Search

Synthetic procedures to obtain size and shape-controlled microparticles hold great promise to achieve structural control on the microscale of macroscopic ceramic- or composite-materials. Lutetium oxide is a material relevant for scintillation due to its high density and the possibility to dope with rare earth emitter ions. However, rare earth sesquioxides are challenging to synthesise using bottom-up methods. Therefore, calcination represents an interesting approach to transform lutetium-based particles to corresponding sesquioxides. Here, the controlled solvothermal synthesis of size-tuneable europium doped Lu(OH)(2)Cl microplatelets and their heat-induced transformation to Eu:Lu2O3 above 800 degrees C are described. The particles obtained in microwave solvothermal conditions, and their thermal evolution were studied using powder X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical microscopy, thermogravimetric analysis (TGA), luminescence spectroscopy (PL/PLE) and infrared spectroscopy (ATR-IR). The successful transformation of Eu:Lu(OH)(2)Cl particles into polycrystalline Eu:Lu2O3 microparticles is reported, together with the detailed analysis of their initial and final morphology., Crystals, 11 (8), ISSN:2073-4352

Luminescent nanoparticles are researched for their potential impact in medical science, but no materials approved for parenteral use have been available so far. To overcome this issue, we demonstrate that Eu3+-doped hafnium dioxide nanocrystals can be used as non-toxic, highly stable probes for cellular optical imaging and as radiosensitive materials for clinical treatment. Furthermore, viability and biocompatibility tests on artificially stressed cell cultures reveal their ability to buffer reactive oxygen species, proposing an anti-cytotoxic feature interesting for biomedical applications.

Titanium dioxide (TiO2) nanoparticles were synthesized by nonaqueous sol–gel route using titanium tetrachloride and benzyl alcohol as the solvent. The obtained 4 nm-sized anatase nanocrystals were readily dispersible in various polar solvents allowing for simple preparation of colloidal dispersions in water, isopropyl alcohol, dimethyl sulfoxide, and ethanol. Results showed that dispersed nanoparticles have acidic properties and exhibit positive zeta-potential which is suitable for their deposition by cathodic electrophoresis. Aluminum substrates were anodized in phosphoric acid in order to produce porous anodic oxide layers with pores ranging from 160 to 320 nm. The resulting nanopores were then filled with TiO2 nanoparticles by electrophoretic deposition. The influence of the solvent, the electric field, and the morphological characteristics of the alumina layer (i.e., barrier layer and porosity) were studied.

Bulk materials with remarkable mechanical properties have been developed by incorporating design principles of biological nacre into synthetic composites. However, this potential has not yet been fully leveraged for the fabrication of tough and strong materials that are also optically transparent. In this work, a manufacturing route that enables the formation of nacre‐like mineral bridges in a bioinspired composite consisting of glass platelets infiltrated with an index‐matching polymer matrix is developed. By varying the pressure applied during compaction of the glass platelets, composites with tunable levels of mineral bridges and platelet interconnectivity can be easily fabricated. The effect of platelet interconnectivity on the mechanical strength and fracture behavior of the bioinspired composites is investigated by performing state‐of‐the‐art fracture experiments combined with in situ electron microscopy. The results show that the formation of interconnections between platelets leads to bulk transparent materials with an unprecedented combination of strength and fracture toughness. This unusual set of properties can potentially fulfill currently unmet demands in electronic displays and related technologies., Advanced Functional Materials, 30 (27), ISSN:1616-3028, ISSN:1616-301X

International audience; The recent trends in scintillator technologies stimulate research efforts toward the development of novel materials morphologies, such as nanoparticles, able to efficiently convert ionizing radiations into light. For example, scintillating nanoparticles attract great interest in medical oncological therapies. In this work, the structural and morphological properties of HfO2:Ti nanoparticles with Ti concentrations from 0.03 to 10 mol% and subjected to calcination up to 1000 °C are thoroughly characterized; moreover, X‐ray photoelectron spectroscopy reveals the incorporation of Ti in both Ti (III) and Ti (IV) chemical states in as prepared samples, while the exclusive presence of Ti(IV) is unambiguously identified in calcined nanoparticles. The optical emission under X‐ray excitation evidences an intense Ti (IV)‐related luminescence at 2.5 eV in high temperature calcined samples with a few microseconds scintillation lifetime, and efficiency comparable to that of Bi4Ge3O12 reference scintillator. Finally, the competitive role of defects in charge carriers capture is demonstrated by the monotonic increase of the 2.5 eV band during prolonged X‐ray irradiation, more evident for nanoparticles with titanium concentration below 1 mol%. HfO2:Ti may also find application in X‐ray triggered oncological therapies by using the Ti (IV)‐related bright radioluminescence to excite photosensitizer molecules for singlet oxygen generation.

