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In this paper, the great sensitivity and selectivity to NO2 detection at low temperature down to ppb level of zinc oxide (ZnO) thick-film sensors are reported. Sensor performances of ZnO films prepared by screen-printing technique were evaluated comparing two different ZnO nano-powders in wurtzite crystal structure. Powders were synthesized by hydrothermal route (HT-ZnO) and by auto-combustion sol–gel synthesis (AC-ZnO). After proper characterization of the nano-powders, the thick-film sensors were fabricated by screen-printing technique onto α-alumina substrates equipped with Pt interdigitated electrodes, followed by a thermal treatment. The sensor response was studied in the range 50–250 °C. Best results were reached at 150 °C, with sensor response R (Zg/Z0)—defined as the ratio between impedance under NO2 (Zg) and impedance under dry air (Z0)—equal to 42.92 for HT-ZnO and to 23.18 for AC-ZnO under 0.5 ppm of NO2 in dry conditions. Finally, response and recovery time were measured, and selectivity of the sensors was determined by exposing the film toward O3, CO2, CH4, N2O and humidity at the best working temperature. Both sensors showed great sensitivity for NO2 detection, supporting the exploitation of these sensors as NO2 detectors at ppb level.

In recent years, there has been a growing interest towards compact high peak-power pulsed laser sources for applications such as LIDAR, range findings, remote sensing, communications and material processing. A common laser architecture used to realize these sources is the Master Oscillator Power Amplifier (MOPA), in which a master oscillator produces a highly coherent beam and a fiber amplifier boosts the output power, while preserving its main spectral properties. Phosphate glasses are recognized to be an ideal host material for engineering the amplification stage of a pulsed MOPA since they enable extremely high doping levels of rare-earth ions to be incorporated in the glass matrix without clustering, thus allowing the fabrication of compact active devices with high gain per unit length. With the aim of realizing compact optical fiber amplifiers operating at 1 and 1.5 µm, a series of highly Yb3+- and Yb3+/Er3+-doped custom phosphate glass compositions were designed and fabricated to be used as active materials for the core of the amplifiers. Suitable cladding glass compositions were explored and final core/cladding glass pairs were selected to realize single-mode and multi-mode optical fibers. Core and cladding glasses were synthesized by melt-quenching technique. The core glass was then cast into a cylindrical mold to form a rod, while the cladding glass was shaped into a tube by rotational casting method or extrusion technique. The latter has been extensively employed for the manufacturing of tellurite and germanate glass preforms, but only recently the first example of active phosphate fiber preform fabricated by this method has been reported by our research team. Phosphate fibers were then manufactured by preform drawing, with the preform being obtained by the rod-in-tube technique. Preliminary results of pulsed optical amplification at 1 and 1.5 µm are presented for a single-stage MOPA.

Ion-exchange in molten nitrate salts containing metal ions (i.e. silver, copper, etc.) represents a well-established technique able to modify the chemical-physical properties of glass materials. It is widely used not only in the field of integrated optics (IO) but also, more recently, in plasmonics due to the possibility to induce the formation of metal nanoparticles in the glass matrix by an ad hoc thermal post-process. In this work, the application of this technology for the realisation of low-cost and stable surface-enhanced Raman scattering (SERS) active substrates, based on soda-lime glass microrods, is reported. The microrods, with a radius of a few tens of microns, were obtained by cutting the end of an ion-exchanged soda-lime fibre for a length less than 1 cm. As ion source, silver nitrate was selected due to the outstanding SERS properties of silver. The ion-exchange and thermal annealing post-process parameters were tuned to expose the embedded silver nanoparticles on the surface of the glass microrods, avoiding the use of any further chemical etching step. In order to test the combined SERS/fluorescence response of these substrates, labelled molecular beacons (MBs) were immobilised on their surface for deoxyribonucleic acid (DNA) detection. Our experiments confirm that target DNA is attached on the silver nanoparticles and its presence is revealed by both SERS and fluorescence measurements. These results pave the way towards the development of low-cost and stable hybrid fibres, in which SERS and fluorescence interrogation techniques are combined in the same optical device.

