0000000000916153
AUTHOR
Linards Skuja
showing 51 related works from this author
<title>Advances in silica-based glasses for UV and vacuum UV laser optics</title>
2003
The origins of pre-existing and laser-induced ultraviolet (UV) and vacuum ultraviolet (VUV) optical absorption in state-of-the-art glassy silicon dioxide and the ways to improve it are reviewed. The main causes of pre-existing absorption in UV/VUV are oxygen vacancies, hydroxyl (silanol) groups, and strained bonds/localized states due to glassy disorder. The main absorption bands induced by UV/VUV excimer lasers are due to oxygen vacancies and due to silicon and oxygen dangling bonds (E'-centers and non-bridging oxygen hole centers, respectively). The optimized glasses are achieved via an intricate balance between a good stoichiometry, use of network modifiers (F or OH) to reduce the number…
In situobservation of the formation, diffusion, and reactions of hydrogenous species inF2-laser-irradiatedSiO2glass using a pump-and-probe technique
2006
We quantitatively studied the formation, diffusion, and reactions of mobile interstitial hydrogen atoms $({\mathrm{H}}^{0})$ and molecules $({\mathrm{H}}_{2})$ in ${\mathrm{F}}_{2}$-laser-irradiated silica $(\mathrm{Si}{\mathrm{O}}_{2})$ glass between 10 and $330\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Two key techniques were used: single-pulse ${\mathrm{F}}_{2}$ laser photolysis of silanol (SiOH) groups to selectively create pairs of ${\mathrm{H}}^{0}$ and oxygen dangling bonds (nonbridging oxygen hole centers, NBOHC), and in situ photoluminescence measurements of NBOHCs to monitor their reactions with ${\mathrm{H}}^{0}$ and ${\mathrm{H}}_{2}$ as a function of time and temperature. A smalle…
Effects of temperature on electron paramagnetic resonance of dangling oxygen bonds in amorphous silicon dioxide
2011
The properties of electron paramagnetic resonance (EPR) signal of oxygen dangling bonds in amorphous SiO2 ("non-bridging oxygen hole centers", NBOHC) in excimer laser-irradiated amorphous SiO2 were studied in the temperature range 20K to 295K. NBOHCs strongly affect optical and chemical properties of amorphous SiO2 -based (nano) structures and their surfaces. The behaviour of their EPR signal is complicated due to a nearly degenerate electronic ground state. It was found that EPR signal has a non-Curie (~1/T) T-dependence down to 40K, indicating that EPR-based concentration estimates routinely obtained at T = 77K underestimate the center concentrations at least by a factor of 1.7. The estim…
Oxygen Exchange at the Internal Surface of AmorphousSiO2Studied by Photoluminescence of Isotopically Labeled Oxygen Molecules
2009
The exchange between lattice and interstitial oxygen species in an oxide was studied by the $^{16}\mathrm{O}\mathrm{\text{\ensuremath{-}}}^{18}\mathrm{O}$ isotope shift of the ${a}^{1}{\ensuremath{\Delta}}_{g}(v=0)\ensuremath{\rightarrow}{X}^{3}{\ensuremath{\Sigma}}_{g}^{\ensuremath{-}}(v=1)$ infrared photoluminescence band of the oxygen molecules (${\mathrm{O}}_{2}$) incorporated into the interstitial voids of amorphous ${\mathrm{SiO}}_{2}$ ($a\mathrm{\text{\ensuremath{-}}}{\mathrm{SiO}}_{2}$) by thermal annealing in $^{18}\mathrm{O}_{2}$ gas. A large site to site variation of the oxygen exchange rate, originating from structural disorder of $a\mathrm{\text{\ensuremath{-}}}{\mathrm{SiO}}_{…
Modification of vacuum-ultraviolet absorption of SiOH groups in SiO2 glass with temperature, F2 laser irradiation, and H–D isotope exchange
2006
Abstract Variations of vacuum-ultraviolet (VUV) absorption of silanol (SiOH) groups in synthetic wet SiO 2 glass with temperature, exposure to F 2 laser light, and with H–D isotope exchange were examined at photon energies below 8 eV. The intensity of the VUV absorption band decreases with cooling or with exposure to F 2 laser light. The spectral changes in both cases are qualitatively similar and are attributed to an alternation of the bonding configuration of SiOH groups from isolated into hydrogen-bonded states. However, the resultant states are distinctly different: the hydrogen-bonded state formed on cooling is restored reversibly to the isolated state on heating, while that induced by…
Site-selective luminescence study of defects. in gamma-irradiated glassy germanium dioxide
1996
Abstract Luminescence of γ-irradiated samples of GeO2 glass was studied using dye laser excitation in the wavelength region between 590 and 656 nm. An inhomogeneously broadened luminescence band with a peak around 1.86 eV, halfwidth of 0.16 eV and decay constant τ ≈ 5.1 μs was found. At temperatures below 20 K a resonance ZPL and a vibronic peak 710 cm−1 below the laser photon energy emerge when laser is tuned to energies between 1.95–1.89 eV. The site-selective luminescence spectra are qualitatively similar to those of the non-bridging oxygen hole center (NBOHC) in SiO2 glass and are attributed to NBOHC in glassy GeO2. The measured ratio between the energies of the observed local vibration…