Defect engineering operated on metal oxides by chemical and structural modifications may strongly affect properties suitable for various applications such as photoelectrochemical behavior, charge transport, and luminescence. In this work, we report the tunable optical features observed in undoped monoclinic HfO2 nanocrystals and their dependence on the structural properties of the material at the nanoscale. Transmission electron microscopy together with X-ray diffraction and surface area measurements were used to determine the fine structural modifications, in terms of crystal growth and coalescence of crystalline domains, occurring during a calcination process in the temperature range from 400 to 1000 °C. The fit of the broad optical emission into spectral components, together with time-resolved photoluminescence, allowed us to identify the dual nature of the emission at 2.5 eV, where an ultrafast defect-related intrinsic luminescence (with a decay time of a few nanoseconds) overlaps with a slower emission (decay of several microseconds) due to extrinsic Ti-impurity centers. Moreover, the evolution of intrinsic visible bands during the material transformation was monitored. The relationship between structural parameters uniquely occurring in nanosized materials and the optical properties was investigated and tentatively modeled. The blue emissions at 2.5 and 2.9 eV are clearly related to defects lying at crystal boundaries, while an unprecedented emission at 2.1 eV enables, at relatively low calcination temperatures, the white luminescence of HfO2 under near-UV excitation.

Here a sustainable approach for the bottom-up fabrication of luminescent carbon dots (CDs) through a green synthetic route by using polymeric waste as a single precursor material is developed. Polylactide has been selected as a carbon-containing model polymeric waste because of its remarkable presence in the packaging field and its associated “white-pollution”. Spherical CDs with diameters of 3 nm have been synthesized through a one-pot hydrothermal reaction of water-dissolved polylactide oligomers (Mn = 1.200–1.900 g mol−1) at mild temperatures. Chemical, structural, morphological and optical properties of the synthesized CDs have been studied. Results reveal that CDs consist of a carbonaceous nucleus having a sp2 conformation with carboxyl and hydroxyl surface groups, making it dispersible in polar media. The optical features of obtained CDs depend on reaction conditions (time and temperature) and on the insertion of nitrogen groups within the CD structure. A proof of concept study of the application of the proposed approach for the production of luminescent CDs from commercial PLA lids for paper hot cups is also provided. The route here reported provides novel cues for a catalyst-free and organic-solvent-free industrial-scale fabrication of photoluminescent nanomaterials from actual polymeric waste as a viable non-toxic and cheap alternative to quantum dots and rare earth based nanophosphors.

Materials combining optical transparency and mechanical strength are highly demanded for electronic displays, structural windows and in the arts, but the oxide-based glasses currently used in most of these applications suffer from brittle fracture and low crack tolerance. We report a simple approach to fabricate bulk transparent materials with a nacre-like architecture that can effectively arrest the propagation of cracks during fracture. Mechanical characterization shows that our glass-based composites exceed up to a factor of 3 the fracture toughness of common glasses, while keeping flexural strengths comparable to transparent polymers, silica- and soda-lime glasses. Due to the presence of stiff reinforcing platelets, the hardness of the obtained composites is an order of magnitude higher than that of transparent polymers. By implementing biological design principles into glass-based materials at the microscale, our approach opens a promising new avenue for the manufacturing of structural materials combining antagonistic functional properties., Nature Communications, 10 (1), ISSN:2041-1723

