Publications

The first vacuum-ultraviolet spectrum of a polysilylene (chain-type polysilane) with aromatic substituents is presented. Assignments of the absorption bands of the model compound poly(methylphenylsilylene) are based on previous experimental data and theoretical electronic band structure calculations for poly(alkylsilylenes) and on ultraviolet spectra of phenyl-containing monomers and polymers. Although aryl orbitals mix with the {sigma}-conjugated orbitals located along the catenated silicon backbone, some transitions are largely localized on the phenyl groups. These assignments elucidate the nature of the bonding in polysilylenes and should be useful in understanding photodegradation mechanisms and in the design of related new optical materials.

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The thermal stability of photo-imprinted Bragg gratings formed in reactive-atmosphere, RF-magnetron sputtered germanosilicate thin films was evaluated in terms of point defect modifications observed during isochronal annealing. Optical and magnetic spectroscopes were utilized to evaluate structural relaxation in these sputtered glasses on both a local and medium-range size scale. Depending upon the substrate temperature used during deposition, significant structural rearrangement was found to occur with increasing post-deposition anneal temperature to 600 C. This resulted in changes in the photobleaching response of the material itself as the identity of optically active structural defects evolved. Based on a color center model for photosensitivity in these materials and measured changes in optical absorption with annealing, the thermal stability of a photo-imprinted Bragg grating was modeled. Good qualitative agreement with experiment was observed.

Germanosilicate glasses exhibit a significant photosensitive response which has been linked to the presence of oxygen- deficient germanium point defects in the glass structure. Based on this correlation, highly photosensitive thin films have been engineered which demonstrate the largest reported ultraviolet-induced refractive index perturbations (Δn) in an as-synthesized material. Our thin-film fabrication process avoids the use of hydrogen sensitizing treatments and, thus, yields stable films which retain their predisposition for large photosensitivity for over one year of storage. Understanding the nature of the defects in such films and their relationship to charge trapping and enhanced photosensitivity is of paramount importance in designing and optimizing the materials. Toward this end, our films have been studied using electron paramagnetic resonance (EPR), capacitance-voltage, and optical bleaching and absorption spectroscopies. We find experimental evidence suggesting a model in which a change in spin state and charge state of isolated paramagnetic neutral Ge dangling bonds form either diamagnetic positively or negatively charged Ge sites which are largely responsible for the charge trapping and photosensitivity in these thin films. We present experimental data and theoretical modeling to support our defect model and to show the relevance of the work. ©2005 Copyright SPIE - The International Society for Optical Engineering.