Detection of Interstitial Oxygen Molecules in SiO2Glass by a Direct Photoexcitation of the Infrared Luminescence of SingletO2
1996
The presence of interstitial oxygen molecules in glassy ${\mathrm{SiO}}_{2}$ has been demonstrated directly by 1064.1 nm $({\ensuremath{\nu}}^{\ensuremath{'}\ensuremath{'}}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0)\ensuremath{\rightarrow}({\ensuremath{\nu}}^{\ensuremath{'}}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}1)$ excitation of the forbidden ${O}_{2}$ molecule $^{1}\ensuremath{\Delta}_{g}({\ensuremath{\nu}}^{\ensuremath{'}}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0)\ensuremath{\rightarrow}^{3}\ensuremath{\Sigma}_{g}({\ensuremath{\nu}}^{\ensuremath{'}\ensuremath{'}}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0)$ luminescence transition at 1272 nm in S…
The nature of the 4.8 eV optical absorption band induced by vacuum-ultraviolet irradiation of glassy SiO2
2000
Abstract The controversial optical absorption band centered at 4.8 eV, which is present in nearly all irradiated silicas, was investigated. It is caused by at least two different defects: non-bridging oxygen hole center (NBOHC) and interstitial ozone (O3). Both species have absorption bands at 4.8 eV, the O3-related band is identified by its susceptibility to bleaching by 4 to 5 eV photons, by a smaller halfwidth and by its independence from the NBOHC-associated 1.9 eV photoluminescence (PL) band. The contribution of NBOHC to the 4.8 eV band is dominant in most cases, while O3 is important in F2 excimer laser-irradiated samples of oxygen-rich glassy SiO2.
Defects in oxide glasses
2005
An insight into the present understanding of point defects in the simplest and the most radiation-resistant oxide glass, glassy silicon dioxide (silica) is presented. The defects and their generation processes in glassy and α-quartz forms of silicon dioxide are significantly different. The only defect, confirmed to be similar in both materials, is oxygen vacancy. In silica, additional defects of dangling bond type are generated from precursor sites formed by strained Si-O bonds, and by modifier ions. The optical absorption spectra of silica are dominated by paramagnetic dangling bond type defects: silicon dangling bond (“E′-center”) and oxygen dangling bond (“non-bridging oxygen hole center…
Novel method of phosphorescent strontium aluminate coating preparation on aluminum
2018
This work was supported by the ERDF , European-Union Project No. 1.1.1.1/16/A/182 .
An increased F2-laser damage in ‘wet’ silica glass due to atomic hydrogen: A new hydrogen-related E′-center
2006
Abstract A dramatic increase of F2-laser induced room temperature-stable point defects in ‘wet’ synthetic silica glass occurs when irradiation temperature is lowered to 80 K. Contrary to the predictions based on the established models of defect processes, a large part of defects induced at 80 K remains stable also at the room temperature. The intensities of the laser-induced optical absorption bands of the non-bridging oxygen hole centers (2.0 and 4.8 eV) and E′-centers (5.8 eV) are comparable to those created by neutron irradiation (1018 n/cm2). A growth of infrared absorption peak at 2237 cm−1 indicates creation of silicon hydride (SiH) groups. A study of irradiation dose dependences and …
Diffusion of oxygen molecules in fluorine-doped amorphous SiO2
2010
Abstract Effects of fluorine doping on the diffusion of interstitial oxygen molecules (O2) in amorphous SiO2 (a-SiO2) were compared to those obtained from a-SiO2 containing SiOH groups. Incorporation of moderate concentration ( ∼ 1 0 19 cm−3) of SiF groups gives rise to minor changes in diffusion parameters between 800 and 1100 ° C: only a slight decrease in solubility and an increase in the activation energy for diffusion can be detected. Incorporation of SiOH groups has similar weak effects on the solubility and activation energy for diffusion. These minor changes are most likely due to the enhancement of the flexibility of local Si–O network as a result of the dissociation of the netwo…
Vacuum-ultraviolet absorption of interstitial O2 and H2O molecules in SiO2 glass
2006
Abstract Vacuum-ultraviolet (VUV) absorption of O 2 and H 2 O molecules incorporated in interstitial voids in SiO 2 glass by thermal annealings was examined. Interactions of the interstitial molecules with the surrounding SiO 2 glass network lead to a redshift of the VUV absorption band of interstitial O 2 , while a blueshift of that of interstitial H 2 O, both accompanied by an increase in the intensity of the absorption bands. The Coulomb repulsion, London dispersion, and hydrogen bonding are the main interactions responsible for the modification of the VUV absorption bands.
