Photoresist composition and preparation method thereof

Abstract

The invention discloses a photoresist composition and a preparation method thereof, and relates to the technical field of photoresist, the photoresist composition comprises the following raw materials by weight: 40-60 parts of a multi-component copolymerized fluorine-containing acrylic resin, 2-5 parts of a composite photoacid generator, 0.5-1 part of an alkaline inhibitor, 0.1-0.3 part of a leveling agent, and 40-60 parts of a composite solvent; the composite photoacid generator comprises a photoacid generator carrier microcapsule and a photoacid generator auxiliary agent; the mass ratio of the photoacid generator carrier microcapsule to the photoacid generator auxiliary agent is 1: (0.2-0.6). The photoresist composition provided by the invention has the advantages of high resolution, high sensitivity, low surface roughness after etching and the like.

Description

Technical Field

[0001] The present application relates to the field of photoresist technology, and in particular to a photoresist composition and a preparation method thereof. Background Art

[0002] Photolithography is the cornerstone of the modern microelectronics industry and plays a vital role in semiconductor manufacturing. With photolithography, complex circuit designs can be precisely transferred onto silicon wafers or other substrates, creating fine structures at the micron or even nanometer level. Photoresist plays a crucial role in achieving high-resolution photolithography. Photoresist, a material sensitive to specific wavelengths of light, has been widely used in photolithography. Depending on the light source used for exposure or radiation, photoresists can be classified into: UV broadband photoresist (300-450nm), G-line (436nm) photoresist, I-line (365nm) photoresist, deep ultraviolet (KrF: 248nm, ArF: 193nm, F2: 157nm) photoresist, extreme ultraviolet (EUV) photoresist (13.5nm), X-ray photoresist (0.4-5nm), and electron beam photoresist.

[0003] As the basic material of photoresist, the optimization of its preparation process and quality control directly affect the resolution and production efficiency of the pattern. In 193nm photolithography technology, the photoresist main resins reported so far are mainly divided into three categories: (1) (methyl) acrylate derivatives; (2) cycloolefin-maleic anhydride copolymers; and (3) polynorbornene derivatives. However, these three types of resins have some limitations in practical applications. During the polymerization process of acrylate derivatives, the double bonds in the acrylic monomers are very easy to undergo polymerization reactions, and the acid-sensitive groups in the monomers are also easy to decompose, so the requirements for purification conditions are extremely strict. In addition, the main chain of acrylates is a linear structure with a low carbon-hydrogen ratio (C / H ratio), resulting in poor corrosion resistance. Although cycloolefin-maleic anhydride copolymers can distinguish 3nm lines in some cases, and even 1nm lines under optimal conditions, their film formation uniformity is poor, which limits their application in high-precision photolithography. Although polynorbornene derivatives, as pure alicyclic compounds, have certain heat resistance and etching resistance, their performance is still insufficient compared with resins containing benzene ring structures. Summary of the Invention

[0004] In order to provide a high-resolution 193nm ArF photoresist, the present application provides a photoresist composition and a preparation method thereof.

[0005] The present application provides a photoresist composition, which adopts the following technical solution:

[0006] A photoresist composition comprises raw materials, in parts by weight, including 40-60 parts of a multi-component copolymerized fluorine-containing acrylic resin, 2-5 parts of a composite photoacid generator, 0.5-1 part of an alkaline inhibitor, 0.1-0.3 parts of a leveling agent, and 40-60 parts of a composite solvent; the composite photoacid generator comprises a photoacid generator carrier microcapsule and a photoacid generator auxiliary; and the mass ratio of the photoacid generator carrier microcapsule to the photoacid generator auxiliary is 1:(0.2-0.6).

[0007] Preferably, the raw materials of the photoresist composition include, by weight, 50 parts of a multi-component copolymerized fluorine-containing acrylic resin, 3.5 parts of a composite photoacid generator, 0.75 parts of an alkaline inhibitor, 0.2 parts of a leveling agent, and 50 parts of a composite solvent.

[0008] Preferably, the preparation method of the multi-component copolymerized fluorine-containing acrylic resin comprises the following steps:

[0009] Perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth)acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate are added to tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution; azobisisobutyronitrile is added to tetrahydrofuran and stirred evenly to obtain an azobisisobutyronitrile solution; the azobisisobutyronitrile solution is added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection and reacted at 70-80°C for 6-8h; after the reaction is completed, the material is cooled to room temperature and discharged to obtain a multi-component copolymerized fluorine-containing acrylic resin.

