阅读说明：本技术 一种由环氧泽泻烯合成的可降解型光刻胶树脂单体及其合成方法 (Degradable photoresist resin monomer synthesized from epoxy alisma alkene and synthesis method thereof ) 是由 傅志伟 贺宝元 邵严亮 毛国平 余文清 薛富奎 刘司飞 于 2020-06-16 设计创作，主要内容包括：本发明公开了一种由环氧泽泻烯合成的可降解型光刻胶树脂单体及其合成方法,涉及光刻胶树脂单体领域,树脂单体的结构式如下所示：<Image he="328" wi="402" file="DDA0002542455650000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R为氢或者甲基,其合成方法如下：第一步氢化反应,在催化剂a催化下,环氧泽泻烯中的不饱和碳碳双键与氢气进行加成反应；第二步酯化反应,氢化后的环氧泽泻烯与另一反应底物经酯化反应后生成树脂单体。本发明提供的树脂单体具有更好的耐刻蚀性能,曝光前后在显影液中溶解速度差增大,有利于改善显影后图形的边缘粗糙度,大大提高了显影后图形的分辨率。(The invention discloses a degradable photoresist resin monomer synthesized by epoxy alisma alkene and a synthesis method thereof, relating to the field of photoresist resin monomers, wherein the structural formula of the resin monomer is as follows: wherein R is hydrogen or methyl, and the synthesis method comprises the following steps: the first step of hydrogenation reaction, wherein unsaturated carbon-carbon double bonds in the epoxy alisma alkene and hydrogen gas are subjected to addition reaction under the catalysis of a catalyst a; and (2) performing esterification reaction, namely performing esterification reaction on the hydrogenated epoxy alisma alkene and another reaction substrate to generate a resin monomer. The resin provided by the inventionThe monomer has better etching resistance, the difference of the dissolving speed in the developing solution before and after exposure is increased, the improvement of the edge roughness of the developed pattern is facilitated, and the resolution of the developed pattern is greatly improved.)

1. A degradable photoresist resin monomer synthesized by epoxy alisma alkene is characterized in that the structural formula of the resin monomer is as follows:

wherein R is hydrogen or methyl.

2. A synthetic method of a degradable photoresist resin monomer synthesized by epoxy alisma alkene is characterized in that the reaction route of the synthetic method is as follows:

r is hydrogen or methyl, and the synthesis steps are as follows:

the first step of hydrogenation reaction, wherein unsaturated carbon-carbon double bonds in the epoxy alisma alkene and hydrogen gas are subjected to addition reaction under the catalysis of a catalyst a;

and (2) performing esterification reaction on the hydrogenated epoxy alisma alkene and another reaction substrate to generate the resin monomer.

3. The method for synthesizing the degradable photoresist resin monomer synthesized from epoxy alisol according to claim 2, wherein the catalyst a for the hydrogenation reaction is palladium-carbon.

4. The method for synthesizing the degradable photoresist resin monomer synthesized from Alisma oxide according to claim 2, wherein the solvent for the hydrogenation reaction is selected from one of methanol, ethanol and tetrahydrofuran.

5. The method for synthesizing the degradable photoresist resin monomer synthesized from epoxy alisol according to claim 2, wherein when R is hydrogen, the other reaction substrate in the esterification reaction is acrylic acid, acryloyl chloride or acrylic anhydride, and when R is methyl, the other reaction substrate in the esterification reaction is methacrylic acid, methacryloyl chloride or methacrylic anhydride.

6. The method for synthesizing the degradable photoresist resin monomer from the epoxy alisma alkene according to claim 5, wherein when the other reaction substrate in the esterification reaction is acrylic acid or methacrylic acid, one of p-toluenesulfonic acid, sulfuric acid, thionyl chloride and hydrochloric acid is added as a catalyst in the reaction, and the reaction solvent is selected from toluene or dichloromethane.

7. The method for synthesizing the degradable photoresist resin monomer synthesized from the epoxy alisma alkene according to claim 5, wherein when another reaction substrate in the esterification reaction is acryloyl chloride or methacryloyl chloride, the reaction is carried out under an alkaline condition, and the acryloyl chloride or the methacryloyl chloride reacts with the hydrogenated epoxy alisma alkene to generate the resin monomer under the catalysis of 4-dimethylaminopyridine.