International audience; In this work, we investigate the optical properties of hafnium dioxide nanocrystals, upon X-ray irradiation, looking for spectral evolution following thermal treatments in air up to 1000 °C that modify the crystal size as well as their point defect concentrations. Radio-luminescence measurements from 10 K up to room temperature reveal a rich and evolving picture of the optical features. A complete spectral analysis of the broad luminescence spectra reveals the presence of several emission components in the visible and UV regions. The lower energy components peaking at 2.1, 2.5, and 2.9 eV are characterized by a thermal quenching energy of 0.08 eV, while the corresponding value for the UV bands at 4.1 and 4.7 eV is close to 0.23 eV. We tentatively assign the components ranging from 2 to 3 eV to the presence of optically active defects of an intrinsic nature, together with the occurrence of titanium impurities; conversely, the bands at higher energies are likely to be of an excitonic nature. The comparison with previous photo-luminescence studies allows evidencing characteristic differences between the features of luminescence emissions caused by intra-centre excitation and those occurring under ionizing irradiation. Finally, scintillation measurements in the visible range reveal the existence of a fast decay in the nanosecond time scale for the smallest hafnia nanocrystals. This study offers a clear description of HfO2 luminescence characteristics upon excitation by X-rays and can lead to a better comprehension of the structure–property relationship at the nanoscale in metal oxides.

The problem of Eu incorporation into silica as dispersed dopants, clusters, separate-phase nanoparticles, or nanocrystals, which is of key importance for applications in the fields of lasers and scintillators, is faced by applying to sol−gel silica doped with nine different Eu3+ concentrations (0.001−10 mol % range) various spectroscopic techniques, including crystal field and vibrational mode analysis by means of Fourier transform absorption and microreflectivity (in the 200−6000 cm−1 and 9−300 K ranges), radioluminescence, and Raman scattering studies at 300 K. The variety of methods revealed the following concordant results: (1) amorphous Eu clusters grow when the Eu concentration is increased up to 3 mol % and (2) Si−OH groups are completely removed and ordered phase separation occurs at 10 mol % doping, as suggested by the remarkable narrowing of the spectral lines. Comparison with polycrystalline Eu oxide, Eu silicates, and α- quartz spectra allowed the unequivocal identification of Eu2Si2O7 pyrosilicate and α-quartz as the main components of nanocrystals in 10 mol % Eu-doped silica. Such conclusions were brilliantly confirmed by transmission electron microscopy and electron diffraction analysis. Phonon coupling and anharmonicity were analyzed and are discussed for a few vibrational modes of nanocrystals.

The fundamental mission of materials science is the description of matter over all length scales. In this review, we apply this concept to particle research. Based on metal oxides, we show that every size range offers its specific features, and every size range had its era, when it was in the center of the research activities. In the first part of the review, we discuss on three metal oxides as examples, how and why the research focus changed its targeted size regime from the micrometer to the nanometer scale and back to the macroscopic world. Next, we present the distinct advantages of using nanoparticles over micrometer-sized particles in selected devices and we point out how such a shift in the size regime opens up new research directions. Finally, we exemplify the methods to introduce nanoparticles into macroscopic objects to make functional ceramics.

In this work a strategy for the control of structure and optical properties of inorganic luminescent oxide-based nanoparticles is presented. The nonaqueous sol-gel route is found to be suitable for the synthesis of hafnia nanoparticles and their doping with rare earths (RE) ions, which gives rise to their luminescence either under UV and X-ray irradiation. Moreover, we have revealed the capability of the technique to achieve the low-temperature stabilization of the cubic phase through the effective incorporation of trivalent RE ions into the crystal lattice. Particular attention has been paid to doping with europium, causing a red luminescence, and with lutetium. Structure and morphology characterization by XRD, TEM/SEM, elemental analysis, and Raman/IR vibrational spectroscopies have confirmed the occurrence of the HfO2 cubic polymorph for dopant concentrations exceeding a threshold value of nominal 5 mol %, for either Lu3+ or Eu3+. The optical properties of the nanopowders were investigated by room temperature radio- and photoluminescence experiments. Specific features of Eu3+ luminescence sensitive to the local crystal field were employed for probing the lattice modifications at the atomic scale. Moreover, we detected an intrinsic blue emission, allowing for a luminescence color switch depending on excitation wavelength in the UV region. We also demonstrate the possibility of changing the emission spectrum by multiple RE doping in minor concentration, while deputing the cubic phase stabilization to a larger concentration of optically inactive Lu3+ ions. The peculiar properties arising from the solvothermal nonaqueous synthesis here used are described through the comparison with thermally treated powders. © 2013 American Chemical Society.

