Visible-ultraviolet vibronic emission of silica nanoparticles

We report the study of the visible-ultraviolet emission properties and the structural features of silica nanoparticles prepared through a laboratory sol-gel technique. Atomic force microscopy, Raman and Infrared investigations highlighted the 10 nm size, purity and porosity of the obtained nanoparticles. By using time resolved photoluminescence techniques in air and in a vacuum we were able to single out two contributions in the visible emission: the first, stable in both atmospheres, is a typical fast blue band centered around 2.8 eV; the second, only observed in a vacuum around the 3.0-3.5 eV range, is a vibrational progression with two phonon modes at 1370 cm(-1) and 360 cm(-1). By fully…

Effect of thermal annealing on the luminescence of defective ZnO nanoparticles synthesized by pulsed laser ablation in water

This work concerns ZnO nanoparticles (NPs), with sizes of tens of nm, produced by ablation with a pulsed Nd:YAG laser of a Zn plate in H2O. TEM images evidence the formation of nanoparticles with sizes of tens of nm. Moreover, HRTEM images and Raman spectra show that the distance between the crystalline planes and the vibrational modes are consistent with ZnO nanocrystal in wurtzite structure. Their optical properties are characterized by two emission bands both excited above the energy gap (3.4 eV): the first at 3.3 eV is associated with excitons recombination, the second at 2.2 eV is proposed to originate from a singly ionized oxygen vacancy. The green emission is independent of water pH,…

Generation and excitation of point defects in silica by synchrotron radiation above the absorption edge

We report photoluminescence measurements carried out on amorphous SiO{sub 2} upon excitation by synchrotron light. Exposure of the as-grown material to above-edge light at low temperature induces the formation of nonbridging oxygen hole centers (NBOHC), localized in a thin layer below the surface limited by the penetration depth (tens of nm) of impinging light. After concluding the exposure to 11 eV light, stable defects are revealed by observing their characteristic 1.9 eV photoemission band excited at 4. 8eV. The local concentration of induced defects, supposedly formed by nonradiative decay of excitons, is very high (close to approx10{sup 21} cm{sup -3}) and independent of the previous h…

Luminescent silicon nanocrystals produced by near-infrared nanosecond pulsed laser ablation in water

Abstract We report the investigation of luminescent nanoparticles produced by ns pulsed Nd:YAG laser ablation of silicon in water. Combined characterization by AFM and IR techniques proves that these nanoparticles have a mean size of ∼3 nm and a core–shell structure consisting of a Si-nanocrystal surrounded by an oxide layer. Time resolved luminescence spectra evidence visible and UV emissions; a 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 SiO 2 shell.

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…

Synthesis of multi-color luminescent ZnO nanoparticles by ultra-short pulsed laser ablation

Abstract Crystalline ZnO nanoparticles (NPs) are synthesized by ultra-short femtosecond (fs) pulsed laser ablation (PLA) of a zinc plate in deionized water, and are investigated by optical absorption and time resolved luminescence spectra in combination with the morphology and structure analysis. The comparison with previous experiments based on short nanosecond (ns) PLA highlights that pulse duration is a crucial parameter to determine the size and the optical properties of ZnO NPs. While short PLA generates NPs with average size S ‾ of ~ 30 nm, ultrashort PLA allows to achieve much smaller NPs, S ‾ ⩽ 10  nm, that evidence weak quantum confinement effects on both the absorption edge and th…

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 structura…

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.

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 …

Facile synthesis of a monolith of silicon nanocrystal embedded in silica

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

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…

Temperature dependence of O2 singlet photoluminescence in silica nanoparticles

Abstract The near infrared singlet emission and photoluminescence lifetime of O 2 molecules embedded in silica nanoparticles are studied from room temperature down to 10 K. The area of the photoluminescence band under infrared excitation decreases for temperature above 100 K and the lifetime is shortened. These observations provide evidence of a thermally activated relaxation channel with activation energy of about 40 meV. This relaxation mechanism adds to the already known temperature independent electronic-to-vibrational coupling involving high energy vibrational modes of the host matrix or its impurities. The thermally activated process is suggested to consist in the breakage of the O 2 …

Luminescenza risolta in tempo del non bridging oxygen hole center in silice: proprietà di volume e di superficie

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••.