8. The method of claim 7, wherein the esterification reaction in the second step is carried out by adding one of triethylamine and pyridine to the reaction system to ensure the alkaline condition of the reaction.

Technical Field

The invention relates to the field of photoresist resin monomers, in particular to a resin monomer and a synthetic method thereof.

Background

The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like.

The main components of the photoresist are resin, photoacid generator, and corresponding additives and solvents, and these materials have chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and undergo a photochemical reaction to change their solubility in a developing solution. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as that of the mask is obtained and is called as a positive photoresist; after exposure, the photoresist has reduced solubility or even no solubility in a developing solution, and a negative photoresist with a pattern opposite to that of the mask is obtained.

The resin is a polymer polymerized by a plurality of resin monomers, wherein the acid-sensitive resin monomer is an important component for realizing the dissolution difference of the resin in the developing solution before and after exposure, the common acid-sensitive resin monomer only has one acid-sensitive group, the resin monomer is a linear polymer and has weaker etching resistance, and the dissolution difference in the developing solution after exposure is only determined by the acid-sensitive resin monomer, so that the phenomenon of insufficient resolution is caused.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a degradable photoresist resin monomer synthesized by epoxy alisma alkene and a synthesis method thereof.

In order to solve the technical problems, the invention provides the following technical scheme:

the invention provides a novel resin monomer, which has the structural formula as follows:

wherein R is hydrogen or methyl.

In addition, the invention also provides a method for synthesizing the degradable photoresist resin monomer synthesized by the epoxy alisma alkene, which comprises the following steps: the reaction route of the synthesis method is as follows:

the synthesis steps are as follows:

the first step of hydrogenation reaction, wherein unsaturated carbon-carbon double bonds in the epoxy alisma alkene and hydrogen gas are subjected to addition reaction under the catalysis of a catalyst a;

and (2) performing esterification reaction, namely performing esterification reaction on the hydrogenated epoxy alisma alkene and another reaction substrate to generate a resin monomer.

Preferably, catalyst a is palladium on carbon.

Preferably, the solvent for the hydrogenation reaction is selected from one of methanol, ethanol and tetrahydrofuran.

In a preferred embodiment of the present invention, when R is hydrogen, the other reaction substrate in the esterification reaction is acrylic acid, acryloyl chloride, or acrylic anhydride, and when R is methyl, the other reaction substrate in the esterification reaction is methacrylic acid, methacryloyl chloride, or methacrylic anhydride.

In a preferred embodiment of the present invention, when the other reaction substrate in the esterification reaction is acrylic acid or methacrylic acid, one of p-toluenesulfonic acid, sulfuric acid, thionyl chloride and hydrochloric acid is added as a catalyst in the reaction, and toluene or dichloromethane is used as a solvent in the esterification reaction.

As a preferred technical scheme of the invention, when another reaction substrate is acryloyl chloride or methacryloyl chloride, the reaction is carried out under alkaline conditions, the acryloyl chloride or the methacryloyl chloride reacts with the hydrogenated epoxy alisma alkene to generate a resin monomer under the catalysis of 4-dimethylaminopyridine, and one of triethylamine and pyridine is added into a reaction system to ensure the alkaline conditions of the reaction.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a new photoresist resin monomer, which contains two unsaturated carbon-carbon double bonds, can generate cross-linking in the polymerization process with other resin monomers (including an acid-sensitive resin monomer containing only one polymerization group) to form a polymer resin with a three-dimensional network structure, the generated cross-linked polymer resin has better etching resistance, in addition, in the post-exposure baking process, the (methyl) acrylate on the main chain is broken under the acid condition, the main chain of the polymer resin is broken to generate a product with smaller molecular weight, the solubility of the exposed resin in a developing solution is increased, the difference of the dissolution speed of the polymer resin before and after exposure in the developing solution is increased, the edge roughness of the developed pattern is favorably improved, the resolution of the developed pattern is greatly improved, in addition, the resin monomer contains a bridge ring structure with larger volume, the etching resistance of the unexposed area is increased, there is also a significant contribution to the resolution improvement.

Detailed Description

The preferred embodiments of the present invention will be described in conjunction with the following examples, which are set forth to illustrate and explain the present invention and are not to be construed as limiting the present invention.