UV–VUV laser induced phenomena in SiO2 glass
2004
Abstract Creation and annihilation of point defects were studied for SiO2 glass exposed to ultraviolet (UV) and vacuum UV (VUV) lights to improve transparency and radiation toughness of SiO2 glass to UV–VUV laser light. Topologically disordered structure of SiO2 glass featured by the distribution of SiOSi angle is a critical factor degrading transmittance near the fundamental absorption edge. Doping with terminal functional groups enhances the structural relaxation and reduces the number of strained SiOSi bonds by breaking up the glass network without creating the color centers. Transmittance and laser toughness of SiO2 glass for F2 laser is greatly improved in fluorine-doped SiO2 glass…
Crucial dependence of excimer laser toughness of “wet” silica on excess oxygen
2011
Creation of point defects by ArF (6.4 eV) and F2 laser (7.9 eV) irradiation in synthetic “wet” silica glass thermally loaded with interstitial O2 molecules was studied by optical absorption, electron paramagnetic resonance and infrared absorption. The presence of excess oxygen caused a significant increase of laser-induced ultraviolet (UV) absorption, which was 4 times (7.9 eV-irradiation) and > 20 times stronger (ArF irradiation) as compared to O2-free samples. The spectral shape of photoinduced absorption nearly completely coincided with the spectral shape of oxygen dangling bonds (NBOHC) in 3 to 6.5 eV regions. The contribution of Si dangling bonds (E' centers) was less than few % and wa…
Role of Mobile Interstitial Oxygen Atoms in Defect Processes in Oxides: Interconversion between Oxygen-Associated Defects inSiO2Glass
2004
The role of mobile interstitial oxygen atoms (${\mathrm{O}}^{0}$) in defect processes in oxides is demonstrated by interconversion between the oxygen dangling bond and the peroxy radical (POR) in ${\mathrm{S}\mathrm{i}\mathrm{O}}_{2}$ glass. Superstoichiometric ${\mathrm{O}}^{0}$ was created by ${\mathrm{F}}_{2}$ laser photolysis of the interstitial ${\mathrm{O}}_{2}$. On annealing above $300\text{ }\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$, ${\mathrm{O}}^{0}$ migrated and converted the oxygen dangling bond to POR. Exposure to 5.0 eV light converted POR back to a pair of the oxygen dangling bond and ${\mathrm{O}}^{0}$ (quantum yield: $\ensuremath{\sim}0.1$). These findings suggest that…
Thermostimulated luminescence of plasma electrolytic oxidation coatings on 6082 aluminium surface
2019
Financial support provided by Scientific Research Project for Students and Young Researchers Nr. SJZ/2016/12 realized at the Institute of Solid State Physics, University of Latvia is greatly acknowledged. Authors are grateful to R. Ignatans for measurements and analysis of XRD spectra and ElGoo Tech ltd. for providing PEO equipment.
