We describe two studies that examine how the enhancement and suppression of the solubility of a 193-nm positive-tone photoresist can be manipulated using crosslinking, thermal-activation and variable-temperature bakes. In our first study, we describe the development of a thin, polymeric film that can transition through three solubility regimes as a response to increasing bake temperatures: (1) low temperature, developer insoluble; (2) medium temperature, developer soluble; (3) high temperature, developer insoluble.
We describe an exploration of small molecules capable of suppressing the solubility of polymers with pendent carboxylic acid groups. We evaluate the use of small molecules such as alkyl amines, benzyl bromide, N,N’-dicyclohexylcarbodiimide (DCC) and N,N-diisopropylcarbodiimide (DIC). We have combined polymers containing carboxylic acids with these reagents and evaluated their changes in dissolution rate in n-butyl acetate and 0.26 N TMAH. We have also conducted model reactions of non-polymeric carboxylic acids in NMR tubes to help characterize the reactions occurring with polymers.
The acid-catalyzed cleavage of carbon-oxygen bonds is one of the most critical reaction occurring during image formation using chemically-amplified photoresists. Described here is an approach to modelling these important reactions using Spartan'18 software. This modelling predicts the activation energies of catalyzed and uncatalyzed C-O bond breaking reactions for over fifty acetate esters. To verify the capabilities of this modelling approach, we compared the modelled predictions of activation energies against experimental values for hydride ion affinity values for forty carbocations. Using similar modelling techniques, we predicted the activation energies of C-O bond breaking of commonly used 193-nm monomers as catalyzed by perfluorobutanesulfonic (PFBuS) acid. Additionally, we evaluated the effect of carboxylic acid size and the effect of increasing alkyl substitution on the carbocation intermediate.
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