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Experimental and Theoretical Study of Structure-Dielectric Property Relationships for Polysilsesquioxanes

  • Sung Mog Kim (a1), Do Y. Yoon (a1), Cattien V. Nguyen (a2), Jie Han (a3) and Richard L. Jaffe (a3)...


Structures of polysilsesquioxanes {(R- SiO1.5)n with R=H, CH3, C6H5} in spin-on thin films are investigated in relation to their dielectric properties. IR spectroscopy in combination with results from quantum chemistry calculations shows that the initial hydrido-silsesquioxane films (cured to 250 °C) exhibit more symmetric ring structures than those for methyl-silsesquioxanes. Moreover, IR spectra indicate that increasing the cure temperature above a critical value, which varies with the Si-R moiety, causes extensive three-dimensional cross-linking in silsesquioxanes via breakage of the Si-R bond and formation of networks of O-Si-O structures with a lower ring symmetry than the initial materials. Dielectric properties do not appear to vary with the structural symmetry about the O-Si-O moiety nor with the R substituents, but rather depend on the extent of three-dimensional cross-linking as seen by the loss of Si-R absorbance. Highly cross-linked silsesquioxanes show a higher dielectric value and no variation with temperature from −100 °C to 150°C range, whereas a lower value and a negative temperature dependence are seen for dielectric constants of silsesquioxane samples with little loss of Si-R absorbance.



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