Giancarlo Battaglin

Silver nanocrystals in silica by sol-gel processing

Abstract Silver nanocrystal doped silica films were prepared by the sol-gel process. The sol was prepared from 1:0.12:12:0.2:6:7 molar ratios of Si(OC2H5)4:AgNO3:H2O:HNO3:C3nH7OH:C4iH9OH. The glassy, highly transparent film with high dopant concentration (silver/silicon atomic ratio = 0.12) was successfully prepared by the dip-coating method. After drying in air at 60°C for 30 min, samples were heat-treated, in air, at 300, 350, 400, 450, 500 and 550°C using 30–100 min soaking periods for each step in a cumulative heating procedure. Measurements on the films were made by ultraviolet-visible and infrared spectroscopy, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry and transmission electron microscopy. Mechanisms of silver colloid formation in the densified silica matrix with respect to the thermal treatment are discussed. To understand the formation of silver nanocrystals from the silver silicate network, the corresponding doped bulk gel samples were analyzed by X-ray diffraction and differential scanning calorimetry.

Formation of copper and silver nanometer dimension clusters in silica by the sol‐gel process

Ag and Cu (pure and/or mixture) nanoclusters doped silica films were prepared by the sol‐gel process. In the case of Ag and Cu codoped silica films, Cu/Ag molar ratio was 1, 2, and 3 at constant (Ag+Cu)/SiO2 molar ratio of 0.175. Separated Ag and Cu nanoclusters are formed in the silica matrix. The size of the clusters and their distribution are dependent on the film composition. Optical absorption was measured from 185 to 800 nm. Intensity‐dependent nonlinear refractive index was measured for pure Cu and Ag–Cu (1:1 molar ratio) samples using z‐scan technique in the wavelength range from 570 to 596 nm. The measured nonlinear refractive index is of the order of 10−13 m2/W at a pulse repetition rate of 15.2 MHz.

Copper in glazes of Renaissance luster pottery: Nanoparticles, ions, and local environment

Following the recent finding that luster decorations in glazes of historical pottery consist of copper and silver nanoparticles dispersed in a glassy medium, the glaze in-depth composition and distribution of copper nanoparticles, copper ions, and their local environment have been studied in original samples of gold and red luster. The study has been fully carried out by nondestructive techniques such as Rutherford backscattering spectrometry, ultraviolet and visible spectroscopy, x-ray fluorescence, and extended x-ray absorption fine structure (EXAFS). Elemental analyses indicate that gold decorations are characterized by silver and copper, while red decorations by copper only. The color is determined mainly by metal nanoparticles. Specifically, silver nanoparticles determine the gold color, while the red color is determined by nanoparticles of copper. EXAFS measurements, carried out at the Cu K edge, indicate that in both gold and red luster copper is mostly the oxidized form (Cu+ and Cu2+) with a large...

Peculiarities and application perspectives of metal-ion implants in glasses

Abstract Ion implantation in insulators causes modifications in the refractive index as a result of radiation damage, phase separation, or compound formation. As a consequence, light waveguides may be formed with interesting applications in the field of optoelectronics. recently implantation of metals ions (e.g. silver, copper, gold, lead, etc.) showed the possibility of small radii colloidal particles formation in a thin surface layer of the glass substrate. These particles exhibit an electron plasmon resonance which depends on the optical constants of the implanted metal and on the refractive index of the glass host. The non-linear optical properties of such colloids, in particular the enhancement of optical Kerr susceptibility, suggest that the ion implantation technique may play an important role for the production of all-optical switching devices. In this paper an analysis of the state-of-the-art of the research in this field will be presented in the framework of ion implantation in glass physics and chemistry.