[0010] Preferably, the mass ratio of perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth)acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate is (1-2):(2-3):(1-2):(4-5).

[0011] Preferably, the mass of the azobisisobutyronitrile is 0.5-1.0% of the total mass of perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate and methyl methacrylate.

[0012] Preferably, the core material of the photoacid generator carrier microcapsule is tetraarylphosphine salt; the shell material is polysiloxane precursor; the surface is functionalized;

[0013] The preparation method of the photoacid generator carrier microcapsule comprises the following steps:

[0014] S1. Add 7.6-11.4 parts of tetraphenylphosphine bromide and 0.8-1.2 parts of pyridine to 44.5-67 parts of tetrahydrofuran by weight and stir until completely dissolved; then slowly add 2.6-3.9 parts of 2-bromobenzothiazole under nitrogen protection, stir and react at 60-80 ° C for 4-6 hours, and obtain the core material tetraarylphosphine salt after separation and purification;

[0015] S2. 20-30 parts of γ-methacryloxypropyltrimethoxysilane and 20-30 parts of methyltrimethoxysilane were mixed and added to 40-80 parts of tetrahydrofuran, stirred until completely dissolved, and then 0.2-0.5 parts of an acidic catalyst were added. Under nitrogen protection, the reaction was carried out at 50-70 ° C for 2-3 hours. The solvent was removed by rotary evaporation, and the shell material polysiloxane precursor was obtained after separation and purification;

[0016] S3. After mixing the emulsifier and water, stirring evenly to obtain an emulsifier-water mixed solution; adding a tetraaryl phosphine salt to tetrahydrofuran, stirring and dissolving to obtain a tetraaryl phosphine salt solution; then adding the tetraaryl phosphine salt solution to the emulsifier-water mixed solution, stirring evenly, and then adding the polysiloxane precursor dropwise while stirring. After the addition is complete, reacting at 60-70°C for 4-6 hours; separating by centrifugation and washing several times with deionized water to obtain microcapsules;

[0017] S4. The microcapsules are dispersed in ethanol, and methyltrimethoxysilane is added. Under nitrogen protection, an acidic catalyst is added, and the mixture is reacted at 50-60°C for 2-3 hours. The mixture is then centrifuged and washed several times with deionized water. After drying, the photoacid generator carrier microcapsules are obtained.

[0018] Preferably, the mass ratio of the emulsifier, tetraarylphosphine salt and polysiloxane precursor in S3 is 1:(9-12):(18-24); the mass ratio of the microcapsules, methyltrimethoxysilane and acidic catalyst in S4 is 1:(0.1-0.3):(0.01-0.03).

[0019] Preferably, the photoacid generator auxiliary agent is an iodonium salt.

[0020] Preferably, the composite solvent consists of propylene glycol methyl ether acetate and cyclopentanone; the mass ratio of the propylene glycol methyl ether acetate to the cyclopentanone is (2-3):1.

[0021] The present application provides a method for preparing a photoresist composition, which adopts the following technical solution:

[0022] A method for preparing a photoresist composition comprises the following steps:

[0023] The perfluorocyclic ether-acrylic acid copolymer, the composite photoacid generator, the alkaline inhibitor and the leveling agent are added to the composite solvent, stirred at room temperature for 4-6 hours, and then filtered through a filter for multiple cycles to obtain a photoresist composition.

[0024] In summary, this application includes at least one of the following beneficial technical effects:

[0025] 1. The present application discloses a fluorine-containing acrylic resin obtained by copolymerizing perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth)acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate; fluorine-containing groups such as perfluorocyclohexyl, perfluoropolyether, and perfluorooctyl have high electron density and low polarity, and can effectively absorb ultraviolet light, thereby increasing the sensitivity of the photoresist to light. The fluorine-containing groups give the resin extremely low surface energy, which helps to form a flatter and smoother film layer during the photolithography process, reduce surface defects and unevenness, and thus improve resolution.

