Top anti-reflection coating composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of semiconductor manufacturing, and particularly relates to a top anti-reflection coating composition and a preparation method and application thereof. The top anti-reflection coating composition comprises polymer resin, a photoacid generator and an organic solvent I; the polymer resin has a structure as shown in a formula (1). The key point of the invention is to design and synthesize a polymer resin with a specific structure, and through the synergistic effect of all unit structures in the polymer resin structure and regulation and control of all the unit structures in a specific proportion range, the surface of the formed top anti-reflection coating has excellent super-hydrophobic performance; the water infiltration defect in immersion photoetching is effectively inhibited, the developing contrast ratio is improved, the line edge roughness is reduced, and meanwhile it is ensured that the top anti-reflection coating has the excellent anti-reflection performance. Formula (1)

Description

Technical Field

[0001] This invention belongs to the field of semiconductor manufacturing technology, specifically relating to a top anti-reflective coating composition, its preparation method, and its application. Background Technology

[0002] As semiconductor process nodes advance to 5nm and below, extreme ultraviolet lithography and high numerical aperture immersion lithography have become mainstream technologies. In these advanced processes, the top anti-reflective coating (TARC) plays a crucial role. An ideal TARC should possess the following characteristics: (1) a precisely tunable refractive index and an extinction coefficient close to zero at a specific wavelength; (2) excellent hydrophobicity to prevent watermark defects in immersion lithography; (3) good interaction with the developer to ensure residue-free removal; and (4) a clear interface with the underlying photoresist to avoid miscibility.

[0003] The main problem with existing TARC materials lies in their insufficient dynamic contact angle, especially the backslip angle, which easily leads to watermark defects during immersion lithography. Simultaneously, their limited development contrast affects the edge roughness of the final pattern. Currently, most research achieves developability and basic hydrophobicity by using polymers containing hexafluoroisopropanol groups. However, with the continuous increase in numerical aperture and the narrowing of the process window, existing TARC materials face challenges: the hydrophobicity provided by hexafluoroisopropanol groups alone has reached its limit, making it difficult to meet the defect control requirements of higher-order immersion lithography; insufficient development contrast may lead to increased edge roughness or trace residues. Therefore, there is an urgent need to develop a novel top anti-reflective coating material that can provide superior surface properties and higher patterning quality without sacrificing optical performance and developability. Summary of the Invention

[0004] The purpose of this invention is to address the problem that existing TARC materials are difficult to improve surface hydrophobicity and reduce line edge roughness (LER) of photolithographic patterns while ensuring optical performance. This invention provides a top anti-reflective coating composition, its preparation method, and its application. The polymer resin with a specific structure provided by this invention can improve the hydrophobicity of the top anti-reflective coating, and when applied in photolithography, it can reduce the line edge roughness of the resulting photolithographic pattern and improve the pattern quality.

[0005] In a first aspect, the present invention provides a top antireflective coating composition. The top antireflective coating composition comprises a polymer resin, a photoacid-generating agent, and an organic solvent I; the polymer resin has the structure shown in formula (1): Equation (1), In equation (1), R 11 R 12R 13 Each is independently a hydrogen atom or a C1~C3 alkyl group, R2 is a C1~C5 alkyl group, R3 is a single bond or a C1~C3 alkylene group, R4 is a C8~C16 perfluoroalkyl group, R5 is an acid-sensitive group, and a:b:c:d=(35~55%):(30~50%):(2~10%):(5~20%).

[0006] In a preferred embodiment, the polymer resin has a weight-average molecular weight of 5000~30000 g / mol and a PDI of 0.80~2.00.

[0007] In a preferred embodiment, the acid-sensitive group is selected from at least one of the following structures: .

[0008] In a preferred embodiment, the polymer resin is prepared as follows: acrylate monomer I shown in formula (2), acrylate monomer II shown in formula (3), acrylate monomer III shown in formula (4), and styrene monomer shown in formula (5) are subjected to free radical copolymerization under the action of an initiator, and the resulting reaction product is a polymer resin having the structure shown in formula (1). Equation (2), Equation (3), Equation (4), Equation (5), In equation (2), R 11 R1 is a hydrogen atom or a C1-C3 alkyl group, and R2 is a C1-C5 alkyl group; In equation (3), R 12 It consists of hydrogen atoms or C1-C3 alkyl groups; In equation (4), R 13 R3 is a hydrogen atom or a C1~C3 alkyl group, R4 is a single bond or a C1~C3 alkylene group, and R5 is a C8~C16 perfluoroalkyl group. In formula (5), R5 is an acid-sensitive group.