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

Luminescent defects induced by sintering of silica nanoparticles

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…

Oxidation of Zn nanoparticles probed by online optical spectroscopy during nanosecond pulsed laser ablation of a Zn plate in H2O

We report online UV-Visible absorption and photoluminescence measurements carried out during and after pulsed laser ablation of a zinc plate in water, which clarify the events leading to the generation of ZnO nanoparticles. A transient Zn/ZnO core-shell structure is revealed by the coexistence of the resonance absorption peak around 5.0 eV due to Zn surface plasmon resonance and the edge at 3.5 eV of ZnO. The growth kinetics of ZnO, selectively probed by the exciton luminescence at 3.3 eV, begins only after a ∼30 s delay from the onset of laser ablation. We also detect the luminescence at 2.3 eV of ZnO oxygen vacancies, yet rising with an even longer delay (∼100 s). These results show that …

Luminescence Efficiency of Si/SiO 2 Nanoparticles Produced by Laser Ablation

Photoluminescence properties of Si(core)/SiO 2 (shell) nanoparticles produced by pulsed laser ablation in aqueous solution are investigated with the purpose to highlight the microscopic processes that govern the emission brightness and stability. Time resolved spectra evidence that these systems emit a µs decaying band centered around 1.95 eV, that is associated with the radiative recombination of quantum-confined excitons generated in the Si nanocrystalline core. Both the quantum efficiency and the stability of this emission are strongly dependent on the pH level of the solution, that is changed after the laser ablation is performed. They enhance in acid environment because of the H + pass…

Enhancing the luminescence efficiency of silicon-nanocrystals by interaction with H+ions

The emission of silicon nanocrystals (Si-NCs), synthesized by pulsed laser ablation in water, was investigated on varying the pH of the solution. These samples emit μs decaying orange photoluminescence (PL) associated with radiative recombination of quantum-confined excitons. Time-resolved spectra reveal that both the PL intensity and the lifetime increase by a factor of ∼20 when the pH decreases from 10 to 1 thus indicating that the emission quantum efficiency increases by inhibiting nonradiative decay rates. Infrared (IR) absorption and electron paramagnetic resonance (EPR) experiments allow addressing the origin of defects on which the excitons nonradiatively recombine. The linear correl…

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…

Luminescence properties of nonbridging oxygen hole centers at the silica surface

Abstract Two variants of the surface-nonbridging oxygen hole center, ( Si–O)3Si–O• and ( Si–O)2(H–O)Si–O•, stabilized in porous films of silica nano-particles were investigated by time resolved luminescence excited in the visible and UV spectral range by a tunable laser system. Both defects emit a photoluminescence around 2.0 eV with an excitation spectrum evidencing two maxima at 2.0 and 4.8 eV, this emission decreases by a factor ∼2 on increasing the temperature from 8 up to 290 K. However, the different local structure influences the emission lineshape, the quantum yield and the decay lifetime. Such peculiarities are discussed on the basis of the symmetry properties of these defects.

Photoluminescence properties of S2 molecule trapped in Melanophlogite

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 t…

Structural and luminescence properties of amorphous SiO2 nanoparticles

We report an experimental study on the photoluminescence band peaked at 2.7 eV (blue band) induced by thermal treatments in nanometric amorphous SiO 2. In particular the emission dependence on the nanometric particles size as a function of their mean diameter from 7 nm up to 40 nm is investigated. We found that the emission amplitude increases on decreasing the particle diameter, showing a strong correlation between the blue band and the nanometric nature of the particles. By Raman spectroscopy measurements it is evidenced that the SiO2 nanoparticles matrix is significantly affected by the reduction of size. Basing on the shell-like model, these findings are interpreted assuming that the de…

Radiation induced generation of Non-Bridging Oxygen Hole Center: intrinsic and extrinsic processes

Temperature dependence of O2 singlet photoluminescence in silica nanoparticles

Defect-related visible luminescence of silica nanoparticles

The high photon emissivity in the visible spectral range is one of the most relevant phenomena emerging from the reduction of silica down to nanoscale; hence it is promising for the development of optical nanotechnologies (down converter, probes, display). It is well accepted that the origin of this luminescence is related to the high specific surface (~100 m2/g) that favors the formation of optically active defects at the nanosilica surface. With the aim to clarify the role of specific luminescent defects, here we report a detailed study of spectral and decay features by time-resolved photoluminescence spectra under a visible-UV tunable laser excitation. Our study is carried out on differe…

Phonon Coupling Properties of Non Bridging Oxygen Hole Centers at a Silica Surface Probed by Site-Selective Luminescence Excitation

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. …

Optical transitions associated with non bridging oxygen hole centers in irradiated silica

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.

