A photoresist composition and a method for preparing the same

Abstract

The application discloses a photoresist composition and a preparation method thereof, relates to the technical field of photoresist, and raw materials thereof include, in terms of weight parts, polyfluorinated acrylic resin 40-60 parts, composite photoacid generator 2-5 parts, alkaline inhibitor 0.5-1 part, leveling agent 0.1-0.3 part, and composite solvent 40-60 parts; the composite photoacid generator includes photoacid generator carrier microcapsules and photoacid generator adjuvant; and the mass ratio of the photoacid generator carrier microcapsules to the photoacid generator adjuvant is 1:0.2-0.6. The photoresist composition has the advantages of high resolution, high sensitivity and low surface roughness after etching.

Description

Technical Field

[0001] This application relates to the field of photoresist technology, and in particular to a photoresist composition and its preparation method. Background Technology

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

[0003] As the basic material of photoresist, the optimization of its preparation process and quality control directly affect the resolution of the pattern and the production efficiency. In 193nm photolithography, the main photoresist resins reported so far are mainly divided into three categories: (1) (meth)acrylate derivatives; (2) cycloolefin-maleic anhydride copolymers; and (3) polynorbornene derivatives. However, all 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 prone to polymerization, and the acid-sensitive groups in the monomers are also prone to decomposition, so the purification conditions are extremely strict. In addition, the main chain of acrylates has a linear structure and a low carbon-hydrogen ratio (C / H ratio), resulting in poor etch resistance. Although cycloolefin-maleic anhydride copolymers can resolve 3nm lines in some cases, and even 1nm lines under optimal conditions, their film 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, this application provides a photoresist composition and a method for preparing the same.

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

[0006] A photoresist composition, comprising, by weight, 40-60 parts of a multi-component copolymer fluorinated 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; wherein the composite photoacid generator comprises photoacid generator carrier microcapsules and photoacid generator additives; the mass ratio of the photoacid generator carrier microcapsules to the photoacid generator additives is 1:(0.2-0.6).

[0007] Preferably, the photoresist composition raw materials include, by weight, 50 parts of multi-component copolymer fluorinated 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.

[0008] Preferably, the preparation method of the multi-component copolymer fluorinated acrylic resin includes the following steps:

[0009] Perfluorocyclohexyl acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate were added to tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution. Azobisisobutyronitrile (AIBN) was added to tetrahydrofuran and stirred until homogeneous to obtain an AIBN solution. The AIBN solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection at 70-80°C for 6-8 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain a multi-component copolymer fluorinated acrylic resin.

[0010] Preferably, the mass ratio of perfluorocyclohexyl 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 acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate.

[0012] Preferably, the core material of the photoacid-producing agent carrier microcapsule is a tetraarylphosphine salt; the shell material is a polysiloxane precursor; and the surface is functionalized.

[0013] The preparation method of the photoacid-producing agent carrier microcapsules includes the following steps:

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

[0015] S2. Mix 20-30 parts of γ-methacryloxypropyltrimethoxysilane and 20-30 parts of methyltrimethoxysilane and add them to 40-80 parts of tetrahydrofuran. Stir until completely dissolved, then add 0.2-0.5 parts of acidic catalyst. Under nitrogen protection, react at 50-70℃ for 2-3 hours. Remove the solvent by rotary evaporation and obtain the shell polysiloxane precursor after separation and purification.

[0016] S3. Mix the emulsifier and water, and stir until homogeneous to obtain an emulsifier-water mixture solution; add the tetraarylphosphine salt to tetrahydrofuran, stir until dissolved, and obtain a tetraarylphosphine salt solution; then add the tetraarylphosphine salt solution to the emulsifier-water mixture solution, stir until homogeneous, and then add the polysiloxane precursor dropwise while stirring. After the addition is complete, react at 60-70℃ for 4-6 hours; after centrifugation and washing several times with deionized water, obtain microcapsules.