[0026] 2. The photoacid generator carrier microcapsules provided in this application use tetraarylphosphine salts as their cores, have a high quantum yield, and can generate sufficient acid at low exposure doses. This allows the photoresist to achieve the desired chemical reaction at low exposure energy, thereby improving sensitivity. The microcapsule structure can evenly release acid, reduce the diffusion of acid in non-exposed areas, and avoid excessively high or low local acid concentrations, thereby ensuring the uniformity of the photoresist during the development process and improving the resolution of the photolithographic pattern. The polysiloxane shell has a low surface energy, which can reduce the surface tension of the photoresist on the substrate, forming a smoother and more uniform film layer, thereby improving resolution. The surface of the microcapsules is functionalized with methyltrimethoxysilane, which can further improve the surface stability and hydrophobicity of the microcapsules and reduce migration and aggregation during the photolithographic process. The use of iodonium salts as auxiliary agents can synergize with the microcapsule structure to further improve the performance of the photoresist. DETAILED DESCRIPTION

[0027] The present application is further described in detail below with reference to the embodiments.

[0028] The chemical reagents used in the preparation examples, embodiments and comparative examples provided in the present invention are all commercially available products.

[0029] Preparation Example 1 Preparation of multi-polymer fluorinated acrylic resin

[0030] Preparation Example 1.1

[0031] 10 g of perfluorocyclohexyl methyl acrylate, 20 g of perfluoropolyether (meth)acrylate, 10 g of perfluorooctyl ethyl acrylate, and 40 g of methyl methacrylate were added to 120 g of tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution; 0.4 g of azobisisobutyronitrile was added to 6 g of tetrahydrofuran and stirred evenly to obtain an azobisisobutyronitrile solution; the azobisisobutyronitrile solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection and reacted at 70° C. for 6 h; after the reaction was completed, the material was cooled to room temperature and discharged to obtain a multi-component copolymerized fluorine-containing acrylic resin.

[0032] Preparation Example 1.2

[0033] 15 g of perfluorocyclohexyl methyl acrylate, 25 g of perfluoropolyether (meth)acrylate, 15 g of perfluorooctyl ethyl acrylate, and 45 g of methyl methacrylate were added to 150 g of tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution; 0.75 g of azobisisobutyronitrile was added to 12 g of tetrahydrofuran and stirred evenly to obtain an azobisisobutyronitrile solution; the azobisisobutyronitrile solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection and reacted at 75° C. for 7 h; after the reaction was completed, the mixture was cooled to room temperature and discharged to obtain a multi-component copolymerized fluorine-containing acrylic resin.

[0034] Preparation Example 1.3

[0035] 20 g of perfluorocyclohexyl methyl acrylate, 30 g of perfluoropolyether (meth)acrylate, 20 g of perfluorooctyl ethyl acrylate, and 50 g of methyl methacrylate were added to 180 g of tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution; 1.2 g of azobisisobutyronitrile was added to 18 g of tetrahydrofuran and stirred evenly to obtain an azobisisobutyronitrile solution; the azobisisobutyronitrile solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection and reacted at 80° C. for 8 h; after the reaction, the mixture was cooled to room temperature and discharged to obtain a multi-component copolymerized fluorine-containing acrylic resin.

[0036] Preparation Example 2 Preparation of Photoacid Generator Carrier Microcapsules

[0037] Preparation Example 2.1

[0038] S1. Add 7.6 g of tetraphenylphosphine bromide and 0.8 g of pyridine to 44.5 g of tetrahydrofuran and stir until completely dissolved; then slowly add 2.6 g of 2-bromobenzothiazole under nitrogen protection, stir and react at 60°C for 4 h, and after separation and purification, obtain the core material tetraarylphosphine salt;

[0039] S2. 20 g of γ-methacryloxypropyltrimethoxysilane and 20 g of methyltrimethoxysilane were mixed and added to 40 g of tetrahydrofuran and stirred until completely dissolved. 0.2 g of 1 M dilute hydrochloric acid was then added and reacted at 50 ° C for 2 h under nitrogen protection. The solvent was removed by rotary evaporation and the shell material polysiloxane precursor was obtained after separation and purification.

