阅读说明：本技术 一种光刻胶酸敏树脂单体及其合成方法和应用 (Photoresist acid-sensitive resin monomer and synthesis method and application thereof ) 是由 傅志伟 潘新刚 薛富奎 纪兴跃 刘司飞 于 2021-06-22 设计创作，主要内容包括：本发明公开了一种光刻胶酸敏树脂单体及其合成方法和应用,所述光刻胶树脂单体的结构式为：其中R-(1)为甲基或者氢,R-(2)和R-(3)独立的为氢或者烷基,或者R-(2)和R-(3)之间通过共价键形成碳原子数3-15的环状结构,R-(4)为酸敏基团。该树脂单体能提高分辨率,减小线宽粗糙度,粘附力好,耐刻蚀。(The invention discloses a photoresist acid-sensitive resin monomer, a synthesis method and application thereof, wherein the structural formula of the photoresist resin monomer is as follows: wherein R is 1 Is methyl or hydrogen, R 2 And R 3 Independently is hydrogen or alkyl, or R 2 And R 3 Form a cyclic structure with 3-15 carbon atoms by covalent bond, R 4 Is an acid labile group. The resin monomer can improve the resolution, reduce the line width roughness, and has good adhesion and etching resistance.)

1. The photoresist acid-sensitive resin monomer is characterized in that the structural formula of the photoresist acid-sensitive resin monomer is as follows:

wherein R is₁Is methyl or hydrogen, R₂And R₃Independently is hydrogen or alkyl, or R₂And R₃Form a cyclic structure with 3-15 carbon atoms by covalent bond, R₄Is an acid labile group.

2. A photoresist acid according to claim 1The photosensitive resin monomer is characterized in that R is₄Selected from one of the following structures:

wherein is linked to the ester group of the photoresist acid-sensitive resin monomer.

3. The photoresist acid-sensitive resin monomer according to claim 1 or 2, wherein the photoresist acid-sensitive resin monomer is specifically selected from one of the following structures:

4. the method for synthesizing the photoresist acid-sensitive resin monomer according to any one of claims 1 to 3, wherein the photoresist acid-sensitive resin monomer is synthesized by the following route:

wherein R is₁Is methyl or hydrogen, R₂And R₃Independently is hydrogen or alkyl, or R₂And R₃Form a cyclic structure with 3-15 carbon atoms by covalent bond, R₄Is an acid labile group; the method comprises the following specific steps:

s1, placing an initial raw material gluconic acid I in a first solvent, and carrying out esterification reaction with acryloyl chloride or methacryloyl chloride under an alkaline condition to generate an intermediate II;

s2. intermediate II andplacing the mixture in a second solvent, and dehydrating the mixture under an acidic condition to generate an intermediate III with a hemiacetal or hemiketal structure;

s3, intermediate III and R₄And (4) placing the-OH in a third solvent, and carrying out esterification reaction under the action of a catalyst to generate a photoresist acid-sensitive resin monomer IV.

5. The method for synthesizing a photoresist acid-sensitive resin monomer as claimed in claim 4, wherein the step S1 further comprises at least one of the following technical features:

a1) the first solvent is at least one selected from dichloromethane, chloroform, N-dimethylformamide and tetrahydrofuran;

a2) the base is an organic base selected from triethylamine, pyridine or diisopropylamine.

6. The method for synthesizing a photoresist acid-sensitive resin monomer as claimed in claim 4, wherein the step S2 further comprises at least one of the following technical features:

b1) the second solvent is selected from toluene, N-dimethylformamide or chloroform;

b2) the acid is selected from sulfuric acid or p-toluenesulfonic acid.

7. The method for synthesizing acid-sensitive resin monomer for photoresist as claimed in claim 4, wherein the method comprisesSelected from one of the following structures:

8. the method for synthesizing a photoresist acid-sensitive resin monomer according to claim 4, wherein in step S3, the third solvent is at least one selected from dichloromethane, tetrahydrofuran, N-dimethylformamide, chloroform and toluene.

9. The method for synthesizing a photoresist acid-sensitive resin monomer as claimed in claim 4, wherein in the step S3, the catalyst is at least one selected from p-toluenesulfonic acid, sulfuric acid, phosphoric acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and dicyclohexylcarbodiimide.

10. A photoresist acid-sensitive resin monomer according to any one of claims 1 to 3 for use in the preparation of a photoresist.