Oxygen-excess amorphous SiO2 with 18O-labeled interstitial oxygen molecules
2011
Abstract Exchange between oxygen molecules embedded in amorphous SiO 2 (interstitial O 2 ) and oxygen atoms in the a -SiO 2 network is found to be remarkably slow at 500 °C. Thermal loading of 18 O 2 at this temperature yields a -SiO 2 containing 18 O-labeled interstitial O 2 whose 18 O fraction is as high as ~ 90%. The 18 O fraction of interstitial O 2 in this sample is quickly decreased by thermal annealing at or above 700 °C because of the oxygen exchange accompanied by the release of 16 O from the a -SiO 2 network. This finding indicates that the oxygen exchange starts at much lower temperatures than indicated by previous works, based on monitoring of the isotopic composition of oxygen …
Isoelectronic series of twofold coordinated Si, Ge, and Sn atoms in glassy SiO2: a luminescence study
1992
Abstract Luminescence centers causing optical absorption bands in the 5 eV region in oxygen-deficient pure (‘Si-doped’), as well as in Ge- and Sn-doped glassy SiO2 were studied. The spectral and particularly kinetic data show that in all cases luminescence centers with closely similar properties exist which constitute an isoelectronic series. They are attributed to defects, formed by electrically neutral twofold coordinated Si, Ge, and Sn atoms (T20 centers) in glassy SiO2. Twofold coordinated Si causes the characteristic ‘B2’ optical absorption band at 5.03 eV. Upon reaction with atomic hydrogen, T20 centers convert to the well known ‘H(I)’, ‘H(II)’ and ‘H(III)’ ESR-active defects. The alt…
Exchange between interstitial oxygen molecules and network oxygen atoms in amorphousSiO2studied byO18isotope labeling and infrared photoluminescence …
2011
Amorphous ${\mathrm{SiO}}_{2}$ ($a$-${\mathrm{SiO}}_{2}$) thermally annealed in an oxygen atmosphere incorporates oxygen molecules (O${}_{2}$) in interstitial voids. When the thermal annealing is performed in $^{18}\mathrm{O}$${}_{2}$ gas, interstitial $^{18}\mathrm{O}$${}_{2}$ as well as interstitial $^{16}\mathrm{O}$$^{18}\mathrm{O}$ and $^{16}\mathrm{O}$${}_{2}$ are formed due to the oxygen exchange with the $a$-${\mathrm{SiO}}_{2}$ network. The ${a}^{1}{\ensuremath{\Delta}}_{g}(v=0)\ensuremath{\rightarrow}{X}^{3}{\ensuremath{\Sigma}}_{g}^{\ensuremath{-}}(v=1)$ infrared photoluminescence band of interstitial ${\mathrm{O}}_{2}$ was utilized to quantitatively analyze the oxygen exchange, t…
Optically active oxygen-deficiency-related centers in amorphous silicon dioxide
1998
Abstract The spectroscopic properties, structure and interconversions of optically active oxygen-deficiency-related point defects in vitreous silica are reviewed. These defects, the E′-centers (oxygen vacancies with a trapped hole or 3-fold-coordinated silicons), different variants of diamagnetic `ODCs' (oxygen-deficiency centers), and their Ge-related analogs play a key role in the fiber-optic Bragg grating writing processes. The controversy surrounding the structural models for the Si- and Ge-related ODCs is discussed and the similarity between the bulk and surface point defects in silica is emphasized. The possible interconversion mechanisms between 2-fold-coordinated Si, neutral oxygen …
Dynamics of Singlet Oxygen Molecule Trapped in Silica Glass Studied by Luminescence Polarization Anisotropy and Density Functional Theory
2020
The support from M-ERANET project “MyND” is acknowledged. A.A., M.M-S., and L.R. were supported by the Research Council of Lithuania (Grant M-ERA.NET-1/2015). The authors thank A. Pasquarello for providing the structures of the amorphous SiO 2 matrix for our computational work and K. Kajihara (Tokyo Metropolitan University) for valuable advice in PL kinetics measurements.
Interconversion between non-bridging oxygen hole center and peroxy radical in F2-laser-irradiated SiO2 glass
2004
Formation processes of the peroxy radical (POR) were examined in high-purity SiO 2 glass exposed to F 2 -laser light which creates mobile atomic oxygen (O 0 ) by photolyzing the interstitial oxygen molecules (O 2 ). It was proved that under these conditions POR is formed by a reaction of the non-bridging oxygen hole center (NBOHC, an oxygen dangling bond) with O 0 , not by a reaction between the E' center (a silicon dangling bond) and O 2 . Subsequent exposure to KrF laser light photolyzes POR and recoveres NBOHC by dissociating the O-O bond in POR. These findings corroborate the important role of O° in defect processes in SiO 2 glass.
The correlation of the 7.6 eV optical absorption band in pure fused silicon dioxide with twofold-coordinated silicon
1992
Abstract The optical absorption band at 7.6 eV, which appears in oxygen deficient pure silica, does not correlate with any ESR signal in non-irradiated samples. Longlasting illumination at 80 K in the range of its absorption leads to an increase of the absorption band at 5 eV. Subsequent heating to 290 K restores the initial absorption. These data can be explained as photodissociation and thermal recreation of a complex defect containing a twofold-coordinated silicon defect. This complex defect is responsible for the 7.6 eV absorption band.
Isotope Effect on the Infrared Photoluminescence Decay of Interstitial Oxygen Molecules in Amorphous SiO2
2009
The decay constants of the a1Δg(v=0)→X3Σg-(v=0) infrared photoluminescence (PL) of isotopically-labeled oxygen molecules 16O18O and 18O2 dissolved in the interstitial voids of a-SiO2 are ~1.7 and ~2.5 times larger than that of 16O2. This difference originates from the isotope shift in the energy of the nonradiative transitions from the a state to the vibronic levels of the X ground state. Calibration of the PL quantum yield using the measured decay constants is essential to measure the correct concentration of isotopically-labeled interstitial O2.