[0017] S4. Disperse the microcapsules in ethanol and add methyltrimethoxysilane. Under nitrogen protection, add an acidic catalyst and react at 50-60℃ for 2-3 hours. After centrifugation and washing several times with deionized water, and drying, the photo-induced acid-producing agent 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); and 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 photo-induced acid-producing agent is an iodonium salt.

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

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

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

[0023] A perfluorocyclic ether-acrylic acid copolymer, a composite photoacid generator, an alkaline inhibitor, and a leveling agent are added to a composite solvent. After stirring at room temperature for 4-6 hours, the mixture is filtered through a filter multiple times to obtain a photoresist composition.

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

[0025] 1. This application describes a fluorinated acrylic resin obtained by copolymerizing perfluorocyclohexyl acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate. The fluorinated groups such as perfluorocyclohexyl, perfluoropolyether, and perfluorooctyl have high electron density and low polarity, which can effectively absorb ultraviolet light, thereby improving the photoresist's light sensitivity. The fluorinated groups endow the resin with extremely low surface energy, which helps to form a smoother and flatter film during the photolithography process, reducing surface defects and non-uniformity, thereby improving resolution.

[0026] 2. The photoacid-generating agent carrier microcapsules provided in this application use tetraarylphosphine salt as the core, exhibiting high quantum yield and the ability to generate sufficient acid at low exposure doses. This allows the photoresist to achieve the required chemical reaction at lower exposure energies, thereby improving sensitivity. The microcapsule structure can uniformly release acid, reducing acid diffusion in non-exposed areas and avoiding excessively high or low local acid concentrations, thus ensuring the uniformity of the photoresist during development and improving the resolution of the photolithographic pattern. The polysiloxane shell has low surface energy, reducing the surface tension of the photoresist on the substrate and forming a smoother and more uniform film layer, thereby improving resolution. Furthermore, functionalization treatment of the microcapsule surface with methyltrimethoxysilane can further improve the surface stability and hydrophobicity of the microcapsules, reducing migration and aggregation during the photolithography process. Using iodonium salt as an additive can synergistically enhance the performance of the photoresist with the microcapsule structure. Detailed Implementation

[0027] The present application will be 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 this invention are all commercially available products.

[0029] Preparation Example 1: Preparation of Multi-component Copolymer Fluorinated Acrylic Resin

[0030] Preparation Example 1.1

[0031] 10g of perfluorocyclohexyl acrylate, 20g of perfluoropolyether (meth) acrylate, 10g of perfluorooctyl ethyl acrylate, and 40g of methyl methacrylate were added to 120g of tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution. 0.4g of azobisisobutyronitrile (AIBN) was added to 6g of tetrahydrofuran and stirred until homogeneous to obtain an AIBN solution. The AIBN solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection at 70°C for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain a multi-component copolymer fluorinated acrylic resin.

[0032] Preparation Example 1.2

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

[0034] Preparation Example 1.3

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

[0036] Preparation Example 2: Preparation of photoacid-producing agent carrier microcapsules

[0037] Preparation Example 2.1

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

[0039] S2. Mix 20g of γ-methacryloxypropyltrimethoxysilane and 20g of methyltrimethoxysilane and add them to 40g of tetrahydrofuran. Stir until completely dissolved, then add 0.2g of 1M dilute hydrochloric acid. Under nitrogen protection, react at 50℃ for 2h. Remove the solvent by rotary evaporation and obtain the shell polysiloxane precursor after separation and purification.

[0040] S3. Mix 1g of emulsifier Tween 80 and 19g of water, and stir until homogeneous to obtain an emulsifier-water mixture solution; add 9g of tetraarylphosphine salt prepared by S1 to 90g of tetrahydrofuran, stir until dissolved to obtain a tetraarylphosphine salt solution; then add the tetraarylphosphine salt solution to the emulsifier-water mixture solution, stir until homogeneous, and then add 18g of polysiloxane precursor prepared by S2 dropwise while stirring. After the addition is complete, react at 60℃ for 4h; after centrifugation and washing three times with deionized water, obtain microcapsules.

