Styrene derivative-methacrylate copolymer containing photo-acid generation groups as well as preparation and application of styrene derivative-methacrylate copolymer

Abstract

The invention provides a styrene derivative-methacrylate multipolymer containing photo-acid generation groups, a synthetic method of the multipolymer and an application of the multipolymer to a photoresist material. The multipolymer is prepared from p-styrenesulfonate, 4-ethenylphenol acetate and methacrylate through a free radical polymerization reaction, an acetoxyl group is converted into a hydroxyl group with an acid catalysis deprotection method, the polymer has an ion exchange reaction with onium salt halide, and the styrene derivative-methacrylate copolymer containing the photo-acid generation groups is obtained. The polymer contains the photo-acid generation groups and produces macromolecular sulfonic acid in an exposure process, so that the polymer can be taken as a macromolecular photo-acid generator used by the chemical amplification type photoresist; besides, part of phenolic hydroxyl groups in the polymer can be protected by acidolysis groups, and the polymer can be used as the photo-acid generator and can be also used for preparing a single-component 248-nm photoresist material. The polymer can be applied to a resist applied to photoetching techniques of deep ultraviolet, extreme ultraviolet, electron beams and the like.

Description

technical field [0001] The technical field of the present invention is the field of polymer photosensitive imaging materials, and what is disclosed is a novel polymer onium salt photoacid generator, its preparation method and its application to chemically amplified photoresist materials. Specifically, Styrene sulfonate, p-acetoxystyrene, and methacrylate are used as comonomers, and free radical copolymerization is carried out to obtain a multi-polymer. The acid-catalyzed hydrolysis of the acetoxy group is converted into a phenolic hydroxyl group. The polymer is then combined with onium The salt halide is subjected to ion exchange reaction to obtain a polymer containing onium salt group in the side chain. The polymer can generate macromolecular sulfonic acid under ultraviolet light, so it can be used as a photoacid generator and other film-forming materials to form a chemically amplified photoresist. The acid generator generates macromolecular sulfonic acid during the exposure ...

AI Technical Summary

Problems solved by technology

The generation, development and improvement of chemical amplification technology have laid the foundation for 248-nm photoresist. The best resolution of 248nm photoresist with KrF laser as light source can reach below 0.15μm. Due to its high sensitivity and photolithography Other excellent properties, the chemically amplified photoresist system has attracted much attention and has become the mainstream technology since then. Traditional photoacid generators are mainly various small molecule onium salt compounds, polymer film-forming resins and these small molecule photoacid generators. There is an inherent incompatibility between acid agents, which will lead to phase separation of photoacid generators, that is, uneven distribution of acid after light irradiation, which will lead to a decrease in imaging quality. In addition, the acids produced by these small molecular compounds are generally small molecular sulfonic acid Acids, such as trifluoromethanesulfonic acid, nonafluorobutylsulfonic acid, etc., are prone to acid migration during post-exposure baking, which will reduce the resolution of graphics and increase the roughness of line edges.

[0004] In order to solve these problems, a class of polymerizable photoacid generators has emerged in recent years, which can graft anionic or cationic photoacid generators onto polymer chains to form macromolecular photoacid generators, namely PAG. -bond system. Some studies on macromolecular photoacid generators have been reported. For example, K.E.Gonsalves et al. used tert-butyl methacrylate, cage silsesquioxane methacrylate and cationic The methacrylate of the group is used as a comonomer to prepare a macromolecular photoacid generator. The disadvantage of this macromolecular photoacid generator is that although the acid-generating group is grafted to the polymer chain, the photoacid generated by light It is a small molecular acid-trifluoromethanesulfonic acid, and there is also the problem of acid migration during the post-baking process.

Images