Luminescence of non-bridging oxygen hole centers as a marker of particle irradiation of {\alpha}-quartz
2021
The origin of the "red" emission bands in the 600 nm-700 nm region, observed in quartz crystals used for luminescence dating and environmental dosimetry, is still controversial. Their reported spectral and lifetime characteristics are often similar to those of oxygen dangling bonds ("non-bridging oxygen hole centers, NBOHCs") in glassy silicon dioxide. The presence of these "surface radical type" centers in quartz crystal requires sites with highly disordered local structure forming nano-voids characteristic to the structure of glassy SiO2. Such sites are introduced in the tracks of nuclear particles ({\alpha}-irradiation, neutrons, ions). In case of electrons they are created only at large…
Luminescence and Raman Detection of Molecular Cl2 and ClClO Molecules in Amorphous SiO2 Matrix
2017
The support from the Latvian Research Program project IMIS 2 (L.S., K.S.) and Latvian Science Council Grant 302/2012 (A.S.) is acknowledged. K.K. was partially supported by the Collaborative Research Project of Materials and Structures Laboratory, Tokyo Institute of Technology. H.H. was supported by the MEXT Element Strategy Initiative to form research cores.
The behavior of interstitial oxygen atoms induced by F2 laser irradiation of oxygen-rich glassy SiO2
2002
Abstract Interstitial oxygen atoms in glassy silicon dioxide were created by photolysis of pre-existing interstitial oxygen molecules O 2 with a fluorine excimer laser (7.9 eV). The concentration of atomic oxygen interstitials was indirectly monitored by the disappearance and subsequent recovery of interstitial molecules which were monitored by their 1272 nm photoluminescence band. Most of the oxygen interstitials (>95%) are immobile at room temperature. The onset of their mobility occurs between 200 and 400 °C where around 95% of them recombine to form O 2 molecules. The high stability of interstitial oxygen atoms is consistent with the theoretical prediction that they are incorporated int…
Decomposition of peroxy radicals in SiO 2 glass with X‐rays or KrF laser light
2005
Decomposition of the peroxy radical (POR) was examined for wet SiO 2 glasses exposed to X-rays from a Rh-target tube or KrF laser light. The exposure to KrF laser light destroys POR resulting in the selective formation ofthe oxygen dangling bond (termed "non-bridging oxygen hole center", NBOHC). In contrast, the exposure to X-rays creates both the silicon dangling bond (E' center) and NBOHC on bleaching of POR. Clear mutual correlation is found between the formation kinetics of the interstitial oxygen molecule (O 2 ) and of the Si-Si bond but not between those of O 2 and the E' center. These observations indicate that O 2 is created mainly from the radiolysis of the Si-O-Si bond by the Fren…
Diffusion and reactions of interstitial oxygen species in amorphous SiO2: A review
2008
This article briefly summarizes the diffusion and reactions of interstitial oxygen species in amorphous SiO 2 (a-SiO 2 ). The most common form of interstitial oxygen species is oxygen molecule (O 2 ), which is sensitively detectable via its characteristic infrared photoluminescence (PL) at 1272 nm. The PL observation of interstitial 0 2 provides key data to verify various processes related to interstitial oxygen species: the dominant role of interstitial O 2 in long-range oxygen transport in a-SiO 2 ; formation of the Frenkel defect pair (Si-Si bond and interstitial oxygen atom, 0°) by dense electronic excitation; efficient photolysis of interstitial O 2 into O° with F 2 laser light (λ= 157…
Diffusion and Reactions of Hydrogen inF2-Laser-IrradiatedSiO2Glass
2002
The diffusion and reactions of hydrogenous species generated by single-pulsed F2 laser photolysis of SiO-H bond in SiO2 glass were studied in situ between 10 and 330 K. Experimental evidence indicates that atomic hydrogen (H0) becomes mobile even at temperatures as low as approximately 30 K. A sizable number of H0 dimerize by a diffusion-limited reaction into molecular hydrogen (H2) that may migrate above approximately 200 K. Activation energies for the diffusion, inherently scattered due to the structural disorder in glass, are separated into three bands centered at approximately 0.1 eV for free H0, approximately 0.2 eV presumably for shallow-trapped H0, and approximately 0.4 eV for H2.