Fluorinated silica glasses with improved vacuum ultraviolet (VUV) transmittance have been synthesized following a sol-gel route starting from fluorinated alkoxide precursors. Matrix dehydration and fluorination have been investigated by Raman, IR, and refractive index measurements. The results show that, during the densification step, the residual hydroxyl and fluorine content can be controlled by governing the kinetic equilibrium between matrix collapse and fluorine evolution. This highlights the pivotal role of in situ reactions of fluorine-containing molecular precursors in the networking mechanism of a sol-gel material after thermal activation. Superior VUV transmittance and radiation hardness with respect to pure commercial silica and undoped sol-gel silica have been confirmed by synchrotron light absorption measurements before and after X-ray exposure. These properties make the material very attractive for applications in VUV photolithography technologies and optical fibers, especially for use in environments with a high level of ionizing radiation, such as spacecrafts and nuclear power plants.

Structural and optical properties of sol–gel silica based glassceramics doped with 0.1 mol% Ce and codoped with Gd at high concentrations, from 5 mol% up to 40 mol%, are investigated and compared to those of analogous samples doped only with Ce. Raman scattering, transmission electron microscopy, and x-ray diffraction reveal the formation of Gd apatite-like silicate (Gd4.67O(SiO4)3) and of Gd pyrosilicate (Gd2Si2O7) nanophases whose morphology and crystallinity depend on the Gd concentration and thermal treatments. Optical absorption measurements demonstrate the role of the densification atmosphere in modifying the charge state of Ce ions. The incorporation of Ce3+ ions in the nanophases is put in evidence by photo- and radio-luminescence results.

Host-tissue integration of medical implants is governed by their surface properties. The capacity to rationally design the surface physico-chemical cues of implantable materials is thus a fundamental prerequisite to confer enhanced biocompatibility. Our previous work demonstrated that different cellular processes are elicited by the nanotexture generated on titanium (cpTi) and Ti6Al4V alloy by chemical oxidation with a H2SO4/H2O2 mixture. Here, we illustrate that by varying the etching parameters such as temperature, concentration, and treatment time, we can create a variety of surface features on titanium which are expected to impact its biological response. The modified submicron and nanotextured surfaces were characterized by scanning electron (SEM) and atomic force (AFM) microscopies. Contact angle measurements revealed the higher hydrophilicity of the modified surfaces compared to untreated samples and Fourier transform infrared spectroscopy (FT-IR) established that the etching generated a TiO2 layer with a thickness in the 40–60 nm range.

The effect of sintering atmosphere on the optical and structural properties of Cerium doped sol-gel silica was investigated. Two sets of xerogels with Ce concentration from 0 to 10 mol% were prepared and densified in different conditions. The effect of a post-densification rapid thermal treatment was also considered. Optical absorption measurements evidenced that in oxidizing conditions Cerium is preferably incorporated inside the silica matrix as Ce4+ while the trivalent state is favoured by reducing conditions. Transmission electron microscopy images show rare-earth clusters formation whose nature was investigated by means of Raman, EDS and microdiffraction measurements. In order to evaluate the efficiency of the glasses as scintillating materials radio-luminescence measurements were carried out. A numerical fit of RL spectra showed the presence of two components peaking at 2.7 and 3.1 eV. After RTT, the relative intensity of the 3.1 eV component increases with Ce concentration. © 2009 Elsevier B.V. All rights reserved.

Elemental Ge nanophases are obtained in silica starting from a sol-gel synthesis. The process comprises the preparation of silica xerogel doped by Ge(IV), substituting for Si(IV) in the oxide network, followed by reduction and phase separation during the sintering process by reaction with H-2 or CO. X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy show that reactions with H-2 give rise in the porous silica network to nanometer-sized crystallization of elemental cubic germanium. (c) 2007 Elsevier Ltd. All rights reserved.

