Relationship between the surface free energy of underlayers and the dissolution kinetics of poly(4-hydroxystyrene) partially protected by t-butoxycarbonyl groups in tetramethylammonium hydroxide aqueous developer

In the lithography used for the high-volume production of semiconductor devices, the photoresist film becomes thin with the reduction in pattern size to prevent the pattern collapse due to the surface tension of rinsing liquids. The interfacial effect becomes strong with the reduction in photoresist film thickness. In the development process, it is of importance to clarify the relationship between the photoresist and the underlayer for fine patterning. In this study, the dissolution kinetics of poly(4-hydroxystyrene) (PHS) partially protected by t-butoxycarbonyl (t-Boc) groups in tetramethylammonium hydroxide (TMAH) aqueous solution was found to be related to the surface free energy of the underlayer. The attenuation rate of developer viscosity first decreased and then increased with the polar-to-dispersion component ratio. An inflection point with the lowest rate existed. The TMAH concentration affected not only the attenuation rate but also the ratio of polar to dispersion components at the minimum attenuation rate.