阅读说明：本技术 一种含氟光刻胶酸敏树脂单体及其制备方法和应用 (Fluorine-containing photoresist acid-sensitive resin monomer and preparation method and application thereof ) 是由 傅志伟 邵严亮 余文卿 陆伟 郭有壹 于 2021-06-22 设计创作，主要内容包括：本发明属于光刻胶树脂单体,公开了一种含氟光刻胶酸敏树脂单体及其制备方法和应用,涉及光刻胶领域,该树脂单体的结构为：其中R-1为氢或者甲基；R-2为C-1-C-(12)的饱和烷烃基,且烃基结构中的亚甲基可以被酯基、醚基、碳酸酯基替代；R-3为为C-1-C-(12)的饱和烷烃基；R-4为全氟代或者部分氟代的C-1-C-(12)的饱和烷烃基。该树脂单体与其它树脂单体聚合后形成光刻胶树脂,可以改善光刻图案的线边缘粗糙度,提高分辨率,在193nm浸没式光刻中,增加光刻胶的疏水性,形成良好光刻图案。(The invention belongs to a photoresist resin monomer, discloses a fluorine-containing photoresist acid-sensitive resin monomer and a preparation method and application thereof, and relates to the field of photoresist, wherein the resin monomer has the following structure: wherein R is 1 Is hydrogen or methyl; r 2 Is C 1 ‑C 12 The methylene in the hydrocarbon group structure can be replaced by ester group, ether group and carbonate group; r 3 Is C 1 ‑C 12 A saturated alkyl group of (a); r 4 Being perfluorinated or partially fluorinated C 1 ‑C 12 A saturated alkyl group of (2). The resin monomer is polymerized with other resin monomers to form photoresist resin, which can improve the line edge roughness of a photoetching pattern and improve the resolution, and in 193nm immersion photoetching, the hydrophobicity of the photoresist is increased to form a good photoetching pattern.)

1. A fluorine-containing photoresist acid-sensitive resin monomer is characterized in that the structure of the resin monomer is as follows:wherein R is₁Is hydrogen or methyl; r₂Is C₁-C₁₂The methylene in the hydrocarbon group structure can be replaced by ester group, ether group and carbonate group; r₃Is C₁-C₁₂A saturated alkyl group of (a); r₄Being perfluorinated or partially fluorinated C₁-C₁₂A saturated alkyl group of (2).

2. The fluorine-containing photoresist acid-sensitive resin monomer according to claim 1, wherein the resin monomer is selected from the following structures:

wherein R is₁Is hydrogen or methyl.

3. The method for preparing the fluorine-containing photoresist acid-sensitive resin monomer according to claim 1 or 2, wherein the synthetic route of the fluorine-containing photoresist acid-sensitive resin monomer is as follows:

wherein R is₁Is hydrogen or methyl; r₂Is C₁-C₁₂The methylene in the hydrocarbon group structure can be replaced by ester group, ether group and carbonate group; r₃Is C₁-C₁₂A saturated alkyl group of (a); r₄Being perfluorinated or partially fluorinated C₁-C₁₂A saturated alkyl group of (a);

the method comprises the following specific steps:

in the step a, under the alkaline condition, a raw material I and acryloyl chloride or methacryloyl chloride are subjected to esterification reaction to generate an intermediate II, and a solvent is toluene, dichloromethane or tetrahydrofuran;

and b, dehydrating and condensing the intermediate II and the intermediate III under acid catalysis and heating reflux to obtain a resin monomer IV, wherein the solvent is toluene.

4. The method for preparing fluorine-containing photoresist acid-sensitive resin monomer as claimed in claim 3, wherein the raw material I is

5. The method for preparing a fluorine-containing photoresist acid-sensitive resin monomer according to claim 3, wherein the base in the step a is triethylamine, diisopropylamine or N, N' -diisopropylethylamine.

6. The method for preparing fluorine-containing photoresist acid-sensitive resin monomer according to claim 3, wherein the intermediate III is selected from the following structures:

7. the method for preparing a fluorine-containing photoresist acid-sensitive resin monomer as claimed in claim 3, wherein the acid in step b is trifluoromethanesulfonic acid or p-toluenesulfonic acid.

8. The fluorine-containing photoresist acid-sensitive resin monomer according to claim 1 or 2 is used for preparing photoresist.

Technical Field

The invention relates to the technical field of photoresist, and discloses a fluorine-containing photoresist acid-sensitive resin monomer and a preparation 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 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.

The photoresist resin is a polymer formed by copolymerizing a plurality of resins with different structures according to a certain proportion, and different resin monomers have different influences on the properties of the polymer, such as acid-sensitive resin monomers for changing the solubility in a developing solution before and after exposure, resin monomers for increasing fat-soluble lactone structures, resin monomers for increasing etching resistance and resin monomers with multiple aliphatic ring structures and other resin monomers with regulating effects.

