Photoresists have been widely used as patterning materials for electric devices such as displays and semiconductor. Understanding pattern formation mechanism is essential for the efficient development of resist materials. In this study, we investigated the dissolution kinetics of poly(4-hydroxystyrene) (PHS) with weight-average molecular weights (Mw) of 9000-30000 and molecular weight distribution (Mw/Mn) of 1.07-1.20. The dissolution kinetics of PHS films was observed in tetramethylammonium hydroxide (TMAH) aqueous developers using a quartz crystal microbalance (QCM) method. The TMAH concentration was changed from 0 to 2.38 wt%. The obtained data were analyzed using polynomial regression to clarify the effects of Mw and Mw/Mn on the dissolution kinetics of PHS films. From the results of analysis, both dissolving and swelling behavior largely depended on Mw/Mn. Mw had a little effect on the dissolving, and however, had a large effect on the swelling in dilute TMAH aqueous solution.
In the development of highly resolving and highly sensitive resist materials, stochastic phenomena (LER and stochastic defect generation) are a critical issue. In this study, the dependence of the transient swelling layer formation of resist backbone polymer on its molecular weight and dispersion was investigated for the development of highly resolving resist materials. The dissolution kinetics was measured for different molecular weights and dispersions using quartz crystal microbalance (QCM) method. The relationship between transient swelling layer and stochastic defect formation is discussed.
We investigated the dissolution kinetics of poly(4-hydroxystyrene) (PHS) in an alkali developer with tetramethylammoniumhydroxide (TMAH). Experiments using PHS with different molecular weights and molecular weight dispersions and developer with different concentrations of TMAH led to the clarification of the dissolution behavior. Not only a change in the dissolution time but also a change in the dissolution behavior was observed upon changing the concentration of the developer. The dissolution behavior depends on an index calculated from values indicating the effects of swelling and dissolving. The dissolution occurred through the swelling of the polymer bulk and the subsequent diffusion of polymer chains into the solution bulk. The development using the alkali aqueous solution system was complex. The swelling rate should not be much larger than the dissolving rate for the development of high-resolution resists because a high swelling rate causes the generation of defects during the fabrication of fine structures.
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