[0041] S4. Disperse 1g of the microcapsules prepared in S3 in 10g of ethanol, add 0.1g of methyltrimethoxysilane, add 0.01g of 1M dilute hydrochloric acid under nitrogen protection, and react at 50℃ for 2h. After centrifugation and washing with deionized water 3 times, and drying, the photo-induced acid-producing agent carrier microcapsules are obtained.

[0042] Preparation Example 2.2

[0043] S1. Add 9.5g tetraphenylphosphine bromide and 1g pyridine to 56g tetrahydrofuran and stir until completely dissolved; then slowly add 3.25g 2-bromobenzothiazole under nitrogen protection and stir at 70℃ for 5h. After separation and purification, the core material tetraarylphosphine salt is obtained.

[0044] S2. Mix 25g of γ-methacryloxypropyltrimethoxysilane and 25g of methyltrimethoxysilane and add them to 60g of tetrahydrofuran. Stir until completely dissolved, then add 0.35g of 1M dilute hydrochloric acid. Under nitrogen protection, react at 60℃ for 2.5h. Remove the solvent by rotary evaporation and obtain the shell polysiloxane precursor after separation and purification.

[0045] S3. Mix 1g of emulsifier Tween 80 and 19g of water, and stir until homogeneous to obtain an emulsifier-water mixture solution; add 10.5g of tetraarylphosphine salt prepared in S1 to 100g of tetrahydrofuran, stir until dissolved to obtain a tetraarylphosphine salt solution; then add the tetraarylphosphine salt solution to the emulsifier-water mixture solution, stir until homogeneous, and then add 21g of polysiloxane precursor prepared in S2 dropwise while stirring. After the addition is complete, react at 65℃ for 5h; after centrifugation and washing 4 times with deionized water, obtain microcapsules.

[0046] S4. Disperse 1g of the microcapsules prepared by S3 in 10g of ethanol, add 0.2g of methyltrimethoxysilane, add 0.02g of 1M dilute hydrochloric acid under nitrogen protection, and react at 55℃ for 2.5h. After centrifugation and washing with deionized water 4 times, and drying, the photo-induced acid-producing agent carrier microcapsules are obtained.

[0047] Preparation Example 2.3

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

[0049] S2. Mix 30g of γ-methacryloxypropyltrimethoxysilane and 30g of methyltrimethoxysilane and add them to 80g of tetrahydrofuran. Stir until completely dissolved, then add 0.5g of 1M dilute hydrochloric acid. Under nitrogen protection, react at 70℃ for 3h. Remove the solvent by rotary evaporation and obtain the shell polysiloxane precursor after separation and purification.

[0050] S3. Mix 1g of emulsifier Tween 80 and 19g of water, and stir until homogeneous to obtain an emulsifier-water mixture solution; add 12g of tetraarylphosphine salt prepared by S1 to 120g of tetrahydrofuran, stir until dissolved to obtain a tetraarylphosphine salt solution; then add the tetraarylphosphine salt solution to the emulsifier-water mixture solution, stir until homogeneous, and then add 24g of polysiloxane precursor prepared by S2 dropwise while stirring. After the addition is complete, react at 70℃ for 6h; after centrifugation and washing 5 times with deionized water, obtain microcapsules.

[0051] S4. Disperse 1g of the microcapsules prepared by S3 in 10g of ethanol, add 0.3g of methyltrimethoxysilane, add 0.03g of 1M dilute hydrochloric acid under nitrogen protection, and react at 60℃ for 3h. After centrifugation and washing with deionized water 5 times, and drying, the photo-induced acid-producing agent carrier microcapsules are obtained.

[0052] Example 1

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

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

[0055] The alkaline inhibitor used is 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] 50g of the multi-component copolymer fluorinated acrylic resin prepared in Preparation Example 1.1, 3.5g of composite photoacid generator, 0.75g of alkaline inhibitor, and 0.2g of leveling agent were added to 50g of composite solvent. After stirring at room temperature for 5h, the mixture was filtered four times through a 0.22μm polytetrafluoroethylene filter to obtain a photoresist composition.

