Silicone ionomers, germanium-containing silicones and glassy films

Carboxyl-containing polysiloxanes were synthesized and characterized. Their lanthanide ionomers including Er(III), Eu(III), Sm(III), Tb(III) and Dy(III) ionomers of copolymers of dimethylsiloxane and 3-carboxypropylmethyl-siloxane were prepared and studied spectroscopically. Near infrared and Raman spectra of the lanthanide silicone ionomers revealed excited state absorptions and fluorescence from excited states.; A new method was developed to form silica and silicates from carboxyl-containing polysiloxanes and their ionomers. The copolymers of dimethylsiloxane and 3-carboxypropylmethylsiloxane discussed in this thesis have carboxylic acid concentrations ranging from 2 to 100 mol%. The introduction of the carboxylic acid side groups into the polymers not only can increase the viscosities of the polymers so that the polymers can be suitable for spinning onto substrates, but also can change the thermal decomposition rate of the organic groups to minimize crack generation in resultant glass films. The carboxyl groups in the polysiloxanes appear to aid in attaching the polymers to the surfaces of various substrates such as silicon and silica through the formation of hydrogen bond between OH group and COOH group. Employing these characteristics and thermal oxidation reactions, silica films as thick as 2 {dollar}mu{dollar}m have been formed in air.; New methods were developed to form metal doped silicate films and patterns on substrates such as silicon or silica. The carboxylated polysiloxanes were cross-linked by ultraviolet radiation through the formation of interchain carbon carbon bonds between two methyl groups or between methyl and vinyl groups attached to silicons. The cross-linked silicone films or patterns were ion-exchanged with metal acetylacetonates or other metal compounds to form metal doped silicone films or patterns which were oxidized in air up to 600{dollar}spcirc{dollar}C to form metal doped silicate films or patterns. This provides a new way to form silicate films or patterns, especially lanthanide silicate films and patterns, for planar waveguide or other optical applications. Glasses comprising Tb(III), Er(III), Ho(III), Sm(III), Eu(III) and Nd(III) were synthesized.; Several synthetic methods were developed to form novel classes of germanium containing silicones. These include copolymeric carboxylated germanosiloxanes, germanium esters of carboxylated siloxanes, siloxane copolymers of hydrolyzed carboxylated germoxanes, and dialkylgermoxanes. Though germanium belongs to the same group as silicon, the chemistry of germanium is different from that of its analog, and the synthesis of Ge-O bond-containing compounds is difficult because the Ge-O bond strength is weak and subject to hydrolysis of water. The syntheses of compounds with Ge-O-Si bonds were carried out using two-phase reaction systems. The {dollar}sp1{dollar}H NMR spectra of the compounds enabled determination of the mole ratio of germanium to silicon and the infrared spectra demonstrated the formation of Ge-O-Si bonds.; Germanosilicate films were prepared from the germanium containing silicones through thermal hydrolysis. The infrared spectra and refractive index of the germanate silicate films were measured and showed the existence of GeO{dollar}sb2{dollar} in the xSiO{dollar}rmsb2cdot(1-x)GeOsb2{dollar} networks.; The carboxylated polysiloxanes and polygermanosiloxanes also were used to form other glassy objects, such as layers to provide for the adhesion of optical fibers to glassy or crystalline Si substrates, and to form microlenses and optical filters.