This work reports the study of ZnO-based anodes for the photoelectrochemical regeneration of the oxidized form of nicotinamide adenine dinucleotide (NAD+). The latter is the most important coenzyme for dehydrogenases. However, the high costs of NAD+ limit the use of such enzymes at the industrial level. The influence of the ZnO morphologies (flower-like, porous film, and nanowires), showing different surface area and crystallinity, was studied. The detection of diluted solutions (0.1 mM) of the reduced form of the coenzyme (NADH) was accomplished by the flower-like and the porous films, whereas concentrations greater than 20 mM were needed for the detection of NADH with nanowire-shaped ZnO-based electrodes. The photocatalytic activity of ZnO was reduced at increasing concentrations of NAD+ because part of the ultraviolet irradiation was absorbed by the coenzyme, reducing the photons available for the ZnO material. The higher electrochemical surface area of the flower-like film makes it suitable for the regeneration reaction. The illumination of the electrodes led to a significant increase on the NAD+ regeneration with respect to both the electrochemical oxidation in dark and the only photochemical reaction. The tests with formate dehydrogenase demonstrated that 94% of the regenerated NAD+ was enzymatically active.

Recently developed calcium-phosphate glass formulations are proposed in this chapter as a new class of materials for biomedical optics and photonics. The glasses have been designed and carefully prepared in our laboratory to be dissolvable in biological fluids while being optically transparent, mechanically reliable both in dry and humid environments, and suitable for both preform extrusion and fiber drawing. Optical fibers have been drawn from these glasses using our custom-made induction heated drawing tower and showed attenuation loss values from one to two orders of magnitude lower than the counterpart polymeric-based bioresorbable devices reported in literature. In addition, the optical fibers have been implanted in living rats for several weeks and no clinical signs of any adverse effect have been found. Results on the inscription and characterization of different types of fiber Bragg grating-based optical filters will be also shown, together with the demonstration of the suitability of the above-mentioned bioresorbable optical fibers for time-domain diffuse optical spectroscopy.

In this paper, the impact of the post-heat-treatment on the structural and spectroscopic properties as well as on the chemical durability of a thermally stable Er3+-doped phosphate glass in the system P2O5 - K2O - Al2O3 - B2O3 - BaO - PbO - La2O3 - Gd2O3 is reported. Two crystalline phases, namely La, Gd-monazite and AlKP2O7, were found to precipitate from the surface of the glass after heat-treatment, as confirmed by both X-ray Diffraction (XRD) and Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX) analyses. Moreover, the heat-treatment was responsible for the formation of a more polymerized glass network close to the surface crystalline layer as evidenced using micro-Raman spectroscopy. From the changes in the Er3+ optical properties, some of the Er3+ ions are suspected to enter in the crystals. Both the as-prepared and heat-treated glasses were subjected to a degradation test in hydrochloric acid (HCl) and showed a congruent and incongruent dissolution behavior, respectively.

Recent developments in sensors are pushing for optimized materials that can increase their usage, bolster their sensitivity and enable new and more efficient transduction mechanisms. We hereby review some of the most relevant applications of glasses and glass–ceramics for photonic sensors considering the recent trends and innovative approaches. This review covers from bulk glasses to thin films and from fiber optics to nanocrystal-based and their applications in sensing.

Silica optical fibers are employed in endoscopy and related minimally invasive medical methods thanks to their good transparency and flexibility. Although silicon oxide is a biocompatible material, its use involves a serious health risk due to its fragility and the fact that potential fiber fragments can freely move inside the body without the possibility of being detected by conventional methods such as X-ray imaging. A possible solution to this issue can be the development of optical fibers based on bioresorbable (i.e., biodegradable and biocompatible) materials, which exhibit the important benefit of not having to be explanted after their functionality has expired. The optical power transmission tests of recently developed single-mode (SM) and multi-mode (MM) bioresorbable optical fibers based on calcium-phosphate glasses (CPGs) are here reported. A continuous-wave (CW) fiber laser at 1080 nm with output power up to 13 W and picosecond laser sources at 515 and 1030 nm with MW pulse peak power were used to test the transmission capabilities of the CPG fibers. No degradation of the CPG fibers transmission under long-term illumination by CW laser was observed. A laser-induced damage threshold (LIDT) at a fluence higher than 0.17 J/cm2 was assessed with the picosecond laser sources.

New perfluoropolyalkylether (PFPAE) monomers, chain extended with different alkyl groups and functionalized with vinyl ether or epoxide end-groups, were employed, together with trimethylolpropane trivinyl ether or trimethylolpropane triglycidyl ether, to produce fluorinated copolymers. The photoinduced cationic polymerization was investigated, and the PFPAE-based copolymer properties were thoroughly characterized. Interesting surface properties and two different values of refractive index were observed: thus, these fluorinated copolymers can be suitable materials for the manufacture of self-cleaning coatings and optical waveguides. Electronic supplementary material The online version of this article (10.1007/s00396-020-04723-3) contains supplementary material, which is available to authorized users.

