Nanoparticles in amorphous oxides are a powerful tool for embedding a wide range of functions in optical glasses, which are still the best solutions in several applications in the ever growing field of photonics. However, the control of the nanoparticle size inside the host material is often a challenging task, even more challenging when detrimental effects on light transmittance have to be avoided. Here we show how the process of phase separation and subsequent nanocrystallization of a Ga-oxide phase can be controlled in germanosilicates - prototypal systems in optical telecommunications - starting from a Ga-modified glass composition designed to favour uniform liquid-liquid phase separation in the melt. Small angle neutron scattering data demonstrate that nanosized structuring occurs in the amorphous as-quenched glass and gives rise to initially smaller nanoparticles, by heating, as in a secondary phase separation. By further heating, the nanophase evolves with an increase of nanoparticle gyration radius, from a few nm to a saturation value of about 10 nm, through an initial growing process followed by an Ostwald ripening mechanism. Nanoparticles finally crystallize, as indicated by transmission electron microscopy and X-ray diffraction, as γ-Ga(2)O(3)- a metastable gallium oxide polymorph. Infrared reflectance and photoluminescence, together with the optical absorption of Ni ions used as a probe, give an indication of the underlying interrelated processes of the structural change in the glass and in the segregated phase. As a result, our data give for the first time a rationale for designing Ga-modified germanosilicates at the nanoscale, with the perspective of a detailed nanostructuring control.
Plasmon resonance of gold nanoparticles is responsible of the electromagnetic (EM) Surface Enhanced Raman Scattering (SERS) effect. Interaction of an amorphous matrix with a SERS substrate was studied. Thin films with different thickness of amorphous TiO2 coated on a Klarite® substrate show a 100 times enhancement of the Raman signal. Distance dependence of the SERS interaction was shown to be less than 60nm.
In order to improve the efficiency of Raman Amplifiers, the Surface Enhanced Raman Scattering (SERS) effect of an amorphous matrix of TiO2 was studied. First, optimisation of the amorphous layer quality was performed by depositing thin films on glass substrates at different temperatures. Then, thin films of amorphous TiO2 were deposited on silicon commercial gold SERS substrates (Klarite®) by a dip-coating process. The SERS effect was demonstrated by the great difference of Raman intensities of the amorphous TiO2 matrix dip-coated on active and inactive parts of Klarite® substrate under 633nm and 780nm laser excitations in the tail of the Surface Plasmon Resonance band of gold nanoparticles.