We show here what kind of modification of the interphase morphology of SnO2 nanoparticles in silica (average nanocrystal radius, \(\hat{r}\approx 4\,\hbox{nm}\) in undoped material; \(\hat{r}\,\approx\,2\,\hbox{nm}\) in erbium doped material) brings to the passivation of interfacial defects. Surface states, which may preclude the exploitation of UV excitonic emission, are reduced after doping by rare earth ions. We demonstrate, by means of transmission-electron-microscopy and small-angle-neutron-scattering data, that a smooth interphase with a non negligible thickness takes the place of the fractal and discontinuous boundary observed in undoped material.

A set of terbium-doped silicate glasses densified up to 1050 °C was prepared by the sol-gel method. A broad range of dopant concentrations (0.001-10 mol%) was considered together with an undoped sample as a reference. The effects of a high-temperature (1600-1800 °C) post-densification rapid thermal treatment (RTT) on the luminescence properties of the samples were investigated. RTT enhances the scintillating efficiency of the samples increasing the radio-luminescence intensity up to two orders of magnitude. The relevant effects induced by RTT on radio- and photo-luminescence spectra (RL, PL) and on PL decay curves indicate the occurrence of modifications of the surroundings of Tb3 + luminescence centres. © 2007 Elsevier Ltd. All rights reserved.

Radiation-induced spectral modifications of the 5 eV excited photoluminescence (PL) of oxygen vacancies have been found in a nanostructured silica-based material. This system, made up of SnO2 nanocrystals embedded in amorphous SiO2, is generated by nano-clustering in oversaturated Sn-doped silica produced by sol-gel method. Treatment in oxygen-poor atmosphere introduces oxygen deficiency in the glassy host and a photo-reactive SnO-like interphase at the SnO2 nanocrystal surface. PL measurements initially show native PL activity at 2.7 eV excited at 5 eV, ascribable to oxygen vacancies in intrinsic two-fold coordinated Si sites. Prolonged UV irradiation at 4.7 eV (fourth harmonic of Nd-YAG pulsed laser) gives rise to extrinsic PL activity at 3.1 eV, ascribable to Sn-variant of oxygen vacancy. The results suggest that the UV irradiation causes a progressive release of Sn from the nanophase surface to the glassy network in oxygen vacancy sites. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim).

We investigate the effects of erbium doping on SnO(2) nanoclustering in Sn-doped silica. Vibrational spectroscopy data from Raman and infrared absorption measurements show nanostructuring effects on the SnO(2) nanophase. Ultraviolet absorption spectra evidence a gap shift ascribable to size-dependent quantum confinement, also suggesting a role of erbium doping in determining cluster sizes and the amount of localized states on the nanophase boundary. Transmission electron microscopy confirms and details the spectroscopic data. As a result of these measurements, we find that the nanocrystal size distribution becomes narrower, increasing the erbium concentration, while the density of localized states at the nanocrystal surface decreases. The distribution of erbium ions among the possible environments is then examined through simultaneous spectroscopy of luminescence excited by nanocrystal-to-erbium energy transfer and the absorption of nanocrystal luminescence by erbium ions. This analysis shows that erbium behaves as an extrinsic nucleation centre of the SnO(2) nanophase at low doping levels, whereas at high concentrations it modifies the matrix, hindering the growth of SnO(2) crystals and passivating the interface.

We present a novel strategy for the synthesis of pure and Eu-doped γ-Ga2O3 nanoparticles with an in situ organic capping resulting from a non-aqueous solution-based benzyl alcohol synthesis route. Photoluminescence spectroscopy highlights the concomitant benzoate-related and γ-Ga2O3 exciton-like Eu3+ excitations in the UV, and a blue emission superimposed onto γ-Ga2O3 donor–acceptor recombination, ascribable to organic moieties different from benzoate.

