阅读说明：本技术 含二氧代双环[2.2.2]辛烷二羧酸脂结构的光刻胶产酸树脂单体及其制备方法 (Photoresist acid-producing resin monomer containing dioxobicyclo [2.2.2] octane dicarboxylic acid ester structure and preparation method thereof ) 是由 邵严亮 傅志伟 贺宝元 潘新刚 薛富奎 汪进波 于 2020-06-18 设计创作，主要内容包括：本发明公开了含二氧代双环[2.2.2]辛烷二羧酸脂结构的光刻胶产酸树脂单体及其制备方法,树脂单体的结构式如下：<Image he="389" wi="549" file="DDA0002544840310000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>为烷基、氟代烷基或含氧烷基,R<Sub>2</Sub>、R<Sub>3</Sub>、R<Sub>4</Sub>各自独立的为氢或者烷基,其制备方法为,丙烯酸2,3-二羟丙基酯Ⅰ与丙烯酸3-羟基-2-羰基酯经缩醛反应形成中间体Ⅱ,中间体Ⅱ依次与2,5-二氧代双环[2.2.2]辛烷-1,4-二羧酸和含羟基的磺酸盐进行酯化反应形成中间体Ⅳ,中间体Ⅳ与卤化硫反应生成树脂单体Ⅴ。本发明的树脂单体结合有光致产酸剂,还包括缩醛结构、多环和多酯结构,能够防止光致产酸剂的扩散,改善边缘粗糙度,增加对比度,提高分辨率,具有优异的耐刻蚀性和脂溶性溶,且制备方法简单方便。(The invention discloses dioxo-containing bicyclo [2.2.2]The photoresist acid-producing resin monomer with octane dicarboxylate structure and the preparation method thereof, the structural formula of the resin monomer is as follows: wherein R is 1 Is alkyl, fluoroalkyl or oxyalkyl, R 2 、R 3 、R 4 Independently of each other hydrogen or alkyl, by the process of the preparation of 2, 3-dihydroxypropyl acrylate I by the aldolisation reaction with 3-hydroxy-2-carbonyl acrylate to form intermediate II which in turn is reacted with 2, 5-dioxobicyclo [2.2.2] methyl acrylate]Carrying out esterification reaction on octane-1, 4-dicarboxylic acid and hydroxyl-containing sulfonate to form an intermediate IV, and reacting the intermediate IV with halideThe sulfur reacts to form resin monomer V. The resin monomer is combined with the photoacid generator, and also comprises an acetal structure, a polycyclic structure and a polyester structure, so that the resin monomer can prevent the diffusion of the photoacid generator, improve the edge roughness, increase the contrast, improve the resolution, has excellent etching resistance and fat-soluble solubility, and has a simple and convenient preparation method.)

1. Containing dioxo-bicyclo [2.2.2]The photoresist acid-producing resin monomer with the octane dicarboxylate structure is characterized in that the resin monomer is 2, 5-dioxo bicyclo [2.2.2]]Octane-1, 4-dicarboxylic acid, wherein the resin monomer comprises anions and cations and has the following structural general formula:

2. The monomer for photoresist acid-producing resin containing dioxobicyclo [2.2.2] octane dicarboxylate structure according to claim 1, wherein the cation is sulfonium cation, comprising the following structure:

3. the dioxo-bicyclo [2.2.2] octane dicarboxylate-structure-containing photoresist acid-producing resin monomer according to claim 1, wherein the resin monomer specifically comprises the following structure:

4. the preparation method of the photoresist acid-producing resin monomer containing the dioxobicyclo [2.2.2] octane dicarboxylic acid ester structure is characterized by comprising the following synthetic steps:

wherein M is an alkali metal, X is a halogen atom, R₁Is alkyl, fluoroalkyl or oxyalkyl, R₂、R₃And R₄Each independently is hydrogen or alkyl;

the specific synthesis steps are as follows:

s1, preparation of intermediate II: 2, 3-dihydroxypropyl acrylate I reacts with 3-hydroxy-2-carbonyl acrylate to generate an intermediate II with a cyclic hemiketal structure;

s2, preparation of intermediate iii: the intermediate II and 2, 5-dioxo-bicyclo [2.2.2] octane-1, 4-dicarboxylic acid are subjected to esterification reaction under the action of a catalyst a to generate an intermediate III;

s3, preparation of intermediate IV: the intermediate III and hydroxyl-containing sulfonate are subjected to esterification reaction under the action of a catalyst b to generate an intermediate IV;

s4, preparation of resin monomer V: and reacting the intermediate IV with triphenyl sulfur halide or substituted phenyl sulfur halide to generate a resin monomer V.

5. The method for preparing acid-producing resin monomer with dioxo-bicyclo [2.2.2] octane dicarboxylic acid ester structure for photoresist according to claim 4, wherein S1 is specifically that 2, 3-dihydroxypropyl acrylate I and 3-hydroxy-2-carbonyl acrylate are dissolved in toluene, and heated under the catalysis of p-toluenesulfonic acid for reflux to react to generate intermediate II with cyclic hemiketal structure.

6. The method for preparing acid-producing resin monomer for photoresist containing dioxobicyclo [2.2.2] octane dicarboxylate structure according to claim 4, wherein catalyst a and catalyst b are both p-toluenesulfonic acid.