[0040] S3. 1 g of emulsifier Tween 80 and 19 g of water were mixed and stirred to obtain an emulsifier-water mixed solution; 9 g of the tetraaryl phosphine salt prepared in S1 was added to 90 g of tetrahydrofuran and stirred to dissolve to obtain a tetraaryl phosphine salt solution; the tetraaryl phosphine salt solution was then added to the emulsifier-water mixed solution, stirred to obtain a tetraaryl phosphine salt solution, and then 18 g of the polysiloxane precursor prepared in S2 was added dropwise with stirring. After the addition was complete, the mixture was reacted at 60°C for 4 h; the mixture was separated by centrifugation and washed three times with deionized water to obtain microcapsules;

[0041] S4. Disperse 1 g of the microcapsules prepared in S3 in 10 g of ethanol, add 0.1 g of methyltrimethoxysilane, add 0.01 g of 1 M dilute hydrochloric acid under nitrogen protection, and react at 50°C for 2 h. After centrifugation and washing three times with deionized water, the photoacid generator carrier microcapsules are obtained after drying.

[0042] Preparation Example 2.2

[0043] S1. 9.5 g of tetraphenylphosphine bromide and 1 g of pyridine were added to 56 g of tetrahydrofuran and stirred until completely dissolved. 3.25 g of 2-bromobenzothiazole was then slowly added under nitrogen and stirred at 70°C for 5 h. After separation and purification, the core material tetraarylphosphine salt was obtained.

[0044] S2. 25 g of γ-methacryloxypropyltrimethoxysilane and 25 g of methyltrimethoxysilane were mixed and added to 60 g of tetrahydrofuran and stirred until completely dissolved. 0.35 g of 1 M dilute hydrochloric acid was then added and reacted at 60 ° C under nitrogen for 2.5 h. The solvent was removed by rotary evaporation and the shell material polysiloxane precursor was obtained after separation and purification.

[0045] S3. 1 g of emulsifier Tween 80 and 19 g of water were mixed and stirred to obtain an emulsifier-water mixed solution; 10.5 g of the tetraaryl phosphine salt prepared in S1 was added to 100 g of tetrahydrofuran and stirred to dissolve to obtain a tetraaryl phosphine salt solution; the tetraaryl phosphine salt solution was then added to the emulsifier-water mixed solution, stirred to obtain a tetraaryl phosphine salt solution, and then 21 g of the polysiloxane precursor prepared in S2 was added dropwise with stirring. After the addition was complete, the mixture was reacted at 65°C for 5 h; microcapsules were obtained after centrifugation and washed four times with deionized water;

[0046] S4. Disperse 1 g of the microcapsules prepared in S3 in 10 g of ethanol, and add 0.2 g of methyltrimethoxysilane. Under nitrogen protection, add 0.02 g of 1 M dilute hydrochloric acid, and react at 55°C for 2.5 h. After centrifugation and washing four times with deionized water, the photoacid generator carrier microcapsules are obtained after drying.

[0047] Preparation Example 2.3

[0048] S1. Add 11.4 g of tetraphenylphosphine bromide and 1.2 g of pyridine to 67 g of tetrahydrofuran and stir until completely dissolved; then slowly add 3.9 g of 2-bromobenzothiazole under nitrogen protection, stir and react at 80°C for 6 h, and after separation and purification, obtain the core material tetraarylphosphine salt;

[0049] S2. 30 g of γ-methacryloxypropyltrimethoxysilane and 30 g of methyltrimethoxysilane were mixed and added to 80 g of tetrahydrofuran and stirred until completely dissolved. 0.5 g of 1 M dilute hydrochloric acid was then added and reacted at 70 ° C for 3 h under nitrogen protection. The solvent was removed by rotary evaporation and the shell material polysiloxane precursor was obtained after separation and purification.

[0050] S3. 1 g of emulsifier Tween 80 and 19 g of water were mixed and stirred to obtain an emulsifier-water mixed solution; 12 g of the tetraaryl phosphine salt prepared in S1 was added to 120 g of tetrahydrofuran and stirred to dissolve to obtain a tetraaryl phosphine salt solution; the tetraaryl phosphine salt solution was then added to the emulsifier-water mixed solution, stirred to obtain a tetraaryl phosphine salt solution, and then 24 g of the polysiloxane precursor prepared in S2 was added dropwise with stirring. After the addition was complete, the mixture was reacted at 70°C for 6 h; the mixture was separated by centrifugation and washed five times with deionized water to obtain microcapsules;

[0051] S4. Disperse 1 g of the microcapsules prepared in S3 in 10 g of ethanol, add 0.3 g of methyltrimethoxysilane, add 0.03 g of 1 M dilute hydrochloric acid under nitrogen protection, and react at 60°C for 3 h. After centrifugation and washing with deionized water five times, the photoacid generator carrier microcapsules were obtained after drying.