As the size of the photolithographic pattern is required to be smaller and smaller, the resolution and edge roughness of the photolithographic pattern are required to be higher and higher, and the improvement of the photoresist performance is more important, therefore, it is necessary to develop a new resin monomer to improve the photoresist performance.

Disclosure of Invention

The invention aims to provide a fluorine-containing photoresist acid-sensitive resin monomer. In order to achieve the purpose, the invention adopts the following technical scheme: a fluorine-containing photoresist acid-sensitive resin monomer is provided, wherein the structure of the resin monomer is as follows:wherein R is₁Is hydrogen or methyl; r₂Is C₁-C₁₂The methylene in the hydrocarbon group structure can be replaced by ester group, ether group and carbonate group; r₃Is C₁-C₁₂A saturated alkyl group of (a); r₄Being perfluorinated or partially fluorinated C₁-C₁₂A saturated alkyl group of (2).

Preferably, the resin monomer is selected from the following structures:

wherein R is₁Is hydrogen or methyl.

Preferably, the synthetic route of the fluorine-containing photoresist acid-sensitive resin monomer is as follows:

wherein R is₁Is hydrogen or methyl; r₂Is C₁-C₁₂The methylene in the hydrocarbon group structure can be replaced by ester group, ether group and carbonate group; r₃Is C₁-C₁₂A saturated alkyl group of (a); r₄Being perfluorinated or partially fluorinated C₁-C₁₂A saturated alkyl group of (a);

the method comprises the following specific steps:

in the step a, under the alkaline condition, a raw material I and acryloyl chloride or methacryloyl chloride are subjected to esterification reaction to generate an intermediate II, and a solvent is toluene, dichloromethane or tetrahydrofuran;

and b, dehydrating and condensing the intermediate II and the intermediate III under acid catalysis and heating reflux to obtain a resin monomer IV, wherein the solvent is toluene.

Preferably, the raw material I is

Preferably, the base in step a is triethylamine, diisopropylamine or N, N' -diisopropylethylamine.

Preferably, said intermediate iii is selected from the following structures:

preferably, the acid in step b is trifluoromethanesulfonic acid or p-toluenesulfonic acid.

The fluorine-containing 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 novel resin monomer, which is polymerized with other resin monomers to form photoresist resin, and under the action of a photoacid generator, an unstable ketal structure of the resin monomer is subjected to acidolysis, so that the solubility of the resin in a developing solution is changed, the line edge roughness of a photoetching pattern is improved, and the resolution is improved. Meanwhile, in 193nm immersion lithography, a water-resistant coating is formed on the surface of the photoresist by the fluorine-containing structure, so that the hydrophobicity of the photoresist is increased, meanwhile, the leaching of components of the photoresist can be effectively prevented, and a good lithography pattern is formed.

Detailed Description

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

Example 1

Step a. hydroxy-2-propanone 1-a (10g, 135mmol) was added to dichloromethane (100mL), triethylamine (34g, 336mmol) was added, cooled to 0 ℃ with an ice water bath, acryloyl chloride (13.4g, 148mmol) was slowly added dropwise, after the addition was complete, the temperature was raised to 25 ℃, stirring was continued for 2 hours, the reaction solution was slowly added to ice water (50mL), saturated solution of sodium carbonate (20mL) was added for neutralization, liquid separation was performed, the aqueous phase was extracted three times with dichloromethane (30mL × 3), the organic phases were combined, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and concentrated in vacuo to give intermediate 1-b (16.2g, 126mmol, 93.7%).

Step b, adding the intermediate 1-b (10g, 78mmol) and 2-hydroxy-2-trifluoromethyl-3, 3, 3-trifluoropropionic acid (16.5g, 78mmol) into toluene (200mL), adding p-toluenesulfonic acid (0.2g, 1.2mmol), heating and refluxing, separating condensed water by using a water separator, refluxing for 16 hours, cooling the reaction solution, adding 5% sodium bicarbonate solution (50mL), extracting an aqueous phase with ethyl acetate (30 mL. times.3) for three times, combining organic phases, washing the organic phase with saturated sodium chloride, drying anhydrous sodium sulfate, concentrating in vacuum to obtain a crude product, adding the crude product into methyl tert-butyl ether (50mL), pulping, filtering, and drying a solid to obtain a resin monomer 1-c (19.2g, 60mmol, 76.4%).