Technical Field

The invention relates to the field of photoresist resin monomers, in particular to a photosensitive resin monomer and a synthesis method and application 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 photoetching developer of the positive photoresist is alkaline, tetramethylammonium hydroxide (TMAH) is commonly used, the dissolution speed difference is required to exist in the developer before and after the photoresist is exposed, the resolution and the edge roughness of a photoetching pattern are greatly influenced by the difference, the dissolution difference depends on the property difference before and after the photosensitive resin monomer is exposed, and some polymerized units containing lactone structures also have the function of improving the dissolution difference. Common photosensitive monomers include: cyclic tert-butyl alcohol ester structure, hemiacetal (ketone) structure, tert-butyl alcohol ester structure.

Disclosure of Invention

The invention provides a photoresist acid-sensitive resin monomer and a synthesis method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a photoresist acid-sensitive resin monomer, which has a structural formula as follows:

wherein R is₁Is methyl or hydrogen, R₂And R₃Independently is hydrogen or alkyl, or R₂And R₃Form a carbon atom number by a covalent bond therebetween3-15 cyclic structure, R₄Is an acid labile group.

Preferably, said R is₄Selected from one of the following structures:

the method comprises the following steps:wherein is linked to the ester group of the photoresist acid-sensitive resin monomer.

Preferably, the specific structure of the photoresist acid-sensitive resin monomer is selected from one of the following structures:

a synthetic method of photoresist acid-sensitive resin monomer comprises the following synthetic route:

wherein R is₁Is methyl or hydrogen, R₂And R₃Independently is hydrogen or alkyl, or R₂And R₃Form a cyclic structure with 3-15 carbon atoms by covalent bond, R₄Is an acid labile group; the method comprises the following specific steps:

s1, placing an initial raw material gluconic acid I in a first solvent, and carrying out esterification reaction with acryloyl chloride or methacryloyl chloride under an alkaline condition to generate an intermediate II;

s2. intermediate II andplacing the mixture in a second solvent, and dehydrating the mixture under an acidic condition to generate an intermediate III with a hemiacetal or hemiketal structure;

s3, intermediate III and R₄And (4) placing the-OH in a third solvent, and carrying out esterification reaction under the action of a catalyst to generate a photoresist acid-sensitive resin monomer IV.

Preferably, step S1 further includes at least one of the following technical features:

a1) the first solvent is selected from dichloromethane, chloroform, N-dimethylformamide or tetrahydrofuran;

a2) the base is an organic base selected from triethylamine, pyridine or diisopropylamine.

Preferably, step S2 further includes at least one of the following technical features:

b1) the second solvent is selected from toluene, N-dimethylformamide and chloroform;

b2) the acid is sulfuric acid or p-toluenesulfonic acid.

Preferably, theSelected from one of the following structures:

preferably, in step S3, the third solvent is at least one selected from the group consisting of dichloromethane, tetrahydrofuran, N-dimethylformamide, chloroform and toluene.

Preferably, in step S3, the catalyst is at least one selected from the group consisting of p-toluenesulfonic acid, sulfuric acid, phosphoric acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, and dicyclohexylcarbodiimide.

The photoresist acid-sensitive resin monomer is used for preparing photoresist.

Compared with the prior art, the invention has the following beneficial effects: the invention provides a photoresist acid-sensitive resin monomer, which contains hydroxyl protected by a plurality of functional groups, the difference of the dissolution speed in an alkaline developing solution before and after exposure is large, ester groups are connected with acid-sensitive groups to further generate carboxylic acid after exposure, the solubility in a developing agent is further increased, the resolution is favorably improved, the line width roughness is reduced, the activation energy of hemiacetal is low, the exposure time is short, the sensitivity is higher, the adhesion with a silicon wafer is increased to a certain extent by the hemiacetal and the ester groups, the anti-etching performance is favorably improved by an aliphatic ring structure, the synthetic raw material is gluconic acid, the price is low, the photoresist acid-sensitive resin monomer is green and pollution-free, and the source is wide.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.

Example 1

Adding gluconic acid I-1 (60g, 306mmol) into dichloromethane (500mL), adding triethylamine (93g, 91.9mmol), cooling to 0 ℃, dropwise adding acryloyl chloride (27.7g, 306mmol), heating to room temperature, stirring for 4 hours, adding water (200mL), quenching the reaction, extracting the water phase with dichloromethane (200mL x 3) for three times, combining the organic phases, washing with saturated saline (200mL), drying with anhydrous sodium sulfate, and spin-drying under vacuum to obtain a crude product, wherein the crude product is purified by distillation to obtain an intermediate II-1 (55.8g, 223mmol, yield: 72.9%).

