Low plasma resistance and roughness formation in an ArF photoresist are serious issues in plasma processes. To resolve these issues, we investigated several factors that affect the roughness formation and plasma resistance in an ArF photoresist. We used our neutral beam process to categorize the effects of species from the plasma on the ArF photoresist into physical bombardment, chemical reactions and ultraviolet/vacuum ultraviolet (UV/VUV) radiation. The UV/VUV radiation drastically increased the etching rates of the ArF photoresist films, and, in contrast, chemical reactions increased the formation of surface roughness. FTIR analysis indicated that the UV/VUV radiation preferentially dissociates C–H bonds in the ArF photoresist, rather than C=O bonds, because of the dissociation energies of the bonds. This indicated that the etching rates of the ArF photoresist are determined by the UV/VUV radiation because this radiation can break C–H bonds, which account for the majority of structures in the ArF photoresist. In contrast, FTIR analysis showed that chemical species such as radicals and ions were likely to react with C=O bonds, in particular C=O bonds in the lactone groups of the ArF photoresist, due to the structural and electronic effects of the lactone groups. As a result, the etching rates of the ArF photoresist can vary in different bond structures, leading to increased surface roughness in the ArF photoresist.

Low etching resistance and roughness formation of ArF photoresist during plasma etching are serious problems. We have previously found that decisive factors affecting the plasma resistance and roughness formation in an ArF photoresist are determined by ultraviolet/vacuum ultraviolet radiation and roughness formation is dominated by chemical reactions. In this paper, on the basis of our previous findings on the interaction between radiation species from plasma and ArF photoresist polymers, we investigated the polymer structural dependence for the degradation mechanism of ArF photoresist in the plasma etching processes. The etching resistance of ArF photoresist was improved by controlling the elemental ratio of oxygen atoms and ring structures in photoresist polymer. Furthermore, lactone C=O bond is found to be a key factor for roughness formation during the etching process. We have revealed the importance of the molecular structure of ArF photoresist for improving the surface roughness and etching resistance during the plasma etching process.

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The serious problem associated with 193-nm lithography using an ArF photoresist is roughness formation of photoresist polymer during plasma processes. We have previously investigated the mechanism of roughness formation caused by plasma. The main deciding factor for roughness formation is a chemical reaction between photoresist polymer and reactive species from plasma. The lactone group in photoresist polymer is highly chemically reactive, and shrinking the lactone structure enhances the roughness formation. In this paper, on the basis of the mechanism of roughness formation, we propose a novel ArF photoresist polymer. The roughness formation was much more suppressed in the novel photoresist polymer during plasma etching process than in the previous type. In the novel photoresist polymer, chemical reactions were spread evenly on the photoresist film surface by adding the polar structure. As a result, decreases in the lactone group were inhibited, leading to suppressing ArF photoresist roughness.