Roberto Lorenzi

Fully inorganic oxide-in-oxide ultraviolet nanocrystal light emitting devices

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.

Nickel-assisted growth and selective doping of spinel-like gallium oxide nanocrystals in germano-silicate glasses for infrared broadband light emission

The target of taking advantage of the near-infrared light-emission properties of nickel ions in crystals for the design of novel broadband optical amplifiers requires the identification of suitable nanostructured glasses able to embed Ni-doped nanocrystals and to preserve the workability of a glass. Here we show that Ni doping of Li(2)O-Na(2)O-Ga(2)O(3)-GeO(2)-SiO(2) glass (with composition 7.5:2.5:20:35:35 and melting temperature 1480 °C, sensibly lower than in Ge-free silicates) enables the selective embedding of nickel ions in thermally grown nanocrystals of spinel-like gallium oxide. The analysis of transmission electron microscopy and x-ray diffraction data as a function of Ni-content (from 0.01 to 1 mol%) indicates that Ni ions promote the nanophase crystallization without affecting nanoparticle size (~6 nm) and concentration (~4 × 10(18) cm(-3)). Importantly, as shown by optical absorption spectra, all nickel ions enter into the nanophase, with a number of ions per nanocrystal that depends on the nanocrystal concentration and ranges from 1 to 10(2). Photoluminescence data indicate that fast non-radiative decay processes become relevant only at mean ion-ion distances shorter than 1.4 nm, which enables the incorporation of a few Ni ions per nanoparticle without too large a worsening of the light-emission efficiency. Indeed, at 0.1 mol% nickel, the room temperature quantum yield is 9%, with an effective bandwidth of 320 nm.

In-line absorption sensor based on coiled optical microfiber

We fabricated and tested an evanescent-wave absorption sensor consisting of an optical microfiber coil resonator embedded in fluidic channel walls. Low concentrations of flowing analyte show optical losses in agreement with a modified Beer-Lambert law. Higher concentration causes a limit value of the measured optical losses arising from adsorption mechanisms

High-energy shift of the Urbach ultraviolet absorption from attenuated dynamical disorder in fluorine modified sol-gel silica

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 8eV, with the absorption coefficient α∝exp[E∕EU(T)] showing Urbach energy values EU(T) ranging between 50 and 66meV. The comparison of EU(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.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 8eV, with the absorption coefficient α∝exp[E∕EU(T)] showing Urbach energy values EU(T) ranging between 50 and 66meV. The comparison of EU(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.

Non-aqueous sol–gel synthesis of hybrid rare-earth-doped γ-Ga2O3 nanoparticles with multiple organic–inorganic-ionic light-emission features

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.

Permanent excimer superstructures by supramolecular networking of metal quantum clusters

Long-life excimer-like structures Metal quantum clusters have ideal properties for medical applications such as imaging. The challenge is to prolong their transient properties for the fabrication of useful devices. Santiago-Gonzalez et al. arranged gold clusters in a supramolecular lattice held together by hydrogen bonding and showed that this material can be used for imaging of fibroblast cells. In the superstructure, the gold molecules can come together in the excited state as excimers and then dissociate to emit radiation. Because they are within a lattice, this behavior shows long-term stability. Furthermore, the lattice superstructure scavenges reactive oxygen species and reduces cell damage. Science, this issue p. 571 Excimer-like superstructures that emerge from hydrogen bond networking of gold clusters can scavenge reactive oxygen species. Excimers are evanescent quasi-particles that typically form during collisional intermolecular interactions and exist exclusively for their excited-state lifetime. We exploited the distinctive structure of metal quantum clusters to fabricate permanent excimer-like colloidal superstructures made of ground-state noninteracting gold cores, held together by a network of hydrogen bonds between their capping ligands. This previously unknown aggregation state of matter, studied through spectroscopic experiments and ab initio calculations, conveys the photophysics of excimers into stable nanoparticles, which overcome the intrinsic limitation of excimers in single-particle applications—that is, their nearly zero formation probability in ultra-diluted solutions. In vitro experiments demonstrate the suitability of the superstructures as nonresonant intracellular probes and further reveal their ability to scavenge reactive oxygen species, which enhances their potential as anticytotoxic agents for biomedical applications.