Example 2

Step a-1. adding 3-hydroxy-1-adamantane acid (10g, 51mmol) and N, N' -carbonyldiimidazole (8.3g, 51mmol) into chloroform (100g), stirring at 25 ℃ for 2 hours, adding hydroxy-2-acetone (3.8g, 51mmol), supplementing chloroform (50g), stirring at room temperature for 3 hours, adding saturated potassium carbonate solution (40g), extracting the aqueous phase with chloroform (30 mL. times.3), washing the organic layer with saturated sodium chloride, drying with anhydrous sodium sulfate, vacuum-concentrating, adding the obtained crude product into methyl tert-butyl ether (30mL), pulping, filtering and drying to obtain intermediate 2-b (11.3g, 45mmol, 87.9%)

Step a, adding the intermediate 2-b (10g, 40mmol) into dichloromethane (100mL), adding diisopropylamine (10g, 99mmol), cooling to 0 ℃ with an ice water bath, slowly dropwise adding acryloyl chloride (3.6g, 40mmol), raising the temperature to 25 ℃ after dropwise adding, continuing stirring for 2 hours, slowly adding the reaction liquid into ice water (50mL), adding saturated solution of sodium carbonate (20mL) for neutralization, separating, extracting the aqueous phase with dichloromethane (30mL × 3) for three times, combining the organic phases, washing the organic phase with saturated solution of sodium chloride, drying with sodium sulfate, and concentrating in vacuum to obtain an intermediate 2-c (11.5g, 38mmol, 94.7%).

Step b, adding the intermediate 2-c (10g, 33mmol) and 2-hydroxy-2-trifluoromethyl-3, 3, 3-trifluoropropionic acid (7g, 33mmol) into toluene (120mL), adding trifluoromethanesulfonic acid (0.2g, 1.3mmol), heating and refluxing for 16 hours, separating condensed water by using a water separator, cooling the reaction solution, adding 5% sodium bicarbonate solution (50mL), extracting the water phase with ethyl acetate (30 mL. times.3) for three times, combining the organic phases, washing the organic phases with saturated sodium chloride, drying the anhydrous sodium sulfate, concentrating in vacuum to obtain a crude product, adding the crude product into methyl tert-butyl ether (50mL) for pulping, filtering, and drying the solid to obtain a resin monomer 2-d (12.4g, 25mmol, 75.9%).

Example 3

Adding the intermediate 1-b (10g, 78mmol) and 2, 2-difluoro-3-hydroxypropionic acid (9.9g, 78mmol) into toluene (120mL), adding p-toluenesulfonic acid (0.2g, 1.2mmol), heating and refluxing for 16 hours, separating condensed water by using a water separator, cooling a reaction solution, adding a 5% sodium bicarbonate solution (50mL), extracting an aqueous phase with ethyl acetate (30mL multiplied by 3) for three times, combining organic phases, washing the organic phase with saturated sodium chloride, drying anhydrous sodium sulfate, concentrating in vacuum to obtain a crude product, adding the crude product into methyl tert-butyl ether (50mL) for pulping, and drying a solid after filtration to obtain the resin monomer 3-b (13.1g, 55mmol, 71.1%).

Example 4

Step a. Synthesis of intermediate 4-b the same procedure as in step a of example 1 was followed, substituting acryloyl chloride (13.4g, 148mmol) for methacryloyl chloride (15g, 143.5mmol), and the remaining reactant amounts were held constant to afford intermediate 4-b (17.8g, 125mmol, 92.8%).

Step b, adding the intermediate 4-b (10g, 70mmol) and 3-hydroxy-2- (trifluoromethyl) propionic acid (11.2g, 71mmol) into toluene (120mL), adding p-toluenesulfonic acid (0.2g, 1.2mmol), heating and refluxing for 16 hours, separating condensed water by using a water separator, cooling a reaction solution, adding a 5% sodium bicarbonate solution (50mL), extracting an aqueous phase with ethyl acetate (30mL multiplied by 3) for three times, combining organic phases, washing the organic phases with saturated sodium chloride, drying with anhydrous sodium sulfate, concentrating in vacuum to obtain a crude product, adding the crude product into methyl tert-butyl ether (50mL) for pulping, filtering, and drying a solid to obtain a resin monomer 4-c (13.8g, 52mmol, 73.2%).

Example 5

Step a. Synthesis of intermediate 5-b the procedure was the same as in step a of example 2, with acryloyl chloride (3.6g, 40mmol) replaced with methacryloyl chloride (4.5g, 43mmol) and the amounts of the other reactants were the same as in example 2 to give intermediate 5-b (11.6g, 36.21mmol, 91.35%).

Step b, adding the intermediate 5-b (10g, 31mmol) and 2,2,3, 3-tetrafluoro-4-hydroxybutyric acid (5.5g, 31mmol) into toluene (120mL), adding p-toluenesulfonic acid (0.2g, 1.2mmol), heating and refluxing for 16 hours, separating condensed water by using a water separator, cooling reaction liquid, adding 5% sodium bicarbonate solution (50mL), extracting an aqueous phase with ethyl acetate (30mL × 3) for three times, combining organic phases, washing the organic phases with saturated sodium chloride, drying the organic phases, concentrating in vacuum to obtain a crude product, adding the crude product into methyl tert-butyl ether (50mL) for pulping, filtering, and drying a solid to obtain a resin monomer 5-c (10.2g, 21mmol, 68.3%).

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.