We present an experimental characterization of the amplification of sub-nanosecond duration laser pulses at a wavelength of 1538 nm in short custom-made Er:Yb phosphate glass fibers with different core diameters. The fibers vary in their diameter from 100 µm (highly multi-mode) down to 12 µm (single-mode). The peak power, energy per pulse, and spectral shape of the amplified signal are presented. With our input pulses, the measurements show that the large core diameter fibers do not increase the amplification of the 1538 nm signal. We believe this is due to the high re-absorption of the E r 3 + ions in the phosphate fiber. The optimal fiber geometry was found to have a core diameter of 20 µm with a length of 14 cm. The maximum peak power is 8.25 kW, corresponding to a net gain of 10.9 dB, with a pulse duration of 0.7 ns and a repetition rate of 40 kHz.

This paper reports the results of the designing, manufacturing and characterization of a jewel obtained by means of coupling the dogmas of industrial design to the analytical engineering approach. The key role in the design of the jewel was played by an in-house synthesized Neodymium (Nd)-doped phosphate glass, selected due to its easy handling and capability to change color according to the incident light wavelength. The glass core was covered by a metal alloy to mitigate its relatively high fragility and sensitivity to thermal shock and, at the same time, to highlight and preserve its beauty. The selection of the proper metal alloy, having thermo-mechanical properties compatible with those exhibited by the glass, was carried out by means of Ashby&rsquo, s maps, a powerful tool commonly adopted in the field of industrial design.

This Conference Presentation, “Bioresorbable phosphate glass microstructured optical fiber for simultaneous light and drug delivery,” was recorded for the SPIE Photonics Europe 2020 Digital Forum.

The well-known enhancement effect of surface-enhanced Raman spectroscopy (SERS) is associated with the presence of metallic nanostructures at the substrate surface. Different bottom-up and top-down processes have been proposed to impart the substrate with such a nanostructured layer. The former approaches are low cost but may suffer from reusability and stability. The latter strategies are expensive, time consuming and require special equipment that complicate the fabrication process. Here, we present the possibility to obtain stable and reusable SERS substrates by a low-cost silver-sodium ion-exchange process in soda-lime glass microrods. The microrods were obtained by cutting the tip of the ion-exchanged soda-lime fiber, resulting in disks of about few millimeters in length and one hundred microns in diameter. A thermal annealing post-process was applied to trigger the reduction of Ag+ ions into nanoparticles (AgNPs) within the ion-exchanged glass microrods. Afterwards, ion-exchange and thermal treatments were carefully tuned to assure the presence of silver NPs exposed on the surface of the microrods, without using any chemical etching. An AFM analysis confirmed the presence of AgNPs with size of tens of nm on the surface of the fiber probe. A SERS affinity bioassay was developed on the probe with the final aim of detecting microRNA fragments acting as biomarkers of different diseases. Specifically a DNA hybridization assay was built up by anchoring a molecular beacon containing a Raman tag on the Ag surface via thiol chemistry. Initial SERS experiments confirmed the presence of the beacon on the NPs embedded on the microrods surface, as monitored by detecting main spectral bands ascribed to the oligonucleotide chain. Finally, the ability of the platform to interact with the target microRNA sequence was assessed. The analysis was repeated on a number of miRNA sequences differing from the target to evaluate the specificity of the proposed assay.

The steps toward the fabrication of directly-extruded microstructured fibre preforms made of a bioresorbable phosphate glass are herein presented. Microstructured fibres show a wide range of applications, i.e. photonic crystal fibres, large mode area fibres, hollow gas/liquid sensors, etc. Nevertheless, the fabrication of bioresorbable microstructured fibres has not been feasible so far due to a lack of bioresorbable transparent glass and more flexible fibre preform fabrication techniques. A custom developed calcium-phosphate glass has been designed and carefully prepared in our laboratory to be dissolvable in a biological fluid while being optically transparent and suitable for both preform extrusion and fibre drawing. This glass has been characterised both in terms of mechanical and optical properties as well as for dissolution in aqueous medium. Furthermore, the proposed glass is thermally stable, i.e. can be processed both in the extruder and in the drawing tower. Several extrusion experiments have been carried out with different glass preforms’ shapes. Analyses of these preforms by means of Optical Profilometry and Atomic Force Microscopy have been carried out to assess the roughness of the surface of the extrudate. To support the production of an optimized die for the preform extrusion, a simplified laminar flow model simulation has been employed. This model is intended as a tool for a fast and reliable way to catch the complex behaviour of glass flow during each extrusion and can be regarded as an effective design guide for the dies to fulfil specific needs for preform fabrication. After die optimisation, extrusion of a capillary was realised, and a stacking of extruded tubes was drawn to produce a microstructured optical fibre made of bioresorbable phosphate glass. The combination of bioresorbability and fibre microstructure, show a promising pathway toward a new generation of implantable biomedical devices.