The development of integrated photonics and lab-on-a-chip platforms for environmental and biomedical diagnostics demands ultraviolet electroluminescent materials with high mechanical, chemical and environmental stability and almost complete compatibility with existing silicon technology. Here we report the realization of fully inorganic ultraviolet light-emitting diodes emitting at 390 nm with a maximum external quantum efficiency of ~0.3%, based on SnO(2) nanoparticles embedded in SiO(2) thin films obtained from a solution-processed method. The fabrication involves a single deposition step onto a silicon wafer followed by a thermal treatment in a controlled atmosphere. The fully inorganic architecture ensures superior mechanical robustness and optimal chemical stability in organic solvents and aqueous solutions. The versatility of the fabrication process broadens the possibility of optimizing this strategy and extending it to other nanostructured systems for designed applications, such as active components of wearable health monitors or biomedical devices.

Silica thin films with embedded SnO 2 nanoparticles have been grown on transparent substrates by the sol–gel method. Tin dioxide crystals with cassiterite structure are semiconductors with a wide band gap of ~ 3.6 eV. Optical absorption spectroscopy in the near ultraviolet–visible range has been exploited to probe nanostructuring features of such nanocrystals. The results show that the sintering conditions modify crystallite mean size and enable the occurrence of quantum confinement effects. The outcome is in accordance with transmission electron microscopy data conducted on analogous bulk samples.

To better understand the scintillation mechanism in SrHfO3-based scintillators we investigate in detail their x-ray excited radioluminescence (RL) emissions. The Gaussian decomposition of the undoped SrHfO3 RL spectra manifests the presence of four emission bands peaking at 3.0, 4.0, 4.6, and 5.1 eV. Based on corresponding photoluminescence emission and excitation spectra we tentatively associate the observed bands with excitonic or defect-related emissions. When doped by Ce3+ or Pb2+ luminescent activators, the RL spectra feature two or three new bands, respectively. The temperature dependence of all RL spectra demonstrates a competition between activators and intrinsic or defect centers in carrier capture. Around room temperature the emission process is completely dominated by recombination at activator centers. In the case of Pb2+ activator we also study in detail the concentration dependence of the RL spectra below room temperature exhibiting an optimal value around 0.3 mol %.

We use acetate–citrate combustion to prepare SrHfO3 powders both undoped and doped with Ce3+ and Pb2+ ions in several concentrations, from 0.01 up to 3 mol%. The evolution of their morphological and structural features during the sintering process is studied by scanning electron microscopy, X-ray diffraction, and Raman experiments. We discuss the dependence of the optical properties, investigated by radioluminescence and time resolved luminescence, on sintering conditions and material structure.

Silica samples with embedded SnO2 nanoparticles have been produced by sol-gel method with a synthesis modified by the introduction of fluorinated silicon precursors. The structural features of silica network and SnO2 nanophase have been mapped inside the samples by means of confocal micro-Raman scattering spectroscopy. The results show that the detection of residual fluorine into the matrix as Si-F groups is accompanied by network dehydration, by intensity depletion of the D2 peak assigned to three-member rings of coordinated tetrahedra, and by SnO2 nanoparticles with much larger sizes than in fluorine-free material. © 2009 Elsevier B.V. All rights reserved.

Silica xerogels doped with Ge(IV), substituting for Si(IV) in the oxide network, are prepared from tetraethylorthosilicate and germanium-tetraethoxide. The sintering process is carried out in reducing atmosphere at 700 - 900° C by reaction with H 2 . Raman spectroscopy and high resolution transmission electron microscopy (TEM) show that reactions with H 2 give rise, in the porous silica network, to uncontrolled islands of crystallites of elemental cubic germanium with average size of 50 nm. Sintering process in reducing H 2 atmosphere at temperatures just below the phase separation, at about 610°C, gives materials where Ge atoms are dispersed in the matrix in conditions of incipient clustering. Evidences of segregation of germanium nanocrystals are observed with electron irradiation during TEM analysis. Furthermore, the electron beam induced precipitation leads to the formation of isolated quantum dots-like nanocrystals (5-6 nm in diameter) and with narrower size dispersion. The ranges of suitable temperature and germanium concentration are analysed, as well as the size dispersion of the resulting Ge nanophases.