Luminescence mechanisms of defective ZnO nanoparticles.

ZnO nanoparticles (NPs) synthesized by pulsed laser ablation (PLAL) of a zinc plate in deionized water were investigated by time-resolved photoluminescence (PL) and complementary techniques (TEM, AFM, μRaman). HRTEM images show that PLAL produces crystalline ZnO NPs in wurtzite structure with a slightly distorted lattice parameter a. Consistently, optical spectra show the typical absorption edge of wurtzite ZnO (Eg = 3.38 eV) and the related excitonic PL peaked at 3.32 eV with a subnanosecond lifetime. ZnO NPs display a further PL peaking at 2.2 eV related to defects, which shows a power law decay kinetics. Thermal annealing in O2 and in a He atmosphere produces a reduction of the A1(LO) Ra…

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

International audience; 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 af…

Photoluminescence and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles

An experimental study by Raman and Photoluminescence (PL) spectroscopies on the emission and diffusion properties of O2 molecules in amorphous SiO2 nanoparticles of commercial origin with diameters from 14 to 40 nm is reported. Stationary and time resolved PL measurements have been carried out to characterize the Near Infrared (NIR) emission at 1272 nm of O2. Emission features similar to those of bulk silica systems with a sharp PL band and excitation channels in the NIR, at 1070 nm, and in the visible, at 765 and 690 nm are found, with peculiarities arising from embedding O2 in nanostructures. The study of the NIR PL lifetime as a function of temperature down to 10 K enabled to reveal the …

Luminescence Properties of Non Bridging Oxygen Hole Centers at a Silica Surface

Oxidative changes in Sicilian extra virgin olive oil under heating treatment detected by FTIR spectroscopy, viscosimetry and time-resolved luminescence

Photoluminescence of Si nanocrystals embedded in SiO2: Excitation/emission mapping

Time-resolved photoluminescence from Si nanocrystals produced by 1100∘C thermal annealing of SiOx/SiO2 multilayers were investigated by tunable laser excitation, achieving a detailed excitation/emission pattern in the visible and UV range. The emission lineshape is a gaussian curve inhomogenously broadened because of the size distribution of Si nanocrystals, the excitation spectrum consists of the overlap of two gaussian bands centered around 3.4 and 5.1 eV. The mapping of luminescence spectral components with the lifetime points out the energy cubic dependence of the spontaneous emission rate. These findings are interpreted on the basis of models proposed in literature that associate this …

Luminescent Silicon nanocrystals produced by ns pulsed laser ablation

The reduction of Si down to nanoscale introduces a peculiar visible luminescence, surprisingly for a not highly emissive material. This feature is relevant in connection with several application fields (optoelectronics, medicine) and has lead the research towards the development of production methods successful to control the physical and chemical properties of the nanosized Si so as to enhance and tune the luminescence. To this purpose, the laser ablation in liquids is particularly promising since it provides effective controlling parameters (laser photon energy, fluence, repetition rate, liquid reactivity) for the morphology and the structure of Si-related products. Here we report a study…

Role of Ce3+ as sensitizer for the infrared luminescence of phosphosilicate Er/Yb doped glasses

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.

Thermal oxidative process in extra-virgin olive oils studied by FTIR, rheology and time-resolved luminescence

Abstract With the aim to characterise the antioxidant properties of different extra-virgin olive oils and to understand in more detail the mechanisms of oil degradation, we have made an experimental study on thermal induced oxidative processes of extra-virgin olive oils by using different techniques: Fourier Transform Infrared (FTIR) spectroscopy, rheology and time-resolved luminescence. The oxidation process was followed at three different heating temperatures (30, 60 and 90 °C) as a function of time up to 35 days. Thermal treatment induced changes in the FTIR spectra in the wavenumbers region 3100–3600 cm −1 : in particular, the absorption profiles show an initial formation of hydroperoxi…

Controlling the oxidation processes of Zn nanoparticles produced by pulsed laser ablation in aqueous solution

We used online UV-VIS optical absorption and photoluminescence spectra, acquired during and after pulsed laser ablation of a Zinc plate in aqueous solution, to investigate the effect of the laser repetition rate and liquid environment on the oxidation processes of the produced nanoparticles. A transient Zn/ZnO core-shell structure was revealed by the coexistence of an absorption peak around 5.0 eV due to Zn surface plasmon resonance and of an edge at 3.4 eV coming from wurtzite ZnO. The growth kinetics of ZnO at the various repetition rates, selectively probed by the excitonic emission at 3.3 eV, began immediately at the onset of laser ablation and was largely independent of the repetition …