High-power, single-frequency, pulsed fiber amplifiers are required in light detection and ranging, coherent laser detection, and remote sensing applications to reach long range within a short acquisition time. However, the power-scaling of these amplifiers is limited by nonlinearities generated in the optical fibers, in particular by stimulated Brillouin scattering (SBS). In this regard, the use of multicomponent phosphate glasses maximizes the energy extraction and minimizes nonlinearities. Here, we present the development of a single-stage, hybrid, pulsed fiber amplifier using a custom-made multicomponent Yb-doped phosphate fiber. The performance of the phosphate fiber was compared to a commercial Yb-doped silica fiber. While the latter showed SBS limitation at nearly 6.5 kW for 40 cm length, the maximum achieved output peak power for the multicomponent Yb-doped phosphate fiber was 11.7 kW for 9 ns pulses using only 20 cm with no sign of SBS.

We report on the design and development of microstructured phosphate glass optical fibers for minimally invasive diagnosis and therapy. We discuss preliminary results of fiber drawing and characterization.

Purpose In this process the electrical contact is brought to the backside of a standard silicon wafer. The details of the entire process are disclosed, from the photolithography processes to the electrodepositing step, and a model for electrical contact was designed. Design/methodology/approach The localized Cu growth of high aspect ratio (AR) microstructures was obtained through an SU-8 photolithography by exploiting the optimal adhesion on the silicon surface and the possibility of generating thick layers with a single spun process Findings The experimental results showed an unexpected behaviour that is theoretically explained in detail considering the energy band theory. The obtained geometries showed a remarkable 6:1 AR without any adhesion problem. The non-invasive front-side manipulation represents a noteworthy improvement and simplification for the design of a multi-step production process. Originality/value An alternative technological approach, called back plate electroplating, has been carried out to obtain Cu growth on the front side of a standard n-type Si wafer through a back side electrical contact. This technique was then applied to fabricate a master for hot-embossing in a LIGA (Lithographie, Galvanoformung, Abformung)-like process flow. For this purpose, an SU-8 thick mask on a standard n-doped wafer was used. Finally, by using this process, it was possible to obtain high AR Cu geometries, avoiding any complex designing and patterning of the contacts on the front side and thus ensuring good adhesion of the SU-8.

Natural cellulose fibres are proposed as promising components for bioderived photoanodes and polymer electrolytes in dye-sensitized solar cells (DSSCs). In particular, TiO2-laden paper foils, prepared by simple papermaking, can be applied to several substrates (conductive glass or plastics) instead of the high-temperature sintered traditional commercial pastes. In addition, nanoscale microfibrillated cellulose is used as reinforcing filler in acrylate/methacrylate-based thermo-set polymer electrolyte membranes prepared by means of fast, low-cost and green UV-induced free-radical photopolymerization. The laboratory-scale quasi-solid state paper-DSSCs assembled with cellulose-based electrodes and electrolytes guarantee sunlight conversion efficiencies as high as 3.55 and 5.20% at simulated light intensities of 1 and 0.2 sun, respectively, along with an excellent efficiency retention of 96% after 1000 h of accelerated aging test. The simple, low cost and green approach here specifically developed opens up intriguing prospects in the design of bio-inspired energy conversion devices showing high performance, outstanding durability and truly sustainable characteristics.

Sodium potassium niobate (KNN) (K0.5Na0.5NbO3) nanopowder with a mean particle size of about 20 - 30 nm was synthesized by wet chemical route using Nb2O5 as Nb source. A solution of K, Na and Nb cations was prepared, which resulted in a clear gel after the thermal treatment. Phase analysis, microstructure and morphology of the powder were determined by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscopy (FESEM). The obtained gel was first analyzed by Thermo Gravimetric Analyzer (TGA) and Differential Scanning Calorimetry (DSC), and then calcined at different temperatures of 400℃, 500℃, 600℃ and 700℃. The X-Ray Diffraction (XRD) patterns of the synthesized samples confirmed the formation of the orthorhombic crystal phase of K0.5Na0.5NbO3 at 500?C, a temperature significantly lower than that typically used in the conventional mixed oxide route. The process developed in this work is convenient to realize the mass production of KNN nanopowders at low cost and suitable for various industrial applications.