Frenkel defect process in amorphous silica
2011
Point defects strongly influence optical properties of synthetic amorphous silica (synthetic a-SiO2) used in excimer laser photolithography and their properties are intensively studied. Decomposition of an Si-O-Si bond into a pair of oxygen vacancy and interstitial oxygen species is an intrinsic defect process in a-SiO2. It is similar to the creation of vacancy-interstitial pairs in crystalline materials and is regarded as "Frenkel defect process" in an amorphous material. Oxygens are also known to be emitted from a-SiO2 surfaces under irradiation with vacuumultraviolet (VUV) light or electron beam. However, the anion part of the Frenkel pair in a-SiO2, interstitial oxygen atom, lacks relia…
Vacuum-ultraviolet absorption of hydrogenated and deuterated silanol groups and interstitial water molecules in amorphousSiO2
2005
Vacuum-ultraviolet (VUV) absorption cross sections of hydrogenated and deuterated silanol groups (SiOX, where $\mathrm{X}=\mathrm{H}$ or D) as well as interstitial water molecules $({\mathrm{X}}_{2}\mathrm{O})$ in amorphous $\mathrm{Si}{\mathrm{O}}_{2}$ $(a\text{\ensuremath{-}}\mathrm{Si}{\mathrm{O}}_{2})$ were determined between photon energies of 7 and $8.2\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$. The absorption bands for the deuterated species are blueshifted compared to those for the hydrogenated ones by $\ensuremath{\sim}0.1\phantom{\rule{0.3em}{0ex}}\text{to}\phantom{\rule{0.3em}{0ex}}0.2\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ as a result of a decrease in the zero-point energy associat…
Oxygen-excess-related point defects in glassy/amorphous SiO2 and related materials
2012
Abstract An insight is given into recent experimental advances in the spectroscopic studies of oxygen-excess intrinsic defects, in glassy SiO 2 and α-quartz. By controlling excess oxygen in a-SiO 2 , and the conditions of F 2 -laser irradiation, SiO 2 glass samples can be obtained with optical absorption almost exclusively dominated by single defect, oxygen dangling bonds (“non-bridging oxygen hole centers” or NBOHCs), without the presence of complementary Si dangling bonds (generic “E′-centers”). This allows for a more accurate determination of the spectral shape of NBOHC optical absorption in UV and vacuum UV spectral regions. The temperature dependence of NBOHC electron paramagnetic reso…
Optical Absorption of Excimer Laser‐Induced Dichlorine Monoxide in Silica Glass and Excitation of Singlet Oxygen Luminescence by Energy Transfer from…
2021
An optical absorption (OA) band of interstitial dichlorine monoxide molecules with peak at 4.7 eV and halfwidth 0.94 eV is identified in F2 laser - irradiated (photon energy=7.9 eV) synthetic silica glass bearing both interstitial O2 and Cl2 molecules. Alongside with intrinsic defects, this OA band can contribute to solarization of silica glasses produced from SiCl4. While the formation of ClClO is confirmed by its Raman signature, its structural isomer ClOCl may also contribute to this induced OA band. Thermal destruction of this band between 300C and 400C almost completely restores the pre-irradiation concentration of interstitial Cl2. An additional weak OA band at 3.5 eV is tentatively a…
-ray-induced intrinsic defect processes in fluorine-doped synthetic SiO2 glasses of different fluorine concentrations
2009
Fluorine-doped synthetic SiO2 glass is suitable for investigating intrinsic defect processes in SiO2 glass because of the high radiation hardness and the low concentrations of defect precursors such as the strained Si O Si bonds and impurity-related network modifiers including SiOH, SiH, and SiCl groups. When the concentrations of the defect precursors are minimized by moderate fluorine doping into SiO2 glass, formation of oxygen vacancy–interstitial pairs (Frenkel pairs) is the primarily Co60γ-ray-induced defect process. However, heavy fluorine doping tends to degrade the radiation hardness and enhance the formation of the silicon and oxygen dangling bonds, suggesting the presence of anoth…
Intrinsic defect formation in amorphousSiO2by electronic excitation: Bond dissociation versus Frenkel mechanisms
2008
Two competing mechanisms of intrinsic defect formation in amorphous ${\text{SiO}}_{2}$ $(a{\text{-SiO}}_{2})$, i.e., the vacancy-interstitial (Frenkel) mechanism and Si-O bond dissociation to form silicon and oxygen dangling bonds, were compared under $\ensuremath{\gamma}$-ray electronic excitation. The Frenkel mechanism was found to be dominant. The concentrations of both kinds of defects strongly correlate with the degree of the structural disorder of $a{\text{-SiO}}_{2}$, providing experimental evidence that both types of intrinsic defect pairs are formed mainly from the strained Si-O-Si bonds. The bond dissociation mechanism is more susceptible to the structural disorder than the vacanc…
Fluorine laser-induced silicon hydride SiH groups in silica