We present the spectroscopic study of the mechanisms of excitation transfer between rare earth ions excited by energy transfer from SnO 2 nanocrystals in silica. Bulk samples of pure and Er-doped silica with SnO 2 nanoparticles were prepared by a sol gel technique and further thermal sintering process. Transmission electron microscopy (TEM) reveals the formation of spherical nanoclusters with a size distribution strongly determined by erbium doping. Small angle neutron scattering (SANS) experiments confirm and detail the TEM data evidencing the existence of a interphase region at the cluster boundaries where a SnOlike phase compensates the structural mismatch between the crystalline lattice in SnO 2 nanoparticles and the amorphous silica network. The analysis of the SANS patterns show what kind of modification of the interphase morphology of SnO 2 nanoparticles in silica brings to the passivation of interfacial defects. Surface states, which may preclude the exploitation of UV excitonic emission, are reduced after doping by rare earth ions. We demonstrate, by means of transmission-electron-microscopy and small-angle-neutron-scattering data, that a smooth interphase with a non negligible thickness takes the place of the fractal and discontinuous boundary observed in undoped material. The time resolved photoluminescence spectra of erbium in the infrared region show the spectral profile ascribable to ions in a ordered environment. Moreover, the absence of the broad contribution of the radiative decay of erbium ions dispersed in the silica amorphous matrix indicates that the excitation transfer follows paths enveloped in the interphase region. The spectroscopic analysis allows us to conclude that the excitation is transferred from ion to ion within a quasi-crystalline region where each site is surrounded by a different distribution of PL quenching sites which are responsible for the multi-exponential decay kinetics.

In this paper different sol gel syntheses strategies are adopted in order to produce Ce - doped silica - glasses scintillators with improved properties. Variations on the synthesis procedure are adopted to reduce the hydroxyl content of the sol gel glass; to this purpose, a fluorine derivative of silicon alkoxide was added in the sol gel reaction. Since a drawback of Ce - doped sol gel glasses is the partial oxidation of Ce 3+ to Ce 4+ in the matrix probably occurring during the sintering procedure, both Ce - doped xerogel and fluorinated xerogel were treated under reducing atmosphere (H 2 :Ar) instead of the usual oxidizing atmosphere. Glasses obtained in such ways are compared with commercial synthetic glasses and with previously produced sol gel samples by spectroscopic IR absorption measurements, and by radio-luminescence experiments.

We show that Sn O2 nanoclusters in silica interact with ultrashort infrared laser pulses focused inside the material generating a hydrostatic compression and photoelastic response of the surrounding glass. This effect, together with the laser-induced nanocluster amorphization, gives rise to positive or negative refractive-index changes, up to 10-2, depending on the beam-power density. This result points out a wide tuning of the refractive index patterns obtainable in silica-based optical technology. © 2006 American Institute of Physics.

We give the spectroscopic evidence of energy transfer to erbium ions provided by ${\mathrm{SnO}}_{2}$ nanocrystals in silica. The spectral and time resolved analysis of the nanocluster luminescence resonant with ${\mathrm{Er}}^{3+}$ transitions demonstrates that erbium ions take part to energy-transfer mechanisms with an efficiency of about $20%$. The spectral features of erbium emission excited by energy transfer allow to ascribe it to ${\mathrm{Er}}^{3+}$ sites in ordered environments, nearby crystalline tin-dioxide nanoclusters.

Silica glass with SnO2 nanocrystals and Er3+ ions are prepared by the sol-gel route and treatment above 1000 °C. Transmission electron microscopy evidences a homogeneous dispersion of nanoclusters 4-6 nm in size in the amorphous silica matrix. Photoluminescence spectra excited at 3.5 eV, outside erbium transitions, show an inhomogeneous spectral distribution of light emission from interface defects, in the range 1.9-2.4 eV, resonant with transitions of erbium ions. The analysis of kinetics and temperature dependence of luminescence allows to quantify the efficiency of the energy transfer channel between nanoclusters and erbium ions. © 2006 Elsevier Ltd. All rights reserved.

A radioluminescent (RL) dosimetric system, based on a SiO2 optical fiber with the core doped by Ce3+ ions as luminescent activators has been investigated. Structural and optical properties of the luminescent fiber have been studied by Raman, refractive index, RL and scintillation time decay measurements, and compared to those obtained on bulk material. The RL response of a composite fiber made of a short portion of active Ce-doped fiber coupled to a long commercial one has been investigated by x-ray irradiation. A linear RL intensity response has been found in the dose rate interval 6x10(-3)-40 mGy/s together with a good radiation hardness, suggesting possible application in low-dose monitoring. (C) 2004 American Institute of Physics.