[0060] The composite photoacid generator used in this embodiment includes photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and photoacid generator adjuvant diphenyliodonium perfluorooctane sulfonate, with a mass ratio of 1:0.2.

[0061] The alkaline inhibitor used is 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] 60g of the multi-component copolymer fluorinated acrylic resin prepared in Preparation Example 1.1, 5g of composite photoacid generator, 1g of alkaline inhibitor, and 0.3g of leveling agent were added to 60g of composite solvent. After stirring at room temperature for 6h, the mixture was filtered three times through a 0.22μm polytetrafluoroethylene filter to obtain a photoresist composition.

[0066] The composite photoacid generator used in this embodiment includes photoacid generator carrier microcapsules prepared in Preparation Example 2.1 and photoacid generator auxiliary agent triphenylthionium trifluoromethanesulfonate, with a mass ratio of 1:0.2.

[0067] The alkaline inhibitor used is 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 photoacid-producing agent carrier microcapsules prepared in Example 2.1 and the photoacid-producing agent adjuvant diphenyliodonium trifluoromethanesulfonate used in Example 4 have a mass ratio of 1:0.4.

[0072] Example 5

[0073] The difference between Example 5 and Example 1 is that the photoacid-producing agent carrier microcapsules prepared in Example 2.1 and the photoacid-producing agent adjuvant diphenyliodonium trifluoromethanesulfonate are used in Example 5 in a mass ratio of 1:0.6.

[0074] Example 6

[0075] The difference between Example 6 and Example 1 is that the photoacid-producing agent carrier microcapsules used in Example 6 were prepared from Preparation Example 2.2.

[0076] Example 7

[0077] The difference between Example 7 and Example 1 is that the photoacid-producing agent carrier microcapsules used in Example 7 were prepared from Preparation Example 2.3.

[0078] Example 8

[0079] The difference between Example 8 and Example 1 is that the multi-component copolymer fluorinated acrylic resin used in Example 8 was prepared from Preparation Example 1.2.

[0080] Example 9

[0081] The difference between Example 9 and Example 1 is that the multi-component copolymer fluorinated acrylic resin used in Example 8 was 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 to 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 to 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 to 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 photoacid-producing agent carrier microcapsules prepared in Comparative Example 1 and the photoacid-producing agent adjuvant diphenyliodonium trifluoromethanesulfonate prepared in Preparation Example 2.1 are used in a mass ratio of 1:0.1.

[0092] Comparative Example 2

[0093] The difference between Comparative Example 2 and Example 1 is that the photoacid-producing agent carrier microcapsules prepared in Comparative Example 2.1 and the photoacid-producing agent adjuvant diphenyliodonium trifluoromethanesulfonate were used in a mass ratio of 1:0.8.

[0094] Comparative Example 3

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

[0096] Comparative Example 4

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

[0098] Comparative Example 5

[0099] The difference between Comparative Example 5 and Example 1 is that the photo-induced acid-producing agent used in Comparative Example 5 is a single diphenyliodonium trifluoromethanesulfonate, with a mass of 2g.

[0100] Comparative Example 6

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

[0102] Performance testing

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

[0104] (i) The obtained structure was exposed using an immersion exposure apparatus (1700i, manufactured by ASML Co.) and baked at 105°C for 60 s; subsequently, the film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution for 40 s, followed by washing and drying; this formed a photoresist pattern using ultrapure water as the immersion medium. The exposure used to form a 0.10 μm line-and-space (L / S) pattern with a 1:1 line width after development was designated as the optimal exposure, and this optimal exposure was designated as the sensitivity (unit: mJ / cm). 2 The smallest pattern size that can be resolved at this point will be specified as the resolution (in nm).

[0105] (ii) In the case of edge roughness (LER), observe the pattern roughness in the 0.10 μm scribe line spacing (L / S) pattern formed after development, and measure the LER (the smaller the value, the better the LER) (unit: nm).