Broadband infrared light-emitting patterns in optical glass by laser-induced nanostructuring of NiO-doped alkali-gallium germanosilicates.

In this Letter, we show functionalization of NiO-doped 7.5Li(2)O·2.5Na(2)O·20Ga(2)O(3)·35SiO(2)·35GeO(2) glass by space-selective nanocrystallization via exposure to the focused beam of a pulsed copper vapor laser (510.6 and 578.2 nm) at temperature close to the glass transition point (570°C). Irradiated areas drastically change their color, caused by electronic transitions of Ni(2+) dopant ions, without any alteration of the optical quality. Importantly, irradiated regions acquire broadband infrared luminescence (centered at about 1400 nm and possessing 400 nm effective bandwidth) typical of Ni(2+) ions in crystalline environment, and by positive change of refractive index (more than 10(-3)). Spectroscopic and diffractometric data of the irradiated regions indeed resemble those previously observed in thermally nanocrystallized glass, with Ni(2+) ions embedded in γ-Ga(2)O(3) nanocrystals. The results demonstrate the possibility of laser writing nanocrystallized multifunction patterns in germanosilicate glasses for the fabrication of active integrated devices.

Microfluorescence Analysis of Nanostructuring Inhomogeneity in Optical Fibers with Embedded Gallium Oxide Nanocrystals

A spectroscopic protocol is proposed to implement confocal microfluorescence imaging to the analysis of microinhomogeneity in the nanocrystallization of the core of fibers belonging to a new kind of broadband fiber amplifier based on glass with embedded nanocrystals. Nanocrystallization, crucial for achieving an adequate light emission efficiency of transition metal ions in these materials, has to be as homogeneous as possible in the fiber to assure optical amplification. This requirement calls for a sensitive method for monitoring nanostructuring in oxide glasses. Here we show that mapping microfluorescence excited at 633 nm by a He-Ne laser may give a useful tool in this regard, thanks to quasi-resonant excitation of coordination defects typical of germanosilicate materials, such as nonbridging oxygens and charged Ge-O-Ge sites, whose fluorescence are shown to undergo spectral modifications when nanocrystals form into the glass. The method has been positively checked on prototypes of optical fibers--preventively characterized by means of scanning electron microscopy and energy dispersive spectroscopy--fabricated from preforms of Ni-doped Li₂O-Na₂O-Sb₂O₃-Ga₂O₃-GeO₂-SiO₂ glass in silica cladding and subjected to heat treatment to activate gallium oxide nanocrystal growth. The method indeed enables not only the mapping of the crystallization degree but also the identification of drawing-induced defects in the fiber cladding.

Spatially selective Au nanoparticle growth in laser-quality glass controlled by UV-induced phosphate-chain cross-linkage

Herein we describe how UV excitation of localized electronic states in phosphate glasses can activate structural rearrangements that influence the kinetics of Au nanoparticle (NP) thermal growth in Au-doped glass. The results suggest a novel strategy to address the problem of controlling nano-assembly processes of metal NP patterns in fully inorganic and chemically stable hard materials, such as laser-quality glasses. We show that the mechanism is promoted by opening and subsequent cross-linkage of phosphate chains under UV excitation of non-bridging groups in the amorphous network of the glass, with a consequent modification of Au diffusion and metal NP growth. Importantly, the micro-Raman mapping of the UV-induced modifications demonstrates that the process is restricted within the beam waist region of the focused UV laser beam. This fact is consistent with the need for more than one excitation event, close in time and in space, in order to promote structural cross-linkage and Au diffusion confinement. The stability of the photo-induced modifications makes it possible to design new metal patterning approaches for the fabrication of three-dimensional metal structures in laser-quality materials for high-power nonlinear applications.

Luminescence study of transition metal ions in natural magmatic and metamorphic yellow sapphires

Optical absorption and luminescence spectra of yellow corundum have been analyzed, both in magmatic and metamorphic materials, looking at the role of localized electronic transitions of transition metal ions at substituted Al sites. By the aid of energy dispersed x-ray fluorescence (EDXRF) elemental analysis and electron paramagnetic resonance (EPR) measurements, the results confirm that Fe 3+ is the dominant impurity ion. However, the results also evidence that Cr