Alessandro Martucci

Sensitizing effects in Ag-Er codoped glasses for optical amplification

A set of samples co-doped with Er and Ag were prepared with a combined sol-gel and ion-exchange route. This multistep process sytnthesizes samples in which the silver atoms are dispersed in the matrix and/or aggregated in Ag multimers or nanoclusters. The samples exhibit a different photo-luminescence response depending on the sensitizing effect due to silver atoms. The spectroscopic properties were correlated with the structural properties investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction. The Er3+ excitation via energy transfer, obtained in a wide range of wavelengths, has been clearly related to the presence in the sample of Ag multimers.

Characterization of laser-written sol-gel strip waveguides

The realization of low-loss optical waveguides by the sol-gel method and the subsequent production of strip waveguides by direct laser densification are described. These waveguides have been characterized by both the optical and structural point of view, and the results are discussed.

Nucleation and Crystallization of Titania Nanoparticles in Silica Titania Planar Waveguides: a Study by Low Frequency Raman Scattering

SiO2 (1-x) TiO2 (x) waveguides, with the mole fraction x in the range 0.07 0.20 and thickness of about 0.4 μm, were deposited on silica substrates by a dip-coating technique. The thermal treatments at 700-900°C, used to fully densify the xerogels, produce nucleation of TiO2 nanocrystals even for the lowest TiO2 content. The nucleation of TiO2 nanocrystals and their growth by thermal annealing up to 1300°C were studied by waveguide Raman spectroscopy, for the SiO2 (0.8) TiO2 (0.2) composition. By increasing the annealing temperature, the Raman spectrum evolves from that typical of the silica-titania glass to that of anatase, but brookite phase is dominant at intermediate temperatures. In the low frequency region (5-50 cm) of the Raman spectra, acoustic vibrations of the nanocrystals are observed. From the measured line shapes, we can deduce the size distribution of the particles. The results are compared with those obtained from the line widths in the X-ray diffraction patterns. Nanocrystals with a mean size in the range 4-20 nm are obtained, by thermal annealing in a corresponding range of 800-1300°C.

One- and two-photon pumped soft lithographed DFB laser systems based on semiconductor core-shell quantum dots

In the last years inorganic semiconductor (particularly CdSe and CdS) quantum dots (QDs) have received great attention for their important optical properties. The possibility to tune the emission wavelength, together with their high fluorescence quantum efficiency and photostability, can be exploited in photonic and optoelectronic technological applications. The design of DFB devices, based on QDs as active optical material, leads to the realization of compact laser systems. In this work we explore the use of an inorganic/organic hybrid material composed of CdSe-ZnS semiconductor quantum dots doped into a zirconia sol-gel matrix for optical gain applications. Through the use of soft lithography on a sol-gel germania-silica hybrid, large scale distributed feedback gratings can be created. Used in conjunction with the CdSe-ZnS/ZrO2 hybrids, these gratings can act as microcavities and allow for the realization of true lasing action. The lasing properties within these devices are characterized in the femtosecond regime by both one- and two-photon excitation. From experimental data the value of the optical gain of the core-shell quantum dot samples has been estimated. Moreover, one- and two-photon lasing threshold and stability are reported.

Photoluminescence properties of organic-inorganic sol-gel films doped with semiconductor quantum dots

Hybrid organic-inorganic thin films doped with lead sulfide nanocrystallites were synthesized by a combination of colloidal chemistry and sol-gel processing. In order to study the influence on the spectroscopic properties of the crystallite surface, and hence the related defect states, PbS-doped films with different sulfur to lead ratios and different surface capping agent concentrations were fabricated. X-ray diffraction measurements showed the presence of nanoparticles with a mean diameter raging from 3 to 5 nm. The absorption spectra showed a large blue shift of the absorption edge to shorter wavelength, indicating strong quantum confinement. Strong photoluminescence emission in the near infrared was found by pumping at 514 or 532 nm. The emission intensity and its position were found to be dependent on the elaboration parameters. The film fabrication process influences only slightly the good particle size distribution of the colloidal PbS solutions. Best results were obtained for films with low sulfur to lead ratio or with high capping agent concentration.

Nonlinear characterization of PbS nanocrystals embedded in sol-gel planar waveguides

Thin silica-titania planar waveguides doped with different concentrations of lead sulfide (10 - 25 mol%) have been prepared by a sol-gel process. It consist of three steps: (a) preparation of a colloidal sol of semiconductor particles; (b) preparation of an alkoxide solution, precursor of the glass- like matrix; (c) mixing of the colloidal sol and the alkoxide solution. Films were deposited on fused silica by dipping and densified for 1 h at 300 degrees Celsius in nitrogen. The mean particle size is 3 nm and the optical absorption edge is situated around 1100 nm. The nonlinear properties have been investigated using degenerated four wave mixing (DFWM) an a nonlinear m-line technique. Different Nd:YAG lasers with pico- and nanosecond pulses at 1064 nm have been used. Depending on the PbS concentration we measured a high negative nonlinear refractive index of n2 equals -3 to -9 10-8 cm2kW for nanosecond pulses (m-lines) and -1 to -10 10-10 cm2/kW for picosecond pulses (m-lines and DFWM). The response time of the nonlinearity is below 30 ps. All observed nonlinear effects are fully reversible and we did not observe any photodarkening. Straight, monomode channel waveguides have been fabricated on theses films.

SiO2-SnO2:Er3+ transparent glass-ceramics: fabrication and photonic assessment

This work focuses on the fabrication processes and photonic assessment of SiO2-SnO2:Er3+ monoliths. To obtain the crack-free and densified system, the sol-gel derived synthesis protocols and heat-treatment processes were optimized. The absorption measurements were employed to assess the effect of the heat-treatment on the samples and specially to estimate the –OH content. The XRD patterns were used to investigate the crystallization as well as the structure of the monoliths. The emission spectra, performed at different excitation wavelengths, evidence the presence of Er3+ in the SnO2 nanocrystals and the energy transfer from SnO2 to the rare earth ions. In addition, the efficient role of SnO2 nanocrystals as Er3+ sensitizers are also experimentally confirmed in this system.

Role of Ag multimers as broadband sensitizers in Tb3+/Yb3+ co-doped glass-ceramics

Rare earth ions (RE3+) have typical photoluminescence emissions due to internal 4f orbital transitions. These emissions are narrow, with long excited state lifetimes and have the capability of spectral manipulation like wavelength shifting, down-conversion or up-conversion processes. Therefore, RE-doped materials are widely used for optical applications. However, the narrow absorption bandwidths and the small excitation cross sections for their optical transitions are major limiting factors for the full exploitation of their potentials. In this work, we show that the addition of metal nanoaggregates as broadband and efficient sensitizers can be a viable strategy to overcome these limits. Silica-zirconia (70% SiO2 – 30% ZrO2) glass-ceramic films doped by Tb3+/Yb3+ ions and an additional 5 mol.% of Na2O were prepared by sol-gel synthesis followed by a thermal annealing at 1000°C. Ag introduction was then obtained by ion-exchange in a molten salt bath and the samples were subsequently annealed in air at 380°C or 430°C to induce the migration and aggregation of the metal. The structural, compositional and optical properties of the materials were investigated, providing evidence for efficient broadband sensitization of the rare earth ions by energy transfer from Ag-dimers or multimers, which could have applications for increasing the efficiency of silicon solar cells.