Short-range structure, the role of bismuth and property-structure correlations in bismuth borate glasses.

Bismuth-containing borate glasses, xBi2O3-(1 - x)B2O3, were synthesized in the broad composition range 0.20 ≤ x ≤ 0.80 by melting in Pt crucibles and splat-quenching between two metal blocks. Infrared reflectance spectra, measured in the range 30-5000 cm-1, were transformed into absorption coefficient spectra and then deconvoluted into component bands to probe the glass structure as a function of composition. Integrated intensities of bands above 800 cm-1 were used in combination with mass and charge balance equations to quantify the short-range borate structure in terms of the molar fractions X4m, X4o, X3, X2, X1 and X0 for borate units BØ4-, BØ2O23-, BØ3, BØ2O-, BØO22- and BO33-, where Ø and O- denote bridging and non-bridging oxygen atoms. Borate tetrahedral units were found to be present in both the meta-borate, BØ4-, and ortho-borate, BØ2O23-, forms with BØ4- constituting the dominating tetrahedral species for 0.20 ≤ x ≤ 0.70. The BØ2O23- units prevail at higher Bi2O3 levels (x > 0.7), and coexist with their isomeric triangular borate species BO33- (BØ2O23- ⇌ BO33-). The present IR results for the total molar fraction of borate tetrahedral units, X4 = X4m + X4o, are in very good agreement with reported NMR results for the fraction of boron atoms in four-fold coordination, N4. Besides evaluating X4m and X4o, the present work reports also for the first time the fractions of all types of triangular borate species X3-n with n = 0, 1, 2 and 3. The IR region below 550 cm-1 was found to be dominated by the Bi-O vibrational activity in coexisting ionic (160-230 cm-1) and distorted BiO6 sites (330-365 cm-1 and 475-510 cm-1), a result reflecting the dual role of Bi2O3 as glass-modifier and glass-former oxide. The latter role dominates in glasses exceeding 60 mol% Bi2O3, and is consistent with the extended glass formation in the bismuth-borate system. The structural results were used to calculate the average number of bridging B-Ø bonds per boron center, the average Bi-O and B-O single bond energy, and the atomic packing density of the studied glasses. These properties vary approximately linearly with Bi2O3 content in the three regimes 0.2 ≤ x ≤ 0.4, 0.4 < x ≤ 0.6 and 0.6 < x ≤ 0.83, and contribute collectively to the composition dependence of glass transition temperature.

Structure and optical properties of amorphous lead-germanate films developed by pulsed-laser deposition.

Lead-germanate materials are attractive systems for photonics applications. In this context, amorphous lead-germanate films were grown by pulsed-laser deposition at different substrate temperatures and oxygen pressures using a glassy target of composition 0.4PbO-0.6GeO(2). Optical and infrared measurements showed that the substrate temperature has a strong influence on the optical quality and stability of the deposited films. An accurate characterization of films was achieved by comparing experimental and simulated transmittance spectra in the infrared, and allowed to probe the structural evolution and variations in composition as a function of oxygen pressure. The results showed that the difference in reactivity of lead and germanium toward oxygen in the laser-produced plasma allows for composition adjustments in the lead-germanate films by varying the oxygen pressure in the deposition chamber.

Cation mass dependence of the nearly constant dielectric loss in alkali triborate glasses.

Electrical ac conductivity measurements on alkali triborate glasses ( M2O x 3B2O3, M = Li, Na, K, and Rb) were performed at temperatures down to 8 K and frequencies up to 1 GHz. All samples show a nearly constant dielectric loss (NCL), at the limit of high frequencies and/or low temperatures. The magnitude of the NCL is found to decrease as m(-1/3) with increasing alkali ion mass m. This quantitative result for the NCL, closely related to the mean-square displacement of ions, indicates that the origin of the NCL might be related to vibrational relaxation of the ions in the anharmonic potentials that cage them, and the cage is decaying very slowly with time.

Refractive index of crystals from transmission and reflection measurements: MgO in the far-infrared region.

In principle, the real n and imaginary k parts of the complex refractive index of a crystal can be determined by measuring, when possible, its transmission and reflection spectra. We show that it is possible to derive the frequency dependence of n and k in a simple way by using exact expressions for the interference-free transmittance and reflectance to describe low-resolution data. We also derive n and k data starting from one high-resolution spectrum. As an example, we have measured the roomtemperature transmittance and reflectance of MgO in the far-infrared region. Reliable n and k data are then obtained in the frequency region 50-250 cm(-1).