[0052] Example 1

[0053] 40 g of the multi-component fluorinated acrylic resin prepared in Preparation Example 1.1, 2 g of a composite photoacid generator, 0.5 g of an alkaline inhibitor, and 0.1 g of a leveling agent were added to 40 g of a composite solvent, stirred at room temperature for 4 h, and then filtered three times through a 0.22 μm polytetrafluoroethylene filter to obtain a photoresist composition;

[0054] The composite photoacid generator used in this example includes the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium trifluoromethanesulfonate, with a mass ratio of 1:0.2;

[0055] The alkaline inhibitor used was tetrabutylammonium hydroxide;

[0056] The leveling agent used is polymethylphenylsiloxane;

[0057] The composite solvent used includes propylene glycol methyl ether acetate and cyclopentanone; the mass ratio of the two is 2:1.

[0058] Example 2

[0059] 50 g of the multi-component copolymerized fluorinated acrylic resin prepared in Preparation Example 1.1, 3.5 g of a composite photoacid generator, 0.75 g of an alkaline inhibitor, and 0.2 g of a leveling agent were added to 50 g of a composite solvent, stirred at room temperature for 5 h, and then filtered four times through a 0.22 μm polytetrafluoroethylene filter to obtain a photoresist composition;

[0060] The composite photoacid generator used in this example includes the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium perfluorooctane sulfonate, with the mass ratio of the two being 1:0.2;

[0061] The alkaline inhibitor used was tetrabutylammonium hydroxide;

[0062] The leveling agent used is polymethylphenylsiloxane;

[0063] The composite solvent used includes propylene glycol methyl ether acetate and cyclopentanone; the mass ratio of the two is 2:1.

[0064] Example 3

[0065] 60 g of the multi-component copolymerized fluorinated acrylic resin prepared in Preparation Example 1.1, 5 g of a composite photoacid generator, 1 g of an alkaline inhibitor, and 0.3 g of a leveling agent were added to 60 g of a composite solvent, stirred at room temperature for 6 h, and then filtered three times through a 0.22 μm polytetrafluoroethylene filter to obtain a photoresist composition;

[0066] The composite photoacid generator used in this example includes the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary triphenylsulfonium trifluoromethanesulfonate, with a mass ratio of 1:0.2;

[0067] The alkaline inhibitor used was tetrabutylammonium hydroxide;

[0068] The leveling agent used is polymethylphenylsiloxane;

[0069] The composite solvent used includes propylene glycol methyl ether acetate and cyclopentanone; the mass ratio of the two is 2:1.

[0070] Example 4

[0071] The difference between Example 4 and Example 1 is that the mass ratio of the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium trifluoromethanesulfonate used in Example 4 is 1:0.4.

[0072] Example 5

[0073] The difference between Example 5 and Example 1 is that the mass ratio of the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium trifluoromethanesulfonate used in Example 5 is 1:0.6.

[0074] Example 6

[0075] The difference between Example 6 and Example 1 is that the photoacid generator carrier microcapsules used in Example 6 are prepared by Preparation Example 2.2.

[0076] Example 7

[0077] The difference between Example 7 and Example 1 is that the photoacid generator carrier microcapsules used in Example 7 are prepared by Preparation Example 2.3.

[0078] Example 8

[0079] The difference between Example 8 and Example 1 is that the multi-component copolymerized fluorine-containing acrylic resin used in Example 8 is prepared by Preparation Example 1.2.

[0080] Example 9

[0081] The difference between Example 9 and Example 1 is that the multi-component copolymerized fluorine-containing acrylic resin used in Example 8 is prepared by Preparation Example 1.3.

[0082] Example 10

[0083] The difference between Example 10 and Example 1 is that the mass ratio of the composite solvent propylene glycol methyl ether acetate and cyclopentanone used in Example 10 is 2.5:1.

