structures of submicron silica particles

We investigated the correlation between the luminescence properties and the surface structures of submicron silica particles prepared by the Stöber method. After annealing in a non-oxidizing atmosphere, the submicron-sized silica particles show a broad photoluminescence (PL) band at 500–540 nm by excitation at an ultraviolet wavelengths (254 and 365 nm), and the one at the 600 nm by excitation an Ar⁺ laser (488 nm). The PL appeared to result from the removal of impurities and subsequent formation of several luminescent structures on the internal surface of the primary particles by thermal annealing.     

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

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

Correlation between dynamic fragility and glass transition temperature for different classes of glass forming liquids

Here we compile literature data for dynamic fragility m for six types of glass forming liquids: polymers, small molecule organics, hydrogen bonding organics, inorganics, ionic and metallic glass formers. Our analysis of the data shows that different categories of glass forming liquids exhibit different behaviors in terms of the correlation between m and T_g, a correlation not previously examined. For example, for hydrogen bonding organics, polymeric and metallic glass formers, there is an approximately linear increase in m with increasing T_g. While for inorganic glass formers, m appears almost independent of T_g, remaining nearly constant over a wide range in T_g. At the same time, another important parameter, the apparent activation energy E_g at T_g has been investigated. It was found that E_g increases with T_g to the 2nd power for hydrogen bonding organics, polymeric and metallic glass forming liquids, while E_g of inorganic glasses has a linear dependence on T_g.     

Annihilation of E′ center defects in silica glass by hydrogen treatment

It was found, using electron paramagnetic resonance (EPR), that the signal of E′ centers in silica glass totally disappeared following a 1 h heat-treatment at 1000 °C under hydrogen atmosphere. However, by subsequent heat-treatment at the same temperature under a dry nitrogen atmosphere, some of the E′ centers re-appeared.     

The transformation balance between two types of structural defects in silica glass in ion-irradiation processes

Structural modification in silica glass irradiated by Au ions was investigated by ultraviolet (UV), photoluminescence and Raman spectrum at the energies from 0.5 to 8 MeV with a fluence of 5 × 10¹³ cm^? 2. In this transit energy region, both nuclear energy loss and electronic energy loss are not negligible. It was found that both the formation of irradiation-induced intrinsic defects and structural transformation from irregular large ring structure (LRS) to small three- and four-member ring structures (SRS) are dominated by the nuclear energy loss. Furthermore, unlike the case of irradiation with β, γ or proton, the concentration of non-bridging oxygen hole center is much enhanced followed with a distinct peak appearing at 5.05 eV in the UV absorption spectra that is attributed to divalent Si. The results suggest that the structural modification in silica glass in the transit energy region is dominated by nuclear energy loss. A mutual transformation balance model among irradiation-induced intrinsic defects, LRS and SRS is established to interpret the identical variation tendencies of intrinsic defects and structural transformation with ion energy.     

The optical properties of a soda-lime-silica glass in the region from 0.006 to 22 eV

From the measured absorption and reflection spectra, we have determined the optical properties of a well-characterized (with respect to impurities and homogeneity) high-purity 21.3 wt% Na₂O?5.2 wt% CaO?73.5 wt% SiO₂ glass over the energy range 0.006–22 eV. The origins of the absorption spectra are discussed.     

Correlation between the low temperature phonon mean free path and glass transition temperature in amorphous solids

An interpretation is offered for the increased chemical resistance of glass surfaces upon treatment with SiF₄/H₂O gaseous mixtures. Scanning electron microscopy examinations of the morphology and evolution of the surface structure, the surface sodium concentration profile as revealed by a nuclear reaction and ion release experiments support the formation of a very adherent amorphous silica layer - still transparent at the earlier stages of treatment - which fits well all experimental findings.     

d-f and f-f transition bands of praseodymium and samarium ions in silica glasses

d-f and f-f transition bands of Pr and Sm ions in silica glasses have been studied by the absorption, excitation and emission spectra. In particular, Sm-doped silica glasses were treated with different atmospheres around the T_g temperature. The change of the valency state and the transition band shown after the treatments are discussed.     

Third-order elastic constants determination in soda–lime–silica glass by Brillouin scattering

Brillouin light scattering allows the measurement of sound velocity and elastic moduli in transparent materials. The ability to select a small scattering volume and to use specific scattering configurations gives important information about the gradient and anisotropy of mechanical properties. Brillouin experiments are often used to measure the second-order elastic constants. When a high accuracy in frequency measurements is achieved, Brillouin scattering may allow the determination of third-order elastic constants in pre-stressed media. Hence, Brillouin scattering provides in principle, a method for the analysis of stress fields in tempered glasses. In order to validate the technique, samples of float soda-lime–silica glass submitted to controlled stresses by four-point flexion were investigated. The results show the expected profile for the velocity of sound waves propagating in directions parallel and perpendicular to the surface of the samples, respectively. They allow the determination of several third-order elastic constants of the investigated glass. This technique was applied to several samples of tempered glass corresponding to different values of the surface stress. The main result is the observation of the expected general trend, namely, through the thickness of the sample, a parabolic variation of the sound velocity whose amplitude increases with the magnitude of the surface stress.     

Femtosecond laser direct processing in wet and dry silica glass

The infrared femtosecond laser damage threshold is found to be independent of OH content in pure silica glass. Additionally, the density and the mean trapping time of electrons excited in the conduction band are also found to be independent on OH concentration.     

Investigation on sol–gel silica coatings for the protection of ancient glass: Interaction with glass surface and protection efficiency

To hinder the phenomenon of weathering of ancient stained glass, the present work proposes the application of sol–gel coatings to the glass surface. Previous investigations [1], [2], [3], [4], [5] and [6], in fact, show that sol–gel silica coatings do not change the appearance of artistic glasses when deposited on their surface. Moreover, the film thickness is so small (around 200 nm) and its composition and structure so compatible with that of the original glass, that the characteristics of the coating and original glass are not distinguishable. In this work, several recipes used to produce sol–gel coatings have been tested in order to understand their behavior when adopted for covering ancient weathered glass. The coatings are made of sol–gel silica prepared with two different catalysts: H⁺, Pb²⁺ and without catalyst. All the investigated samples show a good adhesion of the coating to the glasses used to simulate the behavior of ancient artefacts. The sol–gel silica coatings have been studied before and after accelerated ageing to test the resistance of the protective coatings to weathering. Another important index to test of the efficiency of the sol–gel coatings for the protection of an ancient glass is the lead ion mobility. In ancient stained glass, in fact, this element is present in the metallic lead network, in the grisaille paintings and constitutes a main component of many glass tesserae. The action of water on this highly mobile ion involves the degradation of the glass itself and the release of the ion in the rain solution. Ageing tests show the efficiency of H⁺ and Pb²⁺ catalyzed coatings and the inefficiency of the non-catalyzed sol–gel layers.