阅读说明：本技术 由氧杂螺[4.5]癸烷二酮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 oxaspiro [4.5] decanedione 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 2020-06-18 设计创作，主要内容包括：本发明公开了由氧杂螺[4.5]癸烷二酮合成的可降解型光刻胶树脂单体及其合成方法,涉及光刻胶树脂领域,该树脂单体的结构式为：<Image he="402" wi="322" file="DDA0002545590120000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>为饱和烷烃或者环烷烃,R<Sub>2</Sub>为氢或者甲基。其合成方法为：6-氧杂螺[4.5]癸烷-8,10-二酮(Ⅰ)与烷基格氏试剂或者环烷基格氏试剂反应得到中间体(Ⅱ)；在碱性条件下,中间体(Ⅱ)与丙烯酰氯或者甲基丙烯酰氯反应得到树脂单体(Ⅲ)。本发明提供的树脂单体与其它树脂单体聚合形成的聚合树脂具有更好的耐刻蚀性能,有利于改善显影后图形的边缘粗糙度,大大提高了光刻图案的分辨率,并且,增加了聚合树脂在脂溶性溶剂中的溶解度。(The invention discloses a oxaspiro [4.5]]A degradable photoresist resin monomer synthesized by decanedione and a synthesis method thereof relate to the field of photoresist resin, and the structural formula of the resin monomer is as follows: wherein R is 1 Is a saturated alkane or cycloalkane, R 2 Is hydrogen or methyl. The synthesis method comprises the following steps: 6-oxaspiro [4.5]]The decane-8, 10-dione (I) reacts with an alkyl Grignard reagent or a cycloalkyl Grignard reagent to obtain an intermediate (II); and (3) reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition to obtain a resin monomer (III). The resin monomer provided by the invention is polymerized with other resin monomer to form polymerized resinThe photoresist has better etching resistance, is beneficial to improving the edge roughness of a developed pattern, greatly improves the resolution of a photoetching pattern, and increases the solubility of polymer resin in a fat-soluble solvent.)

1. The degradable photoresist resin monomer synthesized by oxaspiro [4.5] decanedione is characterized in that the structure of the resin monomer is as follows:

2. The degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione according to claim 1, wherein the structure of the resin monomer comprises:

3. the synthesis method of the degradable photoresist resin monomer synthesized by oxaspiro [4.5] decanedione is characterized in that the reaction route of the synthesis method is as follows:

the synthesis steps are as follows:

the first step of Grignard reaction, under the protection of inert gas, 6-oxaspiro [4.5] decane-8, 10-dione (I) reacts with alkyl Grignard reagent or cycloalkyl Grignard reagent, water is added after the reaction is finished for quenching, and the intermediate (II) is obtained after post-treatment and purification;

and (2) performing esterification reaction, namely reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and performing post-treatment and purification to obtain a resin monomer (III).

4. The method for synthesizing the degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione according to claim 3, wherein the temperature of the Grignard reaction is 0 to 30 ℃.

5. The method for synthesizing the degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione according to claim 3, wherein the solvent of the Grignard reaction is anhydrous ethyl ether.

6. The method for synthesizing the degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione according to claim 3, wherein the reaction temperature of the esterification reaction is 0-70 ℃.

7. The method for synthesizing the degradable photoresist resin monomer synthesized from oxaspiro [4.5] decanedione according to claim 3, wherein the solvent for the esterification reaction is selected from tetrahydrofuran, toluene or chloroform.

8. The method for synthesizing a degradable photoresist resin monomer from oxaspiro [4.5] decanedione according to claim 3, wherein triethylamine or pyridine is added to the system to ensure the alkaline condition of the esterification reaction.

Technical Field

The invention relates to the field of photoresist resin, 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 oxaspiro [4.5] decanedione 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 following structure:

wherein R is₁Is a saturated alkane or cycloalkane, R₂Is hydrogen or methyl.

Preferably, the specific structure of the resin monomer comprises:

in addition, the invention also provides a synthetic method of the degradable photoresist resin monomer synthesized by oxaspiro [4.5] decanedione, and the synthetic route of the synthetic method is as follows:

the synthesis steps are as follows:

the first step of Grignard reaction, under the protection of inert gas, 6-oxaspiro [4.5] decane-8, 10-dione (I) reacts with alkyl Grignard reagent or cycloalkyl Grignard reagent, water is added after the reaction is finished for quenching, and the intermediate (II) is obtained after post-treatment and purification;

and (2) performing esterification reaction, namely reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and performing post-treatment and purification to obtain a resin monomer (III).

Preferably, the temperature of the grignard reaction is 0 to 30 ℃.

Preferably, the solvent for the grignard reaction is anhydrous diethyl ether.

Preferably, the temperature of the esterification reaction is 0 to 70 ℃.

Preferably, the solvent for the esterification reaction is selected from tetrahydrofuran, toluene or chloroform.

It is worth mentioning that in order to ensure the alkalinity of the esterification reaction system, a base is added to the system, and the preferred base is triethylamine or pyridine.

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

the invention provides a new photoresist resin monomer, the resin monomer contains two unsaturated carbon-carbon double bonds, can generate cross linking in the polymerization process with other resin monomers (including acid-sensitive resin monomer containing only one polymerization group), form polymer resin with three-dimensional network structure, the generated cross-linked polymer resin has better anti-etching performance, when exposed, the photo-acid generator generates acid, in the exposure area, (methyl) acrylic ester on the main chain is broken under the acid condition, the main chain of the polymer resin is broken to generate product with smaller molecular weight, the solubility of the exposed resin in the developing solution is increased, because the difference of the dissolving speed of the polymer resin before and after exposure in the developing solution is increased, the edge roughness of the developed pattern is improved, the resolution of the photoetching pattern is greatly improved, and the resin monomer contains oxygen-containing heterocyclic ring structure, although the oxygen-containing heterocyclic ring is less effective in increasing the etching resistance than the polycyclic alkane, it also contributes to an improvement in resolution. Furthermore, the oxygenated heterocyclic is high in lipid solubility and better in solubility in ester solvents before spin coating.

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.