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…

Visible luminescence of nanosilica: slow and fast contributions

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

Time-resolved luminescence of non-bridging oxygen hole centre in silica: Bulk and surface properties

Insight into the defect-molecule interaction through the molecular-like photoluminescence of SiO2 nanoparticles

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…

Emissive titanium dioxide nanoparticles synthesized py pulsed laser ablation in liquid phase

The remarkable applications of TiO2 nanomaterials, including, e.g. photocatalysis and dye-sensitized solar cells, have inspired in the last two decades an extensive amount of research aimed at understanding the properties of these materials. Photoluminescence is scarcely used to probe the electronic properties of TiO2, because neither bulk or nanosized TiO2 commonly display room-temperature emission. In particular, the fundamental luminescence due to the recombination of the self-trapped exciton in anatase TiO2 is typically observed only at low temperatures. We report the synthesis of luminescent titanium dioxide nanoparticles (NPs) by pulsed laser ablation of titanium in aqueous solution. …

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

Bright Visible Luminescence in Silica Nanoparticles

International audience; We demonstrate that a porous film of silica nanoparticles emits a bright visible luminescence associated with defects stabilized by oxygen chemisorption at oxygen deficient center sites. Time-resolved spectra excited by a tunable laser allow us to distinguish the luminescence at 1.99 eV, characteristic of the nonbridging oxygen hole center (NBOHC) (Si-O)3 Si-O*, and a fast and a slow emission: the first (lifetime τ ≈ 25 ns) is peaked at 2.27 eV with an excitation spectrum centered at 5.5 eV; the second (τ ≈ 7.5 μs) is peaked at 2.41 eV and is excited around 3.2 and 5.2 eV. Reaction in an air atmosphere leads to the disappearance of the NBOHC luminescence and of the …

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.

Environment assisted photoconversion of luminescent surface defects in SiO 2 nanoparticles

Abstract Time-resolved photoluminescence investigation on SiO 2 nanoparticles was carried out in controlled atmosphere, with the aim to discern the effects induced on the typical blue luminescence band by high power UV Nd:YAG laser photons (4.66 eV) and by some selected molecular species of the air (O 2 , N 2 , CO 2 , H 2 O). These factors ultimately determine both the brightness and photostability of the emitting defect, so as to limit the unique and attracting potentialities offered by this system in many applicative fields. Here it is highlighted that the effects due to photons and molecules, singularly considered, are not additive, the radiation being more dramatic in reducing the emiss…

Multiband light emission and nanoscale chemical analyses of carbonized fumed silica

Fumed silica with a specific area of 295 m2/g was carbonized by successive phenyltrimethoxysilane treatments followed by annealing in inert atmosphere up to 650 °C. Emission, excitation, kinetics, and photo-induced bleaching effects were investigated by steady state and time-resolved photoluminescence spectroscopies. The local chemistry was also studied by infrared transmission spectroscopy. Strong ultraviolet and visible photoluminescence was observed in the samples after the chemical treatments/modifications and thermal annealing. It has been shown that ultraviolet photoluminescence in chemically modified fumed silica is associated with phenyl groups, while near ultraviolet and visible em…

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

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 luminescen…

Vibrational properties of the surface-nonbridging oxygen in silica nanoparticles

By studying the site-selective luminescence spectra of oxidized silica nanoparticles we identify the electronic and the vibrational lines associated with the surface nonbridging oxygen, $\ensuremath{\equiv}{\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$. This defect emits a zero-phonon line inhomogeneously distributed around 2.0 eV with full width at half maximum of 0.04 eV, weakly coupled with the local ${\text{Si-O}}^{\ifmmode\bullet\else\textbullet\fi{}}$ stretching mode whose frequency is measured to be $920\text{ }{\text{cm}}^{\ensuremath{-}1}$. These findings are different from those of the well-characterized defect in the bulk silica thus evidencing structural peculiarities of …

Spectroscopic parameters related to non bridging oxygen hole centers in amorphous-SiO2

