Structure and Properties of Modified and Charge-Compensated Chalcogenide Glasses in the Na/Ba-Ga-Ge Selenide System

Chalcogenide glasses exhibit unique optical properties such as infrared transparency owing to the low-phonon energies, optical non-linearity, and photo-induced effects that have important consequences for a wide range of technological applications. However, to fully utilize these properties, it is necessary to better understand the atomic-scale structure and structure-property relationships in this important class of materials. Of particular interest in this regard are glasses in the stoichiometric system Na2Se/BaSe--Ga 2Se3--GeSe2 as they are isoelectronic with the well-studied, oxide glasses of the type M2O(M'O)--Al 2O3--SiO2 (M = alkali, M' = alkaline earth). This dissertation investigates the structure of stoichiometric Na 2Se/BaSe--Ga2Se3--GeSe2 and off-stoichiometric BaSe--Ga2Se3--GeSe 2+/-Se glasses using a combination of Fourier-transform Raman and solid state nuclear magnetic resonance (NMR) spectroscopies. The spectroscopic data is then compared to composition-dependent trends in physical properties such as density, optical band gap, glass transition temperature, and melt fragility to develop predictive structural models of the short- and intermediate-range order in the glass network. These models significantly improve our current understanding of the effects of modifier addition on the structure and properties of chalcogenide glasses, and thus enable a more efficient engineering of these highly functional materials for applications as solid electrolytes in batteries or as optical components in infrared photonics.;In general, the underlying stoichiometric Ga2Se3--GeSe 2 network consists primarily of corner-sharing (Ga/Ge)Se4 tetrahedra, where the coordination numbers of Ga, Ge, and Se are 4, 4, and 2, respectively. Some edge-sharing exists, but this configuration is relatively unstable and its concentration tends to decrease with any deviation from the GeSe2 composition. Due to the tetrahedral coordination of Ga, the initial addition of Se-deficient Ga2Se3 to GeSe 2 results in the preferential formation of Ge-Ge bonds, which are distributed such that the clustering of ethane-like (Se3)Ge-Ge(Se3) units is avoided to the maximum extent. This behavior is entirely consistent with the continuously-alloyed structural scenario of chalcogenide glasses. However, for contents of Ga2Se3 greater than about 25--30 mol%, the avoidance of Ga-Ga and mixed Ga-Ge bonds results in the appearance of three-coordinated Se as an alternate mechanism to accommodate the Se deficiency.;The addition of either Na2Se or BaSe to Ga2Se 3--GeSe2 glasses introduces an ionic bonding character to an otherwise largely covalently bonded network. As a result, the structure responds by adopting characteristics of the charge-compensated structural scenario of oxide glasses. In the stoichiometric Na2Se/BaSe--Ga 2Se3--GeSe2 glasses, the ratio of Na 2Se/BaSe:Ga2Se3 = 1 serves as a chemical threshold, where the network consists predominantly of corner-sharing (Ga/Ge)e4 tetrahedra, and the charge on the Na(Ba) cations is balanced by the GaSe4- tetrahedra. For glasses with Na 2Se/BaSe:Ga2Se3 < 1, the addition of Se-deficient Ga2Se3 induces the formation of Ge-Ge bonds. However, for glasses with Na2Se/BaSe:Ga2Se3 > 1, the addition of Na2Se/BaSe results in the formation of non-bridging Se atoms, which break up the connectivity of the glassy network. The major difference between the modifying elements Na and Ba is that the high field strength of the Ba cation induces a higher degree of chemical disorder in the glass network. This conclusion is evidenced by the presence of some Ge-Ge bonds in BaSe--Ga2Se3--GeSe2 glasses even at the chemical threshold composition of BaSe:Ga2Se3 = 1.;The structural duality of the Na2Se/BaSe--Ga2Se 3--GeSe2 system is best observed in the off-stoichiometric BaSe--Ga2Se3--GeSe2+/-Se glasses. Here, the removal of Se from a stoichiometric glass with BaSe:Ga2Se 3 > 1 results in Ge-Ge bonds, while its addition in excess of stoichiometry forms Se-Se bonds. Although such behavior is consistent with the continuously-alloyed structural model, it should be contrasted with the response of the network to the removal or addition of BaSe. In the latter case especially, the network responds with the formation of non-bridging Se atoms, which is reminiscent of the charge-compensated structural scenario.;The aforementioned structural conclusions are supported by trends in physical properties. Of all the properties measured, the glass transition temperature Tg responds most predictably to changes in glass structure in the sense that the removal of heteropolar (Ga/Ge)-Se bonds from the glassy network consistently results in a decrease in Tg. Indeed, Tg is observed to be maximized around chemical threshold compositions that are expected to have a fully-connected network of (Ga/Ge)Se¬4 tetrahedra. The formation of homopolar Ge-Ge bonds causes Tg to drop by ~40--80 °C, while the formation of Se-Se and/or non-bridging Se causes Tg to decrease by at least 120 °C.;Trends in density reflect both the packing efficiency of the structural units within the glassy network as well as the masses of the constituent elements, and are generally observed to increase or decrease monotonically. As a result, an increase in density is associated with: 1) the removal of inefficiently packed structural units such as edge-sharing tetrahedra, 2) the formation of efficiently packed units such as three-coordinated Se atoms, 3) the removal of lighter elements like Na, and 4) the addition of heavier elements like Ba.;Optical band gap is related to the bonding character within the glassy network, and tends to decrease as the bonding character becomes increasingly metallic. Therefore, a decrease in optical band gap is observed with the formation of homopolar Ge-Ge bonds when Ga2Se3 is added to GeSe2. However, the stoichiometric BaSe--Ga2Se 3--GeSe2 glasses show an anomaly in this regard because optical band gap decreases with the addition of BaSe, and consequently the removal of Ge-Ge bonds. This observation was ascribed instead to the formation of Ba-Se bonds, which are associated with a lower bandgap compared to the (Ga/Ge)-Se bonds that they replace.;Finally, there is no straightforward structural explanation for trends in fragility, because it is related to the number of structural configurations dynamically available to the supercooled liquid. In the binary Ga2Se3--GeSe2 glasses, the fragility tends to increase with the formation of homopolar Ge-Ge bonds, which is consistent with other chalcogenide systems in which fragility increases with the removal of heteropolar bonds within corner-sharing tetrahedra and pyramids. In the stoichiometric BaSe--Ga2Se3--GeSe2 glasses on the other hand, a shift in trend near the compositions where BaSe:Ga 2Se3 = 1 coincides with a structural shift between the formation of Ge-Ge bonds and Se-Se/non-bridging Se.