Mechanism of amine additive in chemically amplified resist visualized by using Monte Carlo simulation

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Abstract
A novel simulator using the Monte-Carlo method, which simulates molecular-like movements and reactions in chemically amplified resist systems, has been developed in order to clarify the mechanism of amine additive. The simulation program simulates diffusion phenomena with random-walked acids and amine molecules, and reactions of deactivation (neutralization) and inhibitor cleavage in every movement of the molecules. It was found that the amine in the exposed area was rapidly deactivated, and the concentration profile of the remaining amine was rapidly changed to an inversely shaped profile of that of the acid. This means that the remaining amine prevents diffusion of acids outside the exposed area by functioning as a barrier during almost the whole period of post-exposure bake (PEB). These concentration profiles lead to an enhancement of stability of pattern sizes and reduction of edge roughness of the pattern. Environmental stability was also calculated, and amine additive was also found to prevent contamination from the environment in the initial period of the PEB.

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