Rare earth doped phosphate glasses are attractive materials for the engineering of photonic devices, due to their easy processing, good thermal stability, excellent optical properties and high rare-earth ions solubility [1]. Besides, phosphate glasses with a P 2 O 5 content of 50 mol% have been shown to be suitable for fiber drawing. It is well known that if the rare-earth ions are located in crystalline phase of desired nature and structure, the spectroscopic properties of the glasses can be enhanced [2]. Therefore, efforts have been focused on the development of new glass-ceramics (GCS) obtained from the heat treatment of glasses, as these engineered materials possess some of the glass properties (large flexibility of composition and geometry) but also some advantages of the RE-doped single crystals (high absorption and emission as well as long lifetimes).

The use of bioresorbable fibers represents an innovative way to build optical implantable devices and to look inside the body. Recently, a new kind of bioresorbable fibers, based on calcium-phosphate glasses, has been introduced by some of us. They show a good biocompatibility and improved attenuation loss coefficient with respect to other bioresorbable fibers. In this work, we used those fibers to explore their suitability in diffuse optics. Indeed, the time-domain technique is a non-invasive methodology which allows to have an absolute estimate of the absorption and reduced scattering spectra of the diffusive medium. It allows to bring information about concentration of chemical components (water, oxyand deoxy-hemoglobin), thus conveying information about the functional status and/or the scattering properties (changes in tissue microstructure, edema). Such information can then be related to the tissue regeneration, healing process, or to a harmful evolution. This makes the time domain optical spectroscopy coupled to bioresorbable fibers a good candidate for future medical devices. Here we demonstrate the suitability of these fibers for diffuse optics by means of standardized tests and then we use them for a proof-of-principle measurement on ex-vivo chicken breast, obtaining results comparable with standard fibers. Thanks to the encouraging results, we are working on a system based on a single fiber (serving as both injection and collection fiber) to go closer to a single interstitial fiber which can lessen the effect of the implant.

The improvement of neutron imaging towards and beyond the microscale is a well-documented need for the iterative characterization and modeling of numerous microstructured X-ray opaque materials. This work presents the recent progress in evaluating a SCIntillating FIber (SCIFI) proof-of-concept towards micron-level thermal neutron radiography. These SCIFIs are composed of 6Li-enriched silicate glass cores doped with a Ce activator. The cores possess ∼8.5 μm diameters and ∼10 μm pitch following fiber drawing with a cladding glass into an all-solid multicore fiber. A polished 5 mm × 5 mm array of 100 microstructured multicore SCIFI pixels was fabricated into a 1 mm thick faceplate. The neutron efficiency and light yield of the faceplate are characterized as functions of the 7.38 weight percent of Li2O, thickness, and the 70% active volume. It was determined that approximately 39% of a thermal neutron ( $\text{2 }$ A) beam can be absorbed by the faceplate. The $^6{\rm{Li}}({n,\; \alpha })t$ reaction is estimated to produce 7,700 ± 1,000 scintillation photons per event, referencing light collection from 241Am irradiation of the faceplate. Simulations suggest that on average 17.5 ± 1.4% of these photons will be transported to an end of the fiber array for a thermal beam, with at least 7.2% of that total scintillation light being confined into the fiber cores in which it originated. The SCIFI faceplate was integrated into the Neutron Microscope (NM) at the Pulse OverLap DIffractometer (POLDI) beamline located at the Paul Scherrer Institut to image a Siemens star test object. Processed neutron radiographs acquired with the proof-of-concept faceplate resolved features at a state-of-the-art resolution of 16.1 ± 0.5 μm. The potential for even high resolution designs having smaller pitch or different cladding material is discussed.

We report on the realization of different types of optical sensors in a bioresorbable phosphate glass optical fiber using a femtosecond laser operating at 517 nm. We inscribed fiber Bragg grating-based optical filters such as uniform Bragg gratings, chirped gratings, and Fabry-Perot cavities, using the plane-by-plane direct write inscription. The gratings were characterized in reflection and tested as sensors for temperature and relative humidity. We studied the stability and resilience of the gratings when inserted in high humidity environments (>95%) for 52 h and observed the evolution of the grating characteristics during this period.