Microstructural and optical properties of sol-gel silica-titania waveguides

Abstract Two micron silica-titania coatings made by single step sol-gel dip-coating were prepared as planar waveguides. Acid catalyzed solutions of methyltriethoxysilane (MTES) mixed with tetraethoxysilane (TEOS) and tetrabutoxytitanate were used as precursors. Purely inorganic and crackfree silica-titania coatings were obtained after annealing at 500°C. The waveguides had propagation losses, 0.3 dB/cm, of the same order as thin silica-titania films prepared without MTES. Films were studied by infrared spectroscopy. Rutherford backscattering spectrometry, nuclear reactions analysis and elastic recoil detection analysis. The waveguide structural composition after annealing at 500°C was found to be similar to MTES and TEOS derived silica-titania coatings. The waveguides were characterized by measuring refractive index, porosity and shrinkage, with thermal treatment. The MTES derived films showed a higher shrinkage during annealing but the same refractive index and porosity as the TEOS derived waveguides.

Optical and surface properties of inorganic and hybrid organic-inorganic silica-titania sol-gel planar waveguides

Inorganic and hybrid organic–inorganic silica (SiO2)–titania (TiO2) planar waveguides, with a relative molar composition 70–30, have been fabricated by sol–gel dip-coating. The composition and the density of the film samples have been measured by Rutherford backscattering spectrometry, nuclear reaction analysis and elastic recoil detection analysis. The measured compositions have been found to agree with the nominal composition of the sols. The film density of the inorganic samples increased with the firing temperature in the range 1.80–2.58. A root mean square roughness (rms) <1 nm was measured on the surface of the samples by atomic force microscopy. A refractive index in the range 1.61–1.54 was measured (λ=632.8 nm). The inorganic waveguides had smaller losses (∼0.3 dB cm−1) compared to the hybrid waveguides (∼1 dB cm−1).

Interaction of high‐power laser light with silver nanocluster composite glasses

The size and size distribution of silver nanoclusters embedded in soda‐lime glasses (formed by ion irradiation of Ag+–Na+ ion‐exchanged waveguides) has been modified by high‐power laser irradiation. Optical transmittance in the visible range is found to increase above the energy threshold E*=0.3±0.1 J/cm2 for λ=532 nm and E*=5±1 J/cm2 for λ=1064 nm for pulse lengths of about 10 ns. Cluster size reduction has been observed. Small radii silver nanoclusters are also formed after laser irradiation of ion‐exchanged waveguides. The optical response of the composites has been determined by optical absorption spectroscopy. Transmission electron microscopy, x‐ray photoelectron and Auger electron spectroscopies, and Rutherford backscattering spectrometry have been used to characterize the composites.

Z-scan study on the nonlinear refractive index of copper nanocluster composite silica glass

We used the Z-scan technique for measuring the nonlinear refractive index n2 of a thin composite film formed by copper nanoparticles embedded in silica glass. By varying the number of pulses of the laser shot, we evidenced heating effects induced by the laser during measurements. We were able to estimate the nonthermal refractive-index value, n2=(3.0±0.3)×10−12 cm2/W.

Annealing behavior of silver, copper, and silver–copper nanoclusters in a silica matrix synthesized by the sol‐gel technique

Silver, copper, and mixed silver–copper nanocluster‐doped silica thin layers were prepared by the sol‐gel process. Samples were heat treated in different annealing atmospheres (air, argon, or 5%H2–95%N2) in the temperature range 500–1100 °C. Specimens were characterized by optical absorption spectroscopy, Rutherford backscattering spectrometry, x‐ray diffraction, and transmission electron microscopy. Cluster growth and dissolution, as well as migration of metal atoms towards the sample surface, with a subsequent evaporation, were observed to occur at temperatures that depend on the annealing atmosphere. In the mixed silver–copper system, the formation of Ag–Cu phase‐separated clusters was observed.

Synthesis of silver clusters in silica-based glasses for optoelectronics applications

Abstract The techniques of silver–sodium ion exchange and Ag + ion implantation in glass have been successfully applied for producing silver clusters in soda-lime glass optical waveguides. Optical absorption spectroscopy, time and spectrally resolved photoluminescence, Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy and transmission electron microscopy measurements were made. Structural changes of the Ag + environment were observed in ion-exchanged samples prepared in liquids with different Ag + concentrations. Heat treatments in air and in H 2 atmospheres induced cluster formation in ion-exchanged samples through different reduction–migration mechanisms, whereas clusters formation in ion-implanted samples is related to the defect concentrations induced by the radiation damage.