2007
Abstract Formation and destruction of silicon hydride (Si–H) groups in silica by F 2 laser irradiation and their vacuum ultraviolet (VUV) optical absorption was examined by infrared (IR) and VUV spectroscopy. Photoinduced creation of Si–H groups in H 2 -impregnated oxygen deficient silica is accompanied by a growth of infrared absorption band at 2250 cm −1 and by a strong increase of VUV transmission at 7.9 eV. Photolysis of Si–H groups by 7.9 eV photons in this glass was not detected when the irradiation was performed at temperature 80 K. However, a slight destruction of Si–H groups under 7.9 eV irradiation was observed at the room temperature. This finding gives a tentative estimate of VU…
Diffusion and Reactions of Photoinduced Interstitial Oxygen Atoms in Amorphous SiO2 Impregnated with 18O-Labeled Interstitial Oxygen Molecules
2014
Both diffusion and reactions of interstitial oxygen atoms (O0) in amorphous SiO2 (a-SiO2) were examined using oxygen-excess a-SiO2 containing 18O-labeled interstitial oxygen molecules (O2) and exposed to F2 laser light (hν = 7.9 eV). Both the F2 laser photolysis of interstitial O2 at 77 K and subsequent heat treatment at ≳200 °C give rise to oxygen exchange between residual interstitial O2 and oxygen atoms in the a-SiO2 network, and these temperatures are far lower than the temperature at which conventional thermal network-interstitial oxygen exchange in unirradiated a-SiO2 occurs (≳700 °C). However, at the initial stage of the low-temperature F2 laser photolysis, an efficient formation of …
Urbach absorption edge of silica: reduction of glassy disorder by fluorine doping
2004
Abstract The vacuum-ultraviolet fundamental absorption edge (‘Urbach edge’) of four types of synthetic silica glasses, ‘wet’, ‘dry’, and doped by 570 and 6010 ppm wt. fluorine, was studied in the absorption coefficient range (1 cm−1–500 cm−1) at room temperature. The absorption edge has exponential form in agreement with the Urbach’s rule. The well-documented increase of vacuum-ultraviolet transparency upon fluorine doping is due to a steeper absorption edge (shorter ‘Urbach tail’) as compared to undoped silicas. The increase of the edge slope in F-doped silica occurs already the lower dopant concentration (570 ppm), the slope does not increase further in the 6010 ppm doped glass. These fin…
18O-labeled interstitial oxygen molecules as probes to study reactions involving oxygen-related species in amorphous SiO2
2012
Abstract Isotope labeling has been widely used to study reactions involving oxygen species in amorphous SiO 2 ( a -SiO 2 ). This article briefly describes recent progress in 18 O labeling techniques to study reactions involving interstitial oxygen molecules (O 2 ), which is one of the most important excess oxygen species in a -SiO 2 . The primary focus will be on the combination of the 18 O labeling with photoluminescence spectroscopy, which enables sensitive and selective detection of interstitial O 2 . Advantages of this method and results of evaluation of oxygen exchange between interstitial O 2 and the Si―O network of a -SiO 2 will be presented.
Reactivity of SiCl and SiF groups in SiO2 glass with mobile interstitial O2 and H2O molecules
2007
Reactions of common network-bound halogens in synthetic SiO2 glass, SiCl and SiF groups, with interstitial O2 and H2O molecules incorporated by thermally annealing were studied. It was found that the chemical properties are distinctly different between SiCl and SiF groups. SiCl groups react with interstitial O2 and H2O to form interstitial Cl2 and HCl, respectively. In contrast, formation of interstitial F2 and HF due to the reaction of SiF groups with interstitial O2 and H2O is not observed. The reactivity of SiCl and SiF groups is in accord with the properties and thermodynamic data of their respective analogous compounds, SiCl4 and SiF4.
Luminescence properties of chlorine molecules in glassy SiO 2 and optical fibre waveguides
2017
The support from Latvian Research Program IMIS 2, project “Photonics and materials for photonics” is acknowledged. K.K. was partially supported by the Collaborative Research Project of Materials and Structures Laboratory, Tokyo Institute of Technology. The publication costs of this article were covered by the Estonian Academy of Sciences and the University of Tartu.
Spontaneous oxygen loading into SiO2 glass by thermal anneal
2004
The interstitial oxygen molecules (O 2 ) in SiO 2 glass were detected down to ∼10 15 cm -3 by photoluminescence of O 2 at 1272nm excited at 765nm by a continuous-wave titanium sapphire laser. It was evidenced that SiO 2 glass thermally annealed in air between 800 and 1100°C spontaneously absorbs ∼10 16 cm -3 of O 2 from the ambient atmosphere. The time-dependent concentration change of the interstitial O 2 allows the determination of both the diffusion coefficient and the solubility of the interstitial O 2 .