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Calcium-phosphate glass optical fiber and capillaries (with composition identical to the core and the cladding of the fiber) were fabricated and subjected to mechanical characterization. Tensile tests were carried out to determine the strength distribution, the fatigue behavior and the elastic modulus of fibers and capillaries. The tests were performed without the application of any coating, in order to assess the behavior in bare conditions, just like in the provisional application as bio-resorbable elements. Strength ranging from 200 to 350 MPa was measured for both fiber and capillaries, the Weibull's modulus being around 3 to 6, thus revealing quite scattered distributions associated to the presence of variable surface flaws. The elastic modulus of the two glasses was shown to depend on the specific composition, the presence of MgO being responsible for a stiffer material. An evident sub-critical crack growth was also pointed out in the presence of water.

The effect of the incorporation of Er2O3-doped particles on the structural and luminescence properties of phosphate glasses was investigated. A series of different Er2O3-doped TiO2, ZnO, and ZrO2 microparticles was synthesized using soft chemistry and then added into various phosphate glasses after the melting at a lower temperature than the melting temperature. The compositional, morphological, and structural analyses of the particles-containing glasses were performed using elemental mapping by field emission-scanning electron microscopy (FE-SEM) with energy dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD). Additionally, the luminescence spectra and the lifetime values were measured to study the influence of the particles incorporation on the spectroscopic properties of the glasses. From the spectroscopic properties of the glasses with the composition 50P2O5-40SrO-10Na2O, a large amount of the Er2O3-doped particles is thought to dissolve during the glass melting. Conversely, the particles were found to survive in glasses with a composition 90NaPO3-(10 &minus, x)Na2O-xNaF (with x = 0 and 10 mol %) due to their lower processing temperature, thus clearly showing that the direct doping method is a promising technique for the development of new active glasses.

Optical fibers have recently attracted a noticeable interest for biomedical applications because they provide a minimally invasive method for in vivo sensing, imaging techniques, deep-tissue photodynamic therapy or optogenetics. The silica optical fibers are the most commonly used because they offer excellent optical properties, and they are readily available at a reasonable price. The fused silica is a biocompatible material, but it is not bioresorbable so it does not decompose in the body and the fibers must be ex-planted after in vivo use and their fragments can present a considerable risk to the patient when the fiber breaks. In contrast, optical fibers made of phosphate glasses can bring many benefits because such glasses exhibit good transparency in ultraviolet-visible and near-infrared regions, and their solubility in water can be tailored by changing the chemical composition. The bioresorbability and toxicity of phosphate glass-based optical fibers were tested in vivo on male laboratory rats for the first time. The fiber was spliced together with a standard graded-index multi-mode fiber pigtail and an optical probe for in vitro pH measurement was prepared by the immobilization of a fluorescent dye on the fiber tip by a sol-gel method to demonstrate applicability and compatibility of the fiber with common fiber optics.

In this work, the spectroscopy of Er3+ and Nd3+ doped Se-GLS glasses was studied. A structural comparison between doped and non-doped samples was done to assess the differences between the glasses. For this comparison, Raman spectroscopy and thermal analysis were employed. The spectral properties of the samples were studied in order to identify the mechanisms responsible for quenching the fluorescence lifetime of the dopants. In particular, cross-relaxation and concentration quenching were observed in Nd3+ doped samples, whilst co-operative upconversion, radiation trapping and concentration quenching were observed in Er3+ doped samples. The results obtained demonstrated the fundamental role of the phonon energy in the mechanism of fluorescence. The low phonon energy of chalcogenides decreased the rate of non-radiative processes promoting co-operative upconversion. This effect could be exploited to design new lasers and sensitizers for solar energy harvesters.

Optical fibers have been employed for several years in biomedicine and mainly used for light delivery and collection with high efficiency and selectivity. So far most of the research effort has been devoted to the optical configurations and the functions of the fibers rather than on the materials employed. Indeed, this aspect has been mainly considered to assure biocompatibility with tissues and non-toxic behavior limiting the choice mostly to silicate fibers. We report on the recent advances in engineering inorganic glass optical and hollow fibers fabricated with optical glasses which are also resorbable in body fluids. Suitable phosphate glass compositions were designed to combine resorbability and optical transparency. Glasses were fabricated by melt-quenching inside a chamber furnace under a flux of dried air and cast into preheated brass molds. The fibers were obtained by preform drawing, with the core rod fabricated by melt quenching whilst the cladding tube by rotational casting. Extrusion techniques were also applied to obtain more complex cross sections with increased functionalities. Glasses and fibers were characterized in their physical and optical properties. The materials showed high stability toward crystallization and a wide optical transmission window, ranging from the ultraviolet to the near infrared wavelength regions. Hollow fibers were employed to demonstrate multifunctional fiber probes, able to provide drug delivery and light excitation in the prospect of developing resorbable endoscopes for intravital monitoring and therapy, such as photodynamic therapy. Optimization of drug delivery was carried out using functionalization procedures on the surface of both bulk glasses and hollow fibers, aiming to modify the release kinetics: a silanization protocol was developed and successfully tested using different organic compounds. The modification of the surface roughness was monitored using atomic force microscopy, while surface energy changes verified using contact angle measurements. The possibility of performing drug excitation was assessed by guiding light through the capillary using optical beams produced by different wavelength sources covering the visible spectrum. Finally, mechanical characterization of the prepared optical fibers and hollow fibers was carried out to measure the elastic moduli, the tensile strength and the minimum radius of curvature attainable. The overall results allowed to demonstrate the reliability of the proposed optical fibers and hollow fibers for biomedical applications.