Scintillating fibres can be utilized as sensors in many fields such as medical diagnosis, industrial monitoring and other scientific areas. The main advantages of optical-fibre radiation-sensors are the remote sensing and the position-sensitive radiation detection. At present, plastic scintillating fibres present limitation for what concerns both luminescence efficiency and durability (radiation hardness). In this work, new rare-earth-doped high-grade silica glasses are synthesized by a modified sol-gel method. These glasses have an efficiency comparable with the state-of-the-art BGO-sensors, high radiation hardness and high compatibility with the silica-based photonic technology. Powder-in-tube and rod-in-tube techniques are used to fabricate low-loss optical fibres with 135, 220, and 660 microns diameter. Device prototypes are obtained by fusion-splicing these fibres to commercial high NA optical fibres.

The design of nanostructured materials with specific physical properties is generally pursued by tuning nanoparticle size, concentration, or surface passivation. An important step forward is to realize “active” systems where nanoparticles are vehicles for controlling, in situ, some specific, tuneable features of a responsive functional material. In this perspective, this work focuses on the rational design of a nanostructured glass with electrically tuneable dielectric function obtained by injection and accumulation of charge on embedded conductive nanocrystals. This enables electrically controlled switching of semiconducting nanophases to charged polarisable states to be achieved, which could lead to smart, field-enhancement applications in nanophotonics and plasmonics. Here, it is shown that such response switching can be obtained if a percolating charge-transport mechanism is activated through a disordered tree-like network, as is demonstrated to be possible in SiO2 films where suitable dispersions of SnO2 nanocrystals, with conductive interfaces, are obtained as a result of a new synthesis strategy.

Fluorine modified amorphous silica has been synthetized via sol-gel route and studied through analysis of the temperature dependence of the Urbach absorption tail in the vacuum-ultraviolet region. The modified glass has a steep absorption edge above 8 eV, with the absorption coefficient alpha proportional to exp[E/E-U(T)] showing Urbach energy values E-U(T) ranging between 50 and 66 meV. The comparison of E-U(T) with pure silica data indicates a structural softening caused by the reduction of dynamical disorder, and suggests that the F-modified sol-gel synthesis is an appropriate route for achieving high energy shifts of the absorption edge. (C) 2007 American Institute of Physics.

SnO2 nanocrystals are grown in silica starting from a sol-gel method and using Er doping to passivate the cluster boundaries. As a result, emission at 3.8 eV from the decay of SnO2 free excitons is observed in nanostructured SnO2:SiO2, besides the extrinsic 2 eV luminescence of defects in SnO2 and ascribable to substoichiometric nanocluster boundaries. The analysis of the extrinsic emission competitive with the ultraviolet (UV) luminescence evidences the involvement of a phonon mode at 210 cm(-1) from a SnO-like phase. The feasibility of passivated wide-band-gap nanocrystals in silica gives interesting perspectives for UV-emitting optical devices. (c) 2006 American Institute of Physics.

An analysis about the effect of carbon enrichment of allylhydridopolycarbosilane SMP10® with divinylbenzene (DVB) as a promising material for electrical conductive micro electrical mechanical systems (MEMS) is presented. The liquid precursors can be micropipetted and cured in polytetrafluoroethylene (PTFE) molds to produce 14mm diameter disc shaped samples. The effect of pyrolysis temperature and carbon content on the electrical conductivity is discussed. The addition of 28.7wt. of DVB was found to be the optimum amount. Carbon was preserved in the microstructure during pyrolysis and the ceramic yield increased from 77.5 to 80.5wt.. The electrical conductivity increased from 10 6 to 1S/cm depending on the annealing temperature. Furthermore the ceramic samples obtained with this composition were found to be in many cases crack free or with minimal cracks in contrast with the behavior of pure SMP10. Using the same process we demonstrate that also microsized ceramic samples can be produced. © 2014 Elsevier Ltd.