[0084] Example 11

[0085] The difference between Example 11 and Example 1 is that the mass ratio of the composite solvent propylene glycol methyl ether acetate and cyclopentanone used in Example 11 is 3:1.

[0086] Example 12

[0087] The difference between Example 12 and Example 1 is that the mass ratio of the composite solvent propylene glycol methyl ether acetate and cyclopentanone used in Example 12 is 1:1.

[0088] Example 13

[0089] The difference between Example 13 and Example 1 is that the mass ratio of the composite solvent propylene glycol methyl ether acetate and cyclopentanone used in Example 13 is 4:1.

[0090] Comparative Example 1

[0091] The difference between Comparative Example 1 and Example 1 is that the mass ratio of the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium trifluoromethanesulfonate used in Comparative Example 1 is 1:0.1.

[0092] Comparative Example 2

[0093] The difference between Comparative Example 2 and Example 1 is that the mass ratio of the photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and the photoacid generator auxiliary diphenyliodonium trifluoromethanesulfonate used in Comparative Example 2 is 1:0.8.

[0094] Comparative Example 3

[0095] The difference between Comparative Example 3 and Example 1 is that in Comparative Example 3, an equal amount of acrylic resin is used instead of the multi-component copolymerized fluorine-containing acrylic resin.

[0096] Comparative Example 4

[0097] The difference between Comparative Example 4 and Example 1 is that the photoacid generator used in Comparative Example 4 is a single photoacid generator carrier microcapsule prepared in Preparation Example 2.3, with a mass of 2 g.

[0098] Comparative Example 5

[0099] The difference between Comparative Example 5 and Example 1 is that the photoacid generator used in Comparative Example 5 is a single diphenyliodonium trifluoromethanesulfonate with a mass of 2 g.

[0100] Comparative Example 6

[0101] The difference between Comparative Example 6 and Example 1 is that the solvent used in Comparative Example 6 is single propylene glycol methyl ether acetate, with a mass of 40 g.

[0102] Performance testing

[0103] Using a spin coater, an antireflective coating ARC-29 (Nissan Chemical Industries, Ltd.) was coated on a silicon wafer (12 inches), and then baked at 205° C. for 60 seconds to form a 70 nm thick organic antireflective coating. The photoresist compositions prepared in Examples 1 to 13 and Comparative Examples 1 to 6 were then coated, respectively, and dried at 110° C. for 90 seconds to form a film with a thickness of 0.20 μm.

[0104] (i) The resulting structure was exposed using an immersion exposure apparatus (1700i, manufactured by ASML Co.) and baked at 105°C for 60 seconds. Thereafter, the film was developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds, washed, and dried. Thus, a photoresist pattern was formed, using ultrapure water as an immersion medium. The exposure dose used when a line-and-space (L / S) pattern of 0.10 μm was formed with a line width of 1:1 after development was designated as the optimal exposure dose, and the optimal exposure dose was designated as the sensitivity (unit: mJ / cm 2 The minimum pattern size that can be distinguished at this time is designated as resolution (unit: nm).

[0105] (ii) In the case of line edge roughness (LER), the pattern roughness in the 0.10 μm line spacing (L / S) pattern formed after development was observed, and the LER was measured (smaller values ​​indicate better LER) (unit: nm).

[0106] The specific test results are as follows:

[0107] Table 1 Performance test results

[0108]

[0109]

[0110] It can be seen from the test results in Table 1 that the photoresist composition provided by the present application has high sensitivity and resolution, and low surface roughness after etching.

[0111] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A photoresist composition, characterized in that: The raw materials include, by weight, 40-60 parts of a multi-component copolymerized fluorine-containing acrylic resin, 2-5 parts of a composite photoacid generator, 0.5-1 parts of an alkaline inhibitor, 0.1-0.3 parts of a leveling agent, and 40-60 parts of a composite solvent; the composite photoacid generator includes a photoacid generator carrier microcapsule and a photoacid generator auxiliary agent; and the mass ratio of the photoacid generator carrier microcapsule to the photoacid generator auxiliary agent is 1:(0.2-0.6).