We report on the employment of a biodegradable phosphate-based optical fiber as a pH sensing probe in physiological environment. The phosphate-based optical fiber preform was fabricated by the rod-in-tube technique. The fiber biodegradability was first tested in-vitro and then its biodegradability and toxicity were tested in-vivo. Optical probes for pH sensing were prepared by the immobilization of a fluorescent dye on the fiber tip by a sol-gel method. The fluorescence response of the pH-sensor was measured as a ratio of the emission intensities at the excitation wavelengths of 405 and 450 nm.

Titania particles doped with various concentrations of Erbium were synthesized by the sol-gel method followed by different heat treatments. The shape and the grain growth of the particles were noticeably affected by the concentration of Erbium and the heat treatment conditions. An infrared emission at 1530 nm, as well as green and red up-conversion emissions at 550 and 670 nm, were observed under excitation at 976 nm from all of the synthesized particles. The emission spectra and lifetime values appeared to be strongly influenced by the presence of the different crystalline phases. This work presents important guidelines for the synthesis of functional Er3+ -doped titania particles with controlled and tailored spectroscopic properties for photonic applications. publishedVersion

Ion exchange in silver nitrate is a well-established technique for modifying the chemical-physical properties of the glass materials and is widely used in the fields of Integrated Optics (IO) and, more recently, in Plasmonics due to the possibility to induce the formation of silver nanoparticles in the glass matrix by an ad-hoc thermal post-process. Here we report the application of this technology for the realization of SERS planar substrates in commercial soda-lime glasses. This study is preparatory for the development of a glass optical fibre probe, treated by ion-exchange, for SERS applications. The main results obtained on planar samples as well as the preliminary ones on the glass optical fibre will be presented.

Thanks to its very high solubility of laser-active rare earth ions and outstanding thermo-mechanical properties, phosphate glass host represents a genuine alternative to the more traditional and employed silica glass platform to develop compact active devices, such as lasers and amplifiers. In particular, multicomponent phosphate glasses can withstand up to 1021 rare earth ions/cm3, typically about 50 times more than the silica glass matrix, without showing clustering effects.In this work we will report the ongoing activities and the recent results obtained by our research group on the design, processing and characterization of novel Er-, Nd- and Yb-doped custom phosphate glasses to be used as active medium for compact laser systems and optical amplifiers.

UV-Vis spectroscopic measurements have been performed on Dye-Sensitized Solar Cell (DSSC) photoanodes at different dye impregnation times ranging from few minutes to 24 hours. In addition to the traditional absorbance experiments, based on diffuse and specular reflectance of dye impregnated thin films and on the desorption of dye molecules from the photoanodes by means of a basic solution, an alternative in-situ solution depletion measurement, which enables fast and continuous evaluation of dye uptake, has been employed. Two different nanostructured semiconducting oxide films (mesoporous TiO2 and sponge-like ZnO) and two different dyes, the traditional Ruthenizer 535-bisTBA (N719) and a newly introduced metal-free organic dye based on a hemi-squaraine molecule (CT1), have been analyzed. DSSCs have been fabricated with the dye-impregnated photoanodes using a customized microfluidic architecture. The dye adsorption results are discussed and correlated to the obtained DSSC electrical performances such as photovoltaic conversion efficiencies and Incident Photon-to-electron Conversion Efficiency (IPCE) spectra. It is shown that simple UV-Vis measurements can give useful insights on the dye adsorption mechanisms and on the evaluation of the optimal impregnation times.

In this invited proceeding, we report our latest results on the development of Er3+ doped phosphate glass-ceramics. Those new glass-ceramics were processed using different techniques, such as direct doping of particles into the glass melt and glass-ceramics methods. First, we explain the challenges to balance the survival and dispersion of Er3+ doped particles when preparing phosphate glass-ceramics using the direct doping of particles. Then, we discuss the impact of the glass crystallization on the luminescence properties of Er3+ ions.

