D. Vouagner

In situ Raman spectroscopy of pressure-induced changes in LaBGeO5 glass: hysteresis and plastic deformation

In situ micro-Raman spectroscopy was performed on lanthanum borogermanate (LBG) glasses, compressed in a diamond anvil cell at ambient temperature. Up to 5.6xa0GPa the structural changes are reversible, whereas experiments performed at 10xa0GPa and higher are characterized by hysteresis loops. A noticeable change of evolution of the main Raman band at 800xa0cm(-1) has been evidenced around 8xa0GPa. Indeed, at such a pressure, this Raman band is shifted in the opposite direction while the pressure is still increasing. This change of slopes may be the sign of a pressure-induced coordination number change. Upon decompression the Raman shift of this band follows a different path from the one during compression. When the sample is returned to ambient pressure, it shows a shifted and lightly modified Raman spectrum, suggesting that a new amorphous phase for LBG glass is reached under high pressure and still exists at atmospheric pressure. However, a comparison with LaBGeO(5) crystals with the same composition shows that this material has a full elastic behaviour in the same pressure range.

On the nature of the second-order optical nonlinearity of nanoinhomogeneous glasses in the Li2O-Nb2O5-SiO2 system

The submicroscopic structure of lithium niobium silicate glasses of the compositions 2xLiNbO3 · (1 − x)(Li2O · 2SiO2) (x = 0.40, 0.45, 0.50) and 30Li2O · 25Nb2O5 · 45SiO2 in the initial state and after heat treatment for different times at temperatures in the vicinity of the glass transition point Tg are investigated using X-ray powder diffraction, small-angle neutron scattering (SANS), synchrotron small-angle X-ray scattering (SAXS), and electron microscopy. A nanostructure with inhomogeneities ∼40 Å in size is formed in glasses at the initial stages of phase separation at temperatures in the range 600–670°C. This structure is responsible for the appearance of the second-order optical nonlinearity. The SANS, SAXS, and electron microscopic data on the inhomogeneity size are in good agreement with each other. According to the X-ray diffraction, SANS, and SAXS data, the ordering of the glass structure and the difference between the density of inhomogeneities and the density of the matrix increase in the course of heat treatment. At the initial stage of amorphous phase separation, the glass decomposes into regions enriched in SiO2 and regions with an increased content of lithium and niobium. An increase in the temperature or time of heat treatment results in the precipitation of LiNbO3 ferroelectric crystals. The results obtained allow us, for the first time, to make the inference that nanoscale changes in the glass structure lead to considerable changes (by one order of magnitude and more) in the quadratic optical nonlinearity, which can be controlled by heat treatment. The origin of the second-order optical nonlinearity is associated with both the nanosized modulations of the polarizability due to the inhomogeneous glass structure and the polarity of structural nanoinhomogeneities from which the LiNbO3 phase precipitates at the later stages of phase separation.

A-thermal elastic behavior of silicate glasses.

Depending on the composition of silicate glasses, their elastic moduli can increase or decrease as function of the temperature. Studying the Brillouin frequency shift of these glasses versus temperature allows the a-thermal composition corresponding to an intermediate glass to be determined. In an intermediate glass, the elastic moduli are independent of the temperature over a large temperature range. For sodium alumino-silicate glasses, the a-thermal composition is close to the albite glass (NaAlSi3O8). The structural origin of this property is studied by in situ high temperature Raman scattering. The structure of the intermediate albite glass and of silica are compared at different temperatures between room temperature and 600 °C. When the temperature increases, it is shown that the high frequency shift of the main band at 440u2009cm(-1) in silica is a consequence of the cristobalite-like alpha-beta transformation of 6-membered rings. This effect is stronger in silica than bond elongation (anharmonic effects). As a consequence, the elastic moduli of silica increase as the temperature increases. In the albite glass, the substitution of 25% of Si(4+) ions by Al(3+) and Na(+) ions decreases the proportion of SiO2 6-membered rings responsible for the silica anomaly. The effects of the silica anomaly balance the anharmonicity in albite glass and give rise to an intermediate a-thermal glass. Different networks, formers or modifiers, can be added to produce different a-thermal glasses with useful mechanical or chemical properties.

Surface-enhanced Raman scattering of amorphous TiO2 thin films by gold nanostructures: Revealing first layer effect with thickness variation

In this paper, amorphous titanium dioxide (TiO2) thin films have been deposited on a commercially available Klarite substrate using the sol-gel process to produce surface-enhanced Raman scattering (SERS). The substrate consists of square arrays of micrometer-sized pyramidal pits in silicon with a gold coating. Several thin TiO2 layers have been deposited on the surface to study the influence of film thickness. Ultimately, we obtained information on SERS of an amorphous TiO2 layer by gold nanostructures, whose range is less than a few nanometers. Mechanisms responsible for the enhancement are the product of concomitant chemical and electromagnetic effects with an important contribution from plasmon-induced charge transfer.

Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential int...

Structure of low-silica glasses in the K2O-Nb2O5-SiO2 system

The nanostructure and nonlinear optical properties of high-niobium glasses in the (1 − x)KNbO3-xSiO2 system with an SiO2 content x = 0.05–0.35 have been studied by small-angle neutron scattering (SANS), electron microscopy (EM), and second-optical-harmonic generation (SHG). Vitreous samples are manufactured by the methods of fast melt cooling (pressing with metal plates and quenching between rotating rolls). Glasses with x < 0.12 have been established to form a micro-inhomogeneous structure in the form of silica-enriched regions at the cooling rates used. According to SANS data, quenched glasses with x > 0.2 are homogeneous, but form a silica-enriched nanostructure after thermal treatments. At temperatures below ∼Tg + 50°C, silica-enriched regions manifest a very slight tendency to grow, whereas, according to SANS and X-ray diffraction data, their chemical composition is observed to shift appreciably towards SiO2 with thermal treatment. The obtained data on an inhomogeneous structure allows us to clarify the complicated character of the previously revealed dependence Tg(x). Nano-inhomogeneous transparent samples produce a weak SHG signal, which indicates the quasi-periodic modulation of the chemical composition and, correspondingly, polarizability, in the volume of glass. The nonlinear optical phase KNbO3 precipitates at later stages of crystallization, when a glass loses its transparency. In this case, the SHG signal is amplified by several orders of magnitude.