2. A photoresist composition according to claim 1, characterized in that: The raw materials of the photoresist composition include 50 parts of multi-component copolymerized fluorine-containing acrylic resin, 3.5 parts of composite photoacid generator, 0.75 parts of alkaline inhibitor, 0.2 parts of leveling agent and 50 parts of composite solvent in parts by weight.

3. A photoresist composition according to claim 1, characterized in that: The preparation method of the multi-component copolymerized fluorine-containing acrylic resin comprises the following steps: Perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth)acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate are added to tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution; azobisisobutyronitrile is added to tetrahydrofuran and stirred evenly to obtain an azobisisobutyronitrile solution; the azobisisobutyronitrile solution is added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection and reacted at 70-80°C for 6-8h; after the reaction is completed, the material is cooled to room temperature and discharged to obtain a multi-component copolymerized fluorine-containing acrylic resin.

4. A photoresist composition according to claim 3, characterized in that: The mass ratio of the perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth)acrylate, perfluorooctyl ethyl acrylate and methyl methacrylate is (1-2): (2-3): (1-2): (4-5).

5. A photoresist composition according to claim 3, characterized in that: The mass of the azobisisobutyronitrile is 0.5-1.0% of the total mass of perfluorocyclohexyl methyl acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate and methyl methacrylate.

6. A photoresist composition according to claim 1, characterized in that: The core material of the photoacid generator carrier microcapsule is tetraarylphosphine salt; The shell material is a polysiloxane precursor; the surface is functionalized; The preparation method of the photoacid generator carrier microcapsule comprises the following steps: S1. Add 7.6-11.4 parts of tetraphenylphosphine bromide and 0.8-1.2 parts of pyridine to 44.5-67 parts of tetrahydrofuran by weight and stir until completely dissolved; then slowly add 2.6-3.9 parts of 2-bromobenzothiazole under nitrogen protection, stir and react at 60-80 ° C for 4-6 hours, and obtain the core material tetraarylphosphine salt after separation and purification; S2. 20-30 parts of γ-methacryloxypropyltrimethoxysilane and 20-30 parts of methyltrimethoxysilane were mixed and added to 40-80 parts of tetrahydrofuran, stirred until completely dissolved, and then 0.2-0.5 parts of an acidic catalyst were added. Under nitrogen protection, the reaction was carried out at 50-70 ° C for 2-3 hours. The solvent was removed by rotary evaporation, and the shell material polysiloxane precursor was obtained after separation and purification; S3. After mixing the emulsifier and water, stirring evenly to obtain an emulsifier-water mixed solution; adding a tetraaryl phosphine salt to tetrahydrofuran, stirring and dissolving to obtain a tetraaryl phosphine salt solution; then adding the tetraaryl phosphine salt solution to the emulsifier-water mixed solution, stirring evenly, and then adding the polysiloxane precursor dropwise while stirring. After the addition is complete, reacting at 60-70°C for 4-6 hours; separating by centrifugation and washing several times with deionized water to obtain microcapsules; S4. The microcapsules are dispersed in ethanol, and methyltrimethoxysilane is added. Under nitrogen protection, an acidic catalyst is added, and the mixture is reacted at 50-60°C for 2-3 hours. The mixture is then centrifuged and washed several times with deionized water. After drying, the photoacid generator carrier microcapsules are obtained.

7. A photoresist composition according to claim 6, characterized in that: The mass ratio of the emulsifier, tetraarylphosphine salt and polysiloxane precursor in S3 is 1:(9-12):(18-24); the mass ratio of the microcapsules, methyltrimethoxysilane and acidic catalyst in S4 is 1:(0.1-0.3):(0.01-0.03).

8. The photoresist composition according to claim 1, wherein: The photoacid generator auxiliary agent is iodonium salt.

9. A photoresist composition according to claim 1, characterized in that: The composite solvent consists of propylene glycol methyl ether acetate and cyclopentanone; the mass ratio of the propylene glycol methyl ether acetate to the cyclopentanone is (2-3):

1.

10. The method for preparing a photoresist composition according to any one of claims 1 to 9, wherein: The following steps are involved: The perfluorocyclic ether-acrylic acid copolymer, the composite photoacid generator, the alkaline inhibitor and the leveling agent are added to the composite solvent, stirred at room temperature for 4-6 hours, and then filtered through a filter for multiple cycles to obtain a photoresist composition.

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