[0009] In a preferred embodiment, the molar ratio of acrylate monomer one, acrylate monomer two, acrylate monomer three and styrene monomer is (35~55%):(30~50%):(2~10%):(5~20%).

[0010] In a preferred embodiment, the conditions for the free radical copolymerization reaction include: being carried out in an inert gas atmosphere at a temperature of 70-100°C for 6-12 hours.

[0011] In a preferred embodiment, the initiator is selected from at least one of peroxide initiators, azo initiators, and redox initiators.

[0012] In a preferred embodiment, the content of polymer resin in the top antireflective coating composition is 1.0~5.0 wt%; and the content of photoacid generator in the top antireflective coating composition is 0.1~2.0 wt%.

[0013] In a preferred embodiment, the photoacid-producing agent is selected from at least one of sulfonate-based compounds, iodide-based compounds, and organic sulfonic acid compounds; the organic solvent I is selected from at least one of ethyl lactate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

[0014] Secondly, the present invention provides a method for preparing the above-mentioned top anti-reflective coating composition. The preparation method includes: mixing a polymer resin, a photoacid-producing agent, and organic solvent I, followed by filtration, to obtain the top anti-reflective coating composition.

[0015] Thirdly, the present invention also provides the application of the above-described top anti-reflective coating composition in semiconductor manufacturing. The application method involves coating the above-described top anti-reflective coating composition onto a photoresist coating, followed by curing to form a top anti-reflective coating.

[0016] Beneficial effects: The key to this invention lies in designing and synthesizing a polymer resin with a specific structure. Through the synergistic effect of each unit structure in the polymer resin, on the one hand, the surface of the formed top anti-reflective coating has excellent superhydrophobic properties, with a static water contact angle that can stably reach over 100°, and especially a dynamic back-off angle that can be greater than 90°. This effectively suppresses water wetting defects in immersion lithography and significantly improves the yield. On the other hand, it significantly improves the contrast of dissolution rates between the exposed and non-exposed areas, thereby obtaining a more vertical and smoother lithographic pattern and reducing line edge roughness (LER). At the same time, by controlling each unit structure in the polymer resin within a specific ratio range, the refractive index and extinction coefficient of the top anti-reflective coating at 193nm or EUV wavelength reach ideal values, ensuring that the top anti-reflective coating has excellent anti-reflective performance. Detailed Implementation

[0017] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Furthermore, unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and such technical solutions should be considered to be included in the disclosure of the present invention.

[0018] The top antireflective coating composition provided by this invention comprises a polymer resin, a photoacid-generating agent, and an organic solvent I. The polymer resin has the structure shown in formula (1): Equation (1), In equation (1), R 11 R 12 R 13 Each of the following groups is independently a hydrogen atom or a C1-C3 alkyl group, R2 is a C1-C5 alkyl group, R3 is a single bond or a C1-C3 alkylene group, R4 is a C8-C16 perfluoroalkyl group, and R5 is an acid-sensitive group. The ratio of a:b:c:d is (35-55%):(30-50%):(2-10%):(5-20%). Specific examples of C1-C3 alkyl groups include, but are not limited to, any one of methyl, ethyl, n-propyl, and isopropyl. Specific examples of C1-C5 alkyl groups include, but are not limited to, any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, isobutyl, n-pentyl, and neopentyl. Specific examples of C1-C3 alkylene groups include, but are not limited to, any one of -CH2-, -CH2CH2-, -CH(CH3)-, -CH2CH2CH2-, -CH(CH3)2-, and -CH2CH(CH3)-. The C8-C16 perfluoroalkyl group is preferably a C8-C16 perfluoro linear alkyl group, and specific examples include, but are not limited to, any one of: perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl, perfluorododecyl, perfluorotetradecyl, and perfluorohexadecyl.