Intermediate II-1 (55.8g, 223mmol) was added to toluene (400mL), acetone (65g, 1119mmol) and p-toluenesulfonic acid (2.5g, 15mmol) were added, the mixture was heated under reflux for 16 hours, cooled to room temperature, quenched by addition of saturated sodium bicarbonate solution (25mL), water (200mL) was added, the mixture was separated, the aqueous phase was extracted three times with ethyl acetate (150 mL. times.3), the combined organic phases were washed successively with saturated sodium bicarbonate (50mL), saturated brine (50mL), and the organic phase was spin-dried under vacuum to give intermediate III-1 (61.5g, 186mmol, yield: 83.5%).

Adding the intermediate III-1 (20g, 61mmol) into toluene (400mL), adding tert-butyl alcohol (4.5g, 61mmol) and p-toluenesulfonic acid (0.2g, 1mmol), heating and refluxing for 16 hours, cooling to room temperature, adding saturated sodium bicarbonate solution (15mL) to quench the reaction, adding water (200mL), separating, extracting the aqueous phase with ethyl acetate (150mL x 3) for three times, washing the combined organic phases with saturated sodium bicarbonate solution (50mL) and saturated saline solution (50mL), and performing vacuum spin drying on the organic phases to obtain a crude product, wherein the crude product is purified by a distillation mode to obtain the photoresist acid-sensitive resin monomer IV-1 (20.3g, 53mmol, yield: 86.8%).

Example 2

Adding the intermediate III-1 (20g, 61mmol) into toluene (400mL), adding 1-methylcyclopentanol (6.1g, 61mmol) and p-toluenesulfonic acid (0.2g, 1mmol), heating and refluxing for 16 hours, cooling to room temperature, adding saturated sodium bicarbonate solution (15mL) to quench the reaction, adding water (200mL), separating, extracting the aqueous phase with ethyl acetate (150mL x 3) for three times, washing the combined organic phases with saturated sodium bicarbonate (50mL) and saturated saline (50mL), and spin-drying the organic phases in vacuum to obtain a crude product, wherein the crude product is purified by distillation to obtain the photoresist acid-sensitive resin monomer IV-2 (20.2g, 49mmol, yield: 80.9%).

Example 3

Adding the intermediate III-1 (20g, 61mmol) into toluene (400mL), adding 1-methyladamantol (10.1g, 61mmol) and p-toluenesulfonic acid (0.2g, 1mmol), heating and refluxing for 16 hours, cooling to room temperature, adding saturated sodium bicarbonate solution (15mL) to quench the reaction, adding water (200mL), separating, extracting the aqueous phase with ethyl acetate (150mL x 3) for three times, washing the combined organic phases with saturated sodium bicarbonate (50mL) and saturated saline (50mL), and spin-drying the organic phases in vacuum to obtain a crude product, wherein the crude product is purified by distillation to obtain the photoresist acid-sensitive resin monomer IV-3 (22.5g, 47mmol, yield: 77.7%).

Example 4

Intermediate II-1 (60g, 240mmol) was added to toluene (500mL), cyclopentanone (40.4g, 480mmol) and p-toluenesulfonic acid (0.6g, 4mmol) were added, heated under reflux for 16 h, cooled to room temperature, quenched by addition of saturated sodium bicarbonate solution (25mL), water (200mL) was added, the layers were separated, the aqueous phase was extracted three times with ethyl acetate (150mL x 3), the combined organic phases were washed successively with saturated sodium bicarbonate (50mL), saturated brine (50mL), and the organic phase was spin dried in vacuo to give intermediate III-2 (70.2g, 184mmol, yield: 76.5%).

Adding the intermediate III-2 (70.2g, 184mmol) into toluene (600mL), adding 1-methylcyclopentanol (18.4g, 184mmol) and p-toluenesulfonic acid (3.5g, 41mmol), heating and refluxing for 16 hours, cooling to room temperature, adding saturated sodium bicarbonate solution (50mL) to quench the reaction, adding water (300mL), separating, extracting the aqueous phase with ethyl acetate (200mL x 3) for three times, washing the combined organic phases with saturated sodium bicarbonate (100mL), saturated saline (200mL), and vacuum-drying the organic phases to obtain a crude product, wherein the crude product is purified by distillation to obtain the photoresist acid-sensitive resin monomer IV-4 (58.8g, 127mmol, yield: 68.9%).

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.