Er-doped phosphate glasses were fabricated by melt-quenching technique. The changes in their thermal, structural and luminescence properties with the addition of Al2O3, TiO2 or ZnO were studied. Physical and thermal properties were investigated through density measurement and differential thermal analysis. Structural characterization was performed using the Raman and Infrared spectroscopy. In order to study the influence of the composition on the luminescence properties of the glasses, the refractive index, the luminescence spectra and the lifetime values were measured. The results show that with the addition of Al2O3 and TiO2 the phosphate network becomes more connected increasing the glass transition temperature, whereas the addition of ZnO does not show significant changes in the optical, thermal and structural properties but it leads to a larger emission cross-section at 1540 nm as compared to the other glasses. As the site of the Er3+ is not strongly affected by the change in the glass composition, we think that the emission properties of the glasses depend on the glass structure connectivity, which has an impact on the Er3+ ions solubility., 32 pages, 9 figures, 1 table

We show for the first time the aptness of Calcium Phosphate Glass-based bioresorbable fibers for time-domain diffuse optics using tests described by a standardized protocol and we also present a spectroscopic measurement on a chicken breast.

We report on the fabrication and characterization of two Nd-doped active glasses and two compatible cladding compositions. The materials were synthesized to be compatible in terms of thermal expansion and characteristic temperatures. The glass system with higher refractive index and absorption cross-section was selected for the fabrication of a core/cladding cane with a diameter of 800 μm. Laser experiments, performed on a 60 mm-long cane, show laser emission at 1054 nm with output power higher than 2 W and efficiency above 40%. These values, obtained on a very simple geometry, are promising for the development of short-length cane lasers and amplifiers for emission in the 1 μm region.

Phosphate glasses (PGs) are promising host materials for the development of compact fiber amplifiers and lasers thanks to their good chemical durability, easy processing, outstanding optical properties, no clustering effect and very high solubility of rare-earth (RE) ions. Furthermore, some particular calcium-phosphate glasses exhibit unique dissolution properties in aqueous media with degradation rates that can be tailored by properly designing the glass composition. This feature makes them attractive biomaterials and allows the engineering of novel biomedical devices for deep-tissue diagnosis and therapy. In this work we will report the ongoing activities and the recent results obtained by our research group on the design, processing and characterization of novel custom phosphate glasses for both photonic and biomedical applications.

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al2O3, TiO2, and ZnO was investigated. The morphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO3)2 crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er3+ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al2O3, TiO2, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er3+ ions are incorporated in the precipitated crystals only in this glass ceramic. publishedVersion

In this paper, an innovative process flow developed to improve the thermal resistance of power ICs was presented. In this field, one of the major device failure mechanisms is related to the high temperatures reached during the working cycles due to the extremely critical electrical current densities. Therefore, heat transfer and dissipation are crucial aspects that need continuous improvements. Usual approaches to face this issue deal with package heat sinks design, solder selection, and wafer thinning. In this paper, a novel technological approach was settled, in which heat sinks microstructures were successfully integrated at wafer level stage on standard p-i-n diodes. To this aim, the bulk Si on the backside was partially replaced with Cu, a material characterized by a higher thermal conductivity material. Moreover, the well microstructures filled by Cu provide the advantage of wafer self-support, without requiring dedicated and more expensive thinning and handling technologies. An extensive characterization of the final devices was also carried out to evaluate the process and the thermal and electrical improvements. Finally, a failure analysis on selected devices was performed to identify any critical issue with the standard packaging process.

Upcoming medical procedures, such as photodynamic therapy or photochemical tissue bonding, require the local delivery of light and photosensitive dyes in selected deep tissues of the body. To achieve this purpose, it is essential to understand the dye/surface interaction of the materials involved. This work explores the employment of resorbable hollow glass fibers as controlled drug delivery systems and characterizes the release kinetics of four drugs with different chemical behaviors. The designed glass results to be optically transparent, biodegradable and biocompatible. The drugs were chosen in order to understand the interaction mechanism of different chemical species with the glass surface and to assess possible reactions. The results show that all drugs can be delivered, but ionized species tend to be withheld more than neutral molecules, suggesting the occurrence of hydrogen bonding and electrostatic interaction with the hydrophilic glass surface.

A hollow bioresorbable phosphate glass fiber was developed and used for drug and light delivery. The interaction between organic molecules and the fiber’s internal surface was studied. Promising results for the release of Rose Bengal were obtained.