The relationship between the luminescence at 1.9 eV and the absorption bands at 2.0 eV and at 4.8 eV were investigated in a wide variety of synthetic silica samples exposed to different gamma- and beta-ray irradiation doses. We found that the intensities of these optical bands are linearly correlated in agreement with the model in which they are assigned to a single defect. This finding allows to determine spectroscopic parameters related to optical transitions efficiency: the oscillator strength of the 4.8 eV results ~200 times higher than that of the 2.0 eV; the 1.9 eV luminescence quantum yield under 4.8 eV excitation is lower (by a factor ~3) than that under 2.0 eV excitation. These res…

Visible luminescence peculiar to sintered silica nanoparticles: Spectral and decay properties

We report that the sintering at 1000 degrees C of silica nanoparticles (an average diameter of 14 nm) produces a transparent sample that exhibits a bright visible emission under UV excitation. The use of time resolved luminescence spectroscopy and a tunable laser source allows us to single out three contributions centered at 1.96 eV, 2.41 eV and 3.43 eV. The excitation spectra of these emissions evidence bell shaped bands consistent with transitions between localized defects' states. For each emission we study the intensity and the lifetime in the temperature range from 300 K down to 10 K, thus evidencing the competition between radiative and non-radiative processes in the optical cycle of …

Wide range excitation of visible luminescence in nanosilica

The visible luminescence of nanometer-sized silica particles (7 nm mean diameter) was investigated using time resolved spectroscopy. This luminescence is characterized by a wide excitation in the visible and ultraviolet range. The emission spectrum is centred at 2.72 eV with a full width at half maximum of 0.70 eV when excited above 3.5 eV, whereas it progressively empties on the high energy side when excited below 3.5 eV. Moreover, the lifetime falls in the ns timescale and decreases on increasing the emission energy. These features are due to the exceptionally broad inhomogeneous distribution of the emitting centres peculiar to the silica nanoparticles. © 2010 Elsevier B.V. All rights res…

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.

Effects induced by UV laser radiation on the blue luminescence of silica nanoparticles

The effects induced on the blue luminescence centered around 2.8 eV, characteristic of silica nanoparticles, were investigated by monitoring its intensity during and after exposure to the third and the fourth harmonic of a Nd:YAG pulsed laser. The luminescence trend is found to be dependent on the UV photon energy: 3.50 eV photons induce a partial bleaching followed by a recovery in the post-irradiation stage; 4.66 eV photons cause a total bleaching permanent after the irradiation. These results are interpreted as the conversion of luminescent defects towards stable and metastable configurations.

Zero phonon line associated with Non Bridging Oxygen Hole Center in silica: comparison between bulk and surface properties

Luminescence from nearly isolated surface defects in silica nanoparticles

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 findin…

Effect of Hydration Procedure of Fumed Silica Precursor on the Formation of Luminescent Carbon Centers in SiO 2 :C Nanocomposites

The effect of hydration procedure of fumed silica precursor on photoluminescent properties of carbonized silica (SiO2:C) nanocomposite after chemo/thermal treatments is studied. Main structural effect is the formation of chemical bonding of phenyl groups to silica surface via multiple CSiO bonding bridges. Synthesized samples demonstrate very broad photoluminescence (PL) bands in near ultraviolet and visible ranges with maximum intensity dependent on temperature of thermal annealing. Two main trends in luminescence properties are: 1) hydration-induced blue shift of PL in comparison with PL of unhydrated series; 2) red shift of PL bands with increasing synthesis temperature regardless hydr…

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

Quantum confinement effects observed by the photoluminescence of SiOx/SiO2 multilayers

Spectral and decay features related to the red emission from Si nanocrystals were investigated by time-resolved photoluminescence spectra carried out on SiOx/SiO2 nanosized multilayers. On decreasing the SiOx thickness from 8.4 nm to 2.2 nm this luminescence band exhibits a blue-shift from 1.65 eV to 1.75 eV and its lifetime increases from 12μs to 17 μs. These results are discussed on the basis of previous models proposed in literature and agree with quantum confinement effects arising from differently sized Si nanocrystals in our samples.

Radiation induced generation of non-bridging oxygen hole center in silica: Intrinsic and extrinsic processes

Abstract The generation of non-bridging oxygen hole center ( Si–O ) was investigated in a wide variety of natural (fused quartz) and synthetic silica samples exposed to different γ- and β-irradiation doses by looking at its optical bands. We distinguish two different generation processes: intrinsic associated with the cleavage of Si–O bond and characterized by a sublinear law and extrinsic due to the conversion of OH precursor characterized by a growth curve with a saturating tendency. The interplay between the two processes and the role of H are discussed.