[0106] The specific test results are as follows:

[0107] Table 1 Performance Test Results

[0108]

[0109]

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

[0111] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A photoresist composition, characterized in that: The raw materials, by weight, include 40-60 parts of multi-component copolymer fluorinated acrylic resin, 2-5 parts of composite photoacid-generating agent, 0.5-1 parts of alkaline inhibitor, 0.1-0.3 parts of leveling agent, and 40-60 parts of composite solvent; the composite photoacid-generating agent comprises photoacid-generating agent carrier microcapsules and photoacid-generating agent additives; the mass ratio of the photoacid-generating agent carrier microcapsules to the photoacid-generating agent additives is 1:(0.2-0.6); The core material of the photoacid-producing agent carrier microcapsule is a tetraarylphosphine salt; The shell material is a polysiloxane precursor; the surface is functionalized. The preparation method of the photoacid-producing agent carrier microcapsules includes the following steps: S1. Add 7.6-11.4 parts by weight of tetraphenylphosphine bromide and 0.8-1.2 parts by weight of pyridine to 44.5-67 parts by weight of tetrahydrofuran and stir until completely dissolved; then slowly add 2.6-3.9 parts by weight of 2-bromobenzothiazole under nitrogen protection and stir the reaction at 60-80℃ for 4-6 hours. After separation and purification, the core material tetraarylphosphine salt is obtained. S2. Mix 20-30 parts of γ-methacryloxypropyltrimethoxysilane and 20-30 parts of methyltrimethoxysilane and add them to 40-80 parts of tetrahydrofuran. Stir until completely dissolved, then add 0.2-0.5 parts of acidic catalyst. Under nitrogen protection, react at 50-70℃ for 2-3 hours. Remove the solvent by rotary evaporation and obtain the shell polysiloxane precursor after separation and purification. S3. Mix the emulsifier and water, and stir until homogeneous to obtain an emulsifier-water mixture solution; add the tetraarylphosphine salt to tetrahydrofuran, stir until dissolved, and obtain a tetraarylphosphine salt solution; then add the tetraarylphosphine salt solution to the emulsifier-water mixture solution, stir until homogeneous, and then add the polysiloxane precursor dropwise while stirring. After the addition is complete, react at 60-70℃ for 4-6 hours; after centrifugation and washing several times with deionized water, obtain microcapsules. S4. Disperse the microcapsules in ethanol and add methyltrimethoxysilane. Under nitrogen protection, add an acidic catalyst and react at 50-60℃ for 2-3 hours. After centrifugation and washing several times with deionized water, and drying, the photo-induced acid-producing agent carrier microcapsules are obtained.

2. The photoresist composition according to claim 1, characterized in that: The photoresist composition raw materials include, by weight, 50 parts of multi-component copolymer fluorinated 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.

3. The photoresist composition according to claim 1, characterized in that: The preparation method of the multi-component copolymer fluorinated acrylic resin includes the following steps: Perfluorocyclohexyl acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate were added to tetrahydrofuran and stirred until completely dissolved to obtain a mixed solution. Azobisisobutyronitrile (AIBN) was added to tetrahydrofuran and stirred until homogeneous to obtain an AIBN solution. The AIBN solution was added dropwise to the mixed solution while stirring, and then placed in an oil bath under nitrogen protection at 70-80°C for 6-8 hours. After the reaction was completed, the mixture was cooled to room temperature and discharged to obtain a multi-component copolymer fluorinated acrylic resin.

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

5. The 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 acrylate, perfluoropolyether (meth) acrylate, perfluorooctyl ethyl acrylate, and methyl methacrylate.

6. The photoresist composition according to claim 1, 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).

7. The photoresist composition according to claim 1, characterized in that: The photo-induced acid-producing agent is iodonium salt.

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

1.

9. A method for preparing a photoresist composition according to any one of claims 1-8, characterized in that: Includes the following steps: A perfluorocyclic ether-acrylic acid copolymer, a composite photoacid generator, an alkaline inhibitor, and a leveling agent are added to a composite solvent. After stirring at room temperature for 4-6 hours, the mixture is filtered through a filter multiple times to obtain a photoresist composition.

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