阅读说明：本技术 一种含多环β-酮结构的光敏型光刻胶树脂单体及其合成方法 (Photosensitive photoresist resin monomer containing polycyclic beta-ketone structure and synthetic method thereof ) 是由 傅志伟 贺宝元 邵严亮 潘新刚 薛富奎 于 2020-06-16 设计创作，主要内容包括：本发明公开了一种含多环β-酮结构的光敏型光刻胶树脂单体,涉及光刻胶树脂单体领域,其结构式如下所示：<Image he="398" wi="383" file="DDA0002541964360000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sub>1</Sub>为甲基或者H,R<Sub>2</Sub>、R<Sub>3</Sub>分别独立的为氢、烷基、环烷基,R<Sub>4</Sub>为烷基或者环烷基,且R<Sub>2</Sub>和R<Sub>4</Sub>、R<Sub>3</Sub>和R<Sub>4</Sub>或者R<Sub>2</Sub>和R<Sub>3</Sub>可以通过共价键连接形成环状结构；n为1-10的整数,该树脂单体具有曝光前后溶解度差异大,能够降低粗糙度,提高灵敏度和分辨率,有利于形成均一性良好的光刻图案,耐刻蚀性能良好。(The invention discloses a photosensitive photoresist resin monomer containing a polycyclic beta-ketone structure, which relates to the field of photoresist resin monomers and has the following structural formula: wherein R is 1 Is methyl or H, R 2 、R 3 Each independently is hydrogen, alkyl, cycloalkyl, R 4 Is alkyl or cycloalkyl, and R 2 And R 4 、R 3 And R 4 Or R 2 And R 3 Can be linked by covalent bonds to form a cyclic structure; n is an integer of 1-10, the resin monomer has large solubility difference before and after exposure, can reduce roughness, improve sensitivity and resolution, is favorable for forming photoetching patterns with good uniformity, and has good etching resistance.)

1. A photosensitive photoresist resin monomer containing a polycyclic beta-ketone structure is characterized in that the structural formula of the photoresist resin monomer is as follows:wherein R is₁Is methyl or H, R₂、R₃Each independently is hydrogen, alkyl, cycloalkyl, R₄Is alkyl or cycloalkyl, and R₂And R₄、R₃And R₄Or R₂And R₃The cyclic structure can be formed by covalent bonding, and n is an integer of 1 to 10.

2. The photosensitive photoresist resin monomer containing polycyclic beta-ketone structure as claimed in claim 1, wherein the specific structure of the resin monomer comprises:

3. a synthetic method of a photosensitive photoresist resin monomer containing a polycyclic beta-ketone structure is characterized in that the synthetic route of the resin monomer is as follows:

wherein X is halogen, the specific steps are as follows:

a. oxidizing double bonds in the initial raw material A by an oxidizing agent to form an intermediate B of a ternary epoxy group;

b. hydrolyzing the ternary epoxy group of the intermediate B under an acidic condition to generate an intermediate C with an o-dihydroxy structure;

c. under the alkaline condition, the intermediate C is esterified with one equivalent of (methyl) acryloyl chloride to generate an intermediate D with a (methyl) acrylate structure;

d. and reacting the intermediate D with the halide F under an alkaline condition to generate a resin monomer E.

4. The method for synthesizing the photosensitive photoresist resin monomer containing the polycyclic beta-ketone structure as claimed in claim 3, wherein the oxidant in the synthesis step a is m-chloroperoxybenzoic acid or hydrogen peroxide.

5. The method for synthesizing the photosensitive photoresist resin monomer containing the polycyclic beta-ketone structure as claimed in claim 3, wherein the acid in the synthesis step b is sulfuric acid.

6. The method for synthesizing the photosensitive photoresist resin monomer with the polycyclic beta-ketone structure as claimed in claim 3, wherein the basic conditions in the synthesis steps c and d are the same, and the base is selected from organic bases including triethylamine, diisopropylamine and pyridine.

7. The method for synthesizing the photosensitive photoresist resin monomer containing the polycyclic beta-ketone structure as claimed in claim 3, wherein the method for synthesizing the halide F comprises the following steps:

wherein X is halogen, R₄OH and R₂COR₃Generating a halogenated substance F under the action of hydrogen halide and sodium sulfate, and selecting toluene as a solvent.

8. The photosensitive photoresist resin monomer containing polycyclic beta-ketone structure of claim 3, wherein the initial raw material A comprises:

Technical Field

The invention relates to the field of photoresist resin monomers, in particular to a photosensitive resin monomer and a synthesis 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 photosensitive resin monomer is an important component of photoresist polymer resin, and mainly has the main function of generating polarity difference before and after exposure, so that the solubility of the photosensitive resin monomer in a polar developer is different.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a novel photosensitive photoresist resin monomer containing a polycyclic beta-ketone structure and a synthetic method thereof.

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

the invention provides a photosensitive photoresist resin monomer containing a polycyclic beta-ketone structure, which is characterized in that the structural formula of the photoresist resin monomer is as follows: wherein R is₁Is methyl or H, R₂、R₃Each independently is hydrogen, alkyl, cycloalkyl, R₄Is alkyl or cycloalkyl, and R₂And R₄、 R₃And R₄Or R₂And R₃The cyclic structure can be formed by covalent bonding, and n is an integer of 1 to 10.

As a preferred technical solution of the present invention, the specific structure of the resin monomer includes:

the invention also correspondingly provides a synthetic method of the photosensitive photoresist resin monomer containing the polycyclic beta-ketone structure, and the synthetic route of the resin monomer is as follows:

wherein X is halogen, the specific steps are as follows:

a. oxidizing double bonds in the initial raw material A by an oxidizing agent to form an intermediate B of a ternary epoxy group;

b. hydrolyzing the ternary epoxy group of the intermediate B under an acidic condition to generate an intermediate C with an o-dihydroxy structure;

c. under the alkaline condition, the intermediate C is esterified with one equivalent of (methyl) acryloyl chloride to generate an intermediate D with a (methyl) acrylate structure;

d. and reacting the intermediate D with the halide F under an alkaline condition to generate a resin monomer E.

In a preferred embodiment of the present invention, the oxidizing agent in the synthesis step a is m-chloroperoxybenzoic acid or hydrogen peroxide.

As a preferred technical scheme of the invention, the acid in the synthesis step b is sulfuric acid.

As a preferred technical scheme of the invention, the basic conditions in the step c and the step d are synthesized, and the bases are organic bases including triethylamine, diisopropylamine and pyridine.

As a preferred technical solution of the present invention, the method for synthesizing the halide F comprises:

wherein X is halogen, R₄OH and R₂COR₃Generating a halogenated substance F under the action of hydrogen halide and sodium sulfate, and selecting toluene as a solvent.

As a preferred technical solution of the present invention, the initial raw material a includes: and

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

the invention provides a new photoresist resin monomer, which contains photosensitive groups, and is polymerized with other resin monomers to form a photoresist resin polymer, a hemiacetal (ketone) protective group can be removed after exposure, the activation energy of the hemiacetal (ketone) is lower, the sensitivity is higher, a hydroxyl structure is formed after deprotection, so that the polarity is increased, the resin monomer is dissolved in an alkaline developer (generally TMAH), the solubility difference of the resin monomer before and after exposure is large, the roughness can be reduced, the sensitivity and the resolution are improved, a photoetching pattern with good uniformity can be formed, the resin monomer has a polycyclic structure, the etching resistance is higher, the ketone structure enhances the hydrophilicity, and the alkali solubility is improved.

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.