0000000000161789
AUTHOR
Stefania Grandi
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…
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…
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…
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…
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…
Concentration growth and thermal stability of gamma-ray induced germanium lone pair center in Ge-doped sol–gel a-SiO2
Abstract We report an experimental study of the concentration growth by γ-ray irradiation of germanium lone pair center (GLPC) in 10 4 part per million molar Ge-doped sol–gel silica. The data show that γ-ray induced GLPC concentration increases linearly up to ∼5 MGy and then it seems to reach a limit value. In addition to the dose dependence, we have studied the thermal stability of the radiation induced GLPC in ambient atmosphere up to 415 °C. We found that the concentration of this latter GLPC starts to decrease at ∼300 °C, at variance to native GLPC, suggesting that the annealing is related to irradiation products. After the thermal treatments the photoluminescence (PL) activity of the γ…
Synthesis and Characterisation of Functionalized borosilicate nanoparticles for boron neutron capture therapy applications
Boron Neutron Capture Therapy (BNCT) is a promising therapy for the cure of diffuse tumors. The successful clinical application of BNCT requires finding new boron-based compounds suitable for an efficient 10B delivery to the cancerous tissues. The purpose of this work is to synthesize borosilicate nanoparticles by a sol–gel recipe, and to functionalize them with folic acid in order to promote their capture by the tumor cells. Whereas sol–gel is a promising technique for the synthesis of nanoparticles, in case of borosilicate systems this approach is affected by significant boron loss during preparation. Here we show that functionalization of borosilicate nanoparticles with folic acid can re…
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…
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 …
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 activity of surface and interior Ge-oxygen deficient centers in silica
We report a comparative study on the optical activity of surface and interior Ge–oxygen deficient centers in pressed porous and sol–gel Ge-doped silica, respectively. The experimental approach is based on the temperature dependence of the two photoluminescence bands at 4.2 (singlet–singlet emission, S1! S0) and 3.1 eV (triplet–singlet emission, T1! S0), excited within the absorption band at about 5 eV. Our data show that the phonon assisted intersystem crossing process, linking the two excited electronic states, more effective for surface than for interior centers in the temperature range 5–300 K. For both centers, a distribution of the activation energies of the process is found. Based on th…
Refractive index change dependence on Ge(1) defects inγ-irradiated Ge-doped silica
We present an experimental study regarding the effects of the $\ensuremath{\gamma}$ radiation on silica glass doped with Ge up to $10\text{ }000$ ppm molar produced by the sol-gel technique. We have determined the irradiation-induced changes in the refractive index $(\ensuremath{\Delta}n)$ as a function of the oxygen deficiency of the samples, evaluated from the ratio between the germanium lone pair centers (GLPC) and the Ge content. $\ensuremath{\Delta}n$ at 1500 nm have been estimated using optical-absorption spectra in the range 1.5--6 eV. We have found that $\ensuremath{\Delta}n$ is independent of Ge differences for GLPC/Ge values $l{10}^{\ensuremath{-}4}$, while it depends on Ge for la…
Structural inhomogeneity of Ge-doped amorphous SiO2 probed by photoluminescence lifetime measurements under synchrotron radiation.
We report a study of the photoluminescence (PL) time decay of the B-type center, characterized by an optical absorption band peaked at similar to 5.2 eV and two related PL bands peaked at similar to 3.2 eV and similar to 4.3 eV, in sol-gel Ge-doped a- SiO2 under excitation by synchrotron radiation. Measurements were carried out by excitation in UV and in vacuum-UV (VUV), and were performed in the temperature range from 8 K up to 300 K in order to isolate the effects of the intersystem-crossing process, proposed to link the two emission bands of the center. Repeating the time decay measurement at several emission energies falling inside the 4.3 eV band, we have observed a variation of the PL…
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…