Polymers bearing acidic, polar substituents protected by moieties that undergo thermolysis catalyzed by photogenerated acid have been exploited in the design of the Chemically Amplified Resists (CARs) that are used to pattern today’s semiconductor devices. These materials are very photosensitive because the deprotection reaction that is responsible for rendering the materials soluble in base has gain. That is, many bonds are broken by each photogenerated acid molecule. This design has been very successful but it has inherent limitations that are limiting its use for making the next generations of devices. The patterns have bias and edge blur that result from diffusion of the acid catalyst. We have worked for some time to design an imaging system that achieves gain without the use of a catalyst in hope of circumventing these limitations. This system design is based on a new polyester that “unzips” (depolymerizes) upon exposure to radiation. The depolymerization reaction is driven by formation of an aromatic product, toluene and a gas, carbon dioxide. Phase compatible blends of this polymer with an acid soluble matrix resin constitute a very interesting new resist formulation. The polyester inhibits the rate of dissolution of thin films of these matrix polymers in aqueous base, but the radiolysis products do not. Hence, films of the blends function as sensitive positive tone resists. A single radiochemical event results in breaking many, many covalent bonds, hence the resist system demonstrates gain. However, in principle, the new resists do not suffer from limitations that are characteristic of the CAR resists because the unzipping reaction does not require catalyst diffusion and that reaction once initiated is confined to a single chain. The synthesis of the new monomer and the polyester derived from it will be described and the results of electron beam exposure studies of the new materials will be presented.

<b>Award Address</b> (ACS Award in Polymer Chemistry sponsored by the ExxonMobil Chemical Company). Polymer chemistry for microelectronics

255th National Meeting (2018)

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Award Address (ACS Award in Polymer Chemistry sponsored by the ExxonMobil Chemical Company). Polymer chemistry for microelectronics