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We have fabricated the new type of glass (SiO2) like thin film insulator called polysilsesquioxane (POSS) and by spin coating or electro-plating technique followed by a heat-treatment between 150 and 450 °C. Our new type of material, ionic-form silsesquioxane enables us to fabricate a SiO2 film with low temperature heat-treatment of less than 200 °C compared to non-ionic soluble polysilsesquioxane. It was found that the electrical insulating of POSS film strongly depends on the heat-treatment condition, in other words, the network-formation. Finally, the POSS films were then applied to the organic field effect transistors as a gate insulator.