Hydrogen-related radiation defects in SiO2-based glasses
2008
Abstract Spectroscopic properties of hydrogen atom trapped in an oxygen vacancy in SiO2 glass were studied. Samples were loaded with D2 and H2 gases to convert O vacancies to pairs of Si–D and Si–H groups, and subsequently irradiated by F2 laser in order to destroy some of these groups. Electron paramagnetic resonance, infrared absorption and visible/UV absorption spectra were measured. Proton hyperfine doublet with splitting of 1.05 mT was found in all H2-treated/irradiated samples. UV-bleaching treatment showed that this signal is independent of the other, well-known hydrogen-related signals in silica. The size of the hyperfine splitting corresponds to twice the 1H nuclear Zeeman splittin…
Electronic Structure of Oxygen Dangling Bond in GlassySiO2: The Role of Hyperconjugation
2003
The electronic structure and the nature of optical transitions in oxygen dangling bond in silica glass, the nonbridging oxygen hole center (NBOHC), were calculated. The calculation reproduced well the peak positions and oscillator strengths of the well-known optical absorption bands at 2.0 and 4.8 eV, and of the recently discovered absorption band at 6.8 eV. The 2.0 eV band was attributed to transition from the $\ensuremath{\sigma}$ bond between Si and dangling oxygen to nonbonding $\ensuremath{\pi}$ orbital on the dangling oxygen. The uniquely small electron-phonon coupling associated with the 2.0 eV transition is explained by stabilization of Si-O bond in the excited state by hyperconjuga…
Creation of glass-characteristic point defects in crystalline SiO2 by 2.5 MeV electrons and by fast neutrons
2019
The support from M -ERANET project “MyND” is acknowledged. K.K. was partially supported by the Collaborative Research Project of Laboratory for Materials and Structures, Tokyo Institute of Technology . Visiting researcher support from Ecole Polytechnique, Palaiseau is appreciated. Mr. Olivier Cavani is thanked for the expert help with irradiations.
Infrared photoluminescence of preexisting or irradiation-induced interstitial oxygen molecules in glassySiO2and α-quartz
1998
A sensitive technique for detecting interstitial ${\mathrm{O}}_{2}$ molecules in ${\mathrm{SiO}}_{2}$ is demonstrated by measuring their infrared $\stackrel{\ensuremath{\rightarrow}}{a}X$ luminescence at 1272.2 nm under a Ti-sapphire laser excitation into the ${\mathrm{O}}_{2}\stackrel{\ensuremath{\rightarrow}}{X}b$ absorption band at 765 nm. Contrary to the case of ${\mathrm{O}}_{2}$ trapped in inert gas matrices, the visible emission of ${\mathrm{O}}_{2}$ corresponding to the direct $\stackrel{\ensuremath{\rightarrow}}{b}X$ transition is not found. Examination of different neutron- and gamma-irradiated glassy ${\mathrm{SiO}}_{2}$ and \ensuremath{\alpha}-quartz samples reveals radiation-in…
The origin of the intrinsic 1.9 eV luminescence band in glassy SiO2
1994
Abstract The current controversy over the nature of the centers giving rise to the 1.9 eV photoluminescence (PL) band (the R-band), the suggested defect models and the relevant experimental data are briefly reviewed. The luminescence emission, excitation and polarization spectra of neutron-irradiated synthetic silica were studied between 6 and 300 K using site-selective dye-laser and Ar ion laser excitation. Resonant zero-phonon lines (ZPL) were observed below 80 K both in luminescence emission and excitation spectra in the 1.9–2.1 eV region. A vibration line in emission spectra 890 cm−1 below the ZPL energy is attributed to the symmetric stretching vibration of the silicon-non-bridging oxy…
Visible to vacuum-UV range optical absorption of oxygen dangling bonds in amorphous SiO2
2011
Synthetic silica glass with an optical absorption spectrum dominated by oxygen dangling bonds (nonbridging oxygen hole centers, or NBOHCs) and having negligible (1%) contribution from the usually copresent Si dangling bonds (E\ensuremath{'}-centers), was prepared by room temperature ultraviolet photobleaching of high SiOH content (``wet'') silica, irradiated by F${}_{2}$ laser (7.9 eV) at $T$ = 80 K. This allowed us to obtain the up-to-now controversial optical absorption spectrum of NBOHC in the ultraviolet and vacuum-ultraviolet (UV-VUV) region of the spectrum and to show that it is semicontinuous from 4 to 7.8 eV and cannot be represented by a pair of distinct Gaussian bands. Since NBOHC…
Optical properties of chlorine-and oxygen-related defects in SiO$_2$ glass and optical fibers
2018
International audience; Photoinduced processes involving chlorine molecules in synthetic silica were studied. Interstitial Cl$_2$ in SiO$_2$ are prevented from VIS/UV photolysis by cage effect. However, they react with oxygen interstitials yielding photosensitive ClClO molecules absorbing at 264nm.