7. The method for preparing the acid-producing resin monomer for photoresist containing dioxobicyclo [2.2.2] octane dicarboxylate structure according to claim 4, wherein the triphenylsulfur halide is triphenylsulfur bromide, and the substituted phenylsulfur halide is substituted phenylsulfur bromide.

8. The method for preparing the acid-producing resin monomer for photoresist containing dioxobicyclo [2.2.2] octane dicarboxylate structure according to claim 4, wherein the hydroxyl group-containing sulfonate comprises:

wherein M is an alkali metal.

Technical Field

The invention relates to the field of degradable photoresist resin monomers, in particular to a photoresist acid-producing resin monomer containing a dioxo bicyclo [2.2.2] octane dicarboxylic acid ester structure.

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 material are resin, photoacid generator, and corresponding additives and solvents, and the material has chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and changes its solubility in developer through photochemical reaction. 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.

Photoacid generators are one of the key components in chemically amplified photoresists, and their structure and properties have a large influence on the image formed by the photoresist system. The acid-sensitive resin is a compound which can be decomposed to generate specific acid under the irradiation of a specific light source or radiation, the generated acid can enable the acid-sensitive resin to generate decomposition or crosslinking reaction, and the acid-sensitive resin monomer is an important component for realizing the dissolution difference of the resin in a developing solution before and after exposure.

As Integrated Circuit (IC) feature sizes have decreased, the problem of photoacid generator diffusion has become increasingly important.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a novel degradable acid-producing photoresist resin monomer and a preparation method thereof.

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

the photoresist acid-producing resin monomer containing the structure of the dioxobicyclo [2.2.2] octane dicarboxylic acid ester is synthesized by 2, 5-dioxobicyclo [2.2.2] octane-1, 4-dicarboxylic acid, comprises an anion and a sulfonium cation, and has the following structural general formula:

wherein R is₁Is alkyl, fluoroalkyl or oxyalkyl, R₂、R₃And R₄Each independently is hydrogen or alkyl. Preferably, R₁For fluoroalkyl groups, the greater the number of fluorine atoms or the closer the fluorine atom is to the sulfonate group, the more acidic the photoacid generator generates upon exposure to light.

In a preferred embodiment of the present invention, the cation is a sulfonium cation, and comprises the following structure:

as a preferred technical solution of the present invention, the resin monomer specifically includes the following structure:

the preparation method of the acid-producing resin monomer for the photoresist comprises the following reaction route:

wherein M is an alkali metal, X is a halogen atom, R₁Is alkyl, fluoroalkyl or oxyalkyl, R₂、R₃And R₄Each is independentAnd is independently hydrogen or alkyl; preferably, M is K, Na or Li;

the specific synthesis steps are as follows:

s1, preparation of intermediate II: 2, 3-dihydroxypropyl acrylate I reacts with 3-hydroxy-2-carbonyl acrylate to generate an intermediate II with a cyclic hemiketal structure;

s2, preparation of intermediate iii: the intermediate II and 2, 5-dioxo-bicyclo [2.2.2] octane-1, 4-dicarboxylic acid are subjected to esterification reaction under the action of a catalyst a to generate an intermediate III;

s3, preparation of intermediate IV: the intermediate III and hydroxyl-containing sulfonate are subjected to esterification reaction under the action of a catalyst b to generate an intermediate IV;

s4, preparation of resin monomer V: and reacting the intermediate IV with triphenyl sulfur halide or substituted phenyl sulfur halide to generate a resin monomer V.

As a preferred technical scheme of the invention, S1 is specifically that 2, 3-dihydroxypropyl acrylate I and 3-hydroxy-2-carbonyl acrylate are dissolved in toluene and heated and refluxed under the catalysis of p-toluenesulfonic acid to react to generate an intermediate II with a cyclic hemiketal structure.

As a preferable technical scheme of the invention, the catalyst a and the catalyst b are both p-toluenesulfonic acid.

As a preferred technical scheme of the invention, the triphenyl sulfur halide is triphenyl sulfur bromide, and the substituted phenyl sulfur halide is substituted phenyl sulfur bromide.

As a preferred embodiment of the present invention, the hydroxyl group-containing sulfonic acid salt includes:

wherein M is an alkali metal.

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

(1) the resin monomer provided by the invention is combined with the photoacid generator, so that the diffusion of the photoacid generator in the post-exposure baking process can be effectively prevented, and the improvement of the edge roughness of a photoetching pattern is facilitated.

(2) The resin monomer also contains an acetal structure, during exposure, a photoacid generator group on the resin can generate sulfonic acid, and under the action of acid, a hemiketal structure at one end can be disconnected, so that a main chain generated by polymerization is disconnected, small fragments are generated, the edge roughness of a photoetching pattern is further improved, the resolution of the photoresist is improved, meanwhile, hydroxyl with good alkali solubility is formed, the dissolution in the developing process is facilitated, the dissolution speed of the photoresist in a developing solution after exposure is increased, and the contrast of the photoresist is increased.

(3) The multi-ring structure of the 2, 5-dioxobicyclo [2.2.2] octane-1, 4-dicarboxylic acid also greatly increases the etching resistance of the photoresist, and the polyester-based structure also increases the solubility of the photoresist in a fat-soluble solvent, so that the spin coating is convenient and uniform.

(4) The resin monomer of the invention contains two unsaturated groups, and can generate crosslinking when forming polymers with other monomers to form a polymer resin with better etching resistance.

(5) The invention has simple synthetic route and convenient operation.

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.