[0019] In formula (1), the molar amount of structural units containing the R2 group is represented by a, the molar amount of structural units containing hexafluoroisopropanol is represented by b, the molar amount of structural units containing C8~C16 perfluoroalkyl groups is represented by c, and the molar amount of structural units containing benzene rings is represented by d. Based on the total molar content of a, b, c, and d, a is 35~55%, which can be 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, or any value between them; b is 30~50%, which can be 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, or any value between them; c is 2~10%, which can be 2%, 3%, 4%, 5%, 8%, 10%, or any value between them; and d is 5~20%, which can be 5%, 8%, 10%, 12%, 15%, 18%, 20%, or any value between them. When the molar amount of each unit structure in the polymer resin is controlled within the above-mentioned range, it is beneficial in two ways: firstly, it allows the refractive index and extinction coefficient of the top antireflective coating composition to reach ideal values ​​at 193 nm or EUV wavelength, thus endowing it with excellent antireflective optical properties; secondly, it facilitates the synergistic cooperation of each unit structure to improve the hydrophobic properties of the top antireflective coating surface and the corresponding exposure contrast, thereby reducing the roughness of the line edges. Furthermore, formula (1) is only used to indicate the type and proportion of each structural unit and should not be construed as a specific limitation on the copolymerization reaction type or the connection relationship between the structural units. The polymer resin can be a random copolymer, homopolymer copolymer, or block copolymer, preferably a random copolymer.

[0020] In this invention, the weight-average molecular weight (Mw) of the polymer resin is preferably 5000~30000 g / mol, such as 5000 g / mol, 8000 g / mol, 10000 g / mol, 15000 g / mol, 18000 g / mol, 20000 g / mol, 25000 g / mol, 30000 g / mol or any value between them; the PDI is preferably 0.80~2.00, such as 0.80, 0.90, 1.00, 1.20, 1.50, 1.80, 2.00 or any value between them.

[0021] In this invention, the acid-sensitive group can be any group structure that can be removed under acid catalysis to expose the hydroxyl group on the benzene ring. Specific examples include, but are not limited to, at least one of the following structures: .

[0022] In this invention, the preparation method of the polymer resin can be as follows: acrylate monomer I shown in formula (2), acrylate monomer II shown in formula (3), acrylate monomer III shown in formula (4) and styrene monomer shown in formula (5) are subjected to free radical copolymerization under the action of an initiator, and the resulting reaction product is the polymer resin with the structure shown in formula (1). Equation (2), Equation (3), Equation (4), Equation (5), In equation (2), R 11 R1 is a hydrogen atom or a C1~C3 alkyl group, and R2 is a C1~C5 alkyl group; in formula (3), R 12 It is a hydrogen atom or a C1~C3 alkyl group; in formula (4), R 13 R3 is a hydrogen atom or a C1-C3 alkyl group, R4 is a single bond or a C1-C3 alkylene group, and R5 is a C8-C16 perfluoroalkyl group; in formula (5), R5 is an acid-sensitive group. Specific examples of C1-C3 alkyl groups, C1-C5 alkyl groups, C1-C3 alkylene groups, C8-C16 perfluoroalkyl groups, and acid-sensitive groups are as described above and will not be repeated here.

[0023] In this invention, the preferred molar ratio of acrylate monomer I shown in formula (2), acrylate monomer II shown in formula (3), acrylate monomer III shown in formula (4), and styrene monomer shown in formula (5) is (35~55%):(30~50%):(2~10%):(5~20%).

[0024] In this invention, the initiator can be selected from any one or more of peroxide initiators, azo initiators, and redox initiators. The peroxide initiator, azo initiator, and redox initiator are conventional choices in the art, as long as they can initiate free radical polymerization of acrylate monomers I, II, III, and styrene monomers; this invention does not impose any particular limitation. The initiator is preferably an azo initiator, and specific examples include, but are not limited to, any one or more of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azodicarbonamide, azobisisopropylimidazoline hydrochloride, azoisobutylcyanoformamide, azobiscyclohexylformitrile, azobiscyanopentanoic acid, and azobisisopropylimidazoline, with azobisisobutyronitrile being particularly preferred.

[0025] In this invention, the preferred conditions for the free radical copolymerization reaction include: being carried out in an inert gas atmosphere, wherein the inert gas can be selected from any one or more of nitrogen, argon, xenon, and radon; the temperature is 70~100℃, such as 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and the time is 6~12h, such as 6h, 8h, 10h, 12h or any value between them.

[0026] In this invention, the free radical polymerization reaction is preferably carried out in the presence of organic solvent II. Specific examples of solvent II include, but are not limited to, any one or more of the following: propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, dibutyl ether, tetrahydrofuran, γ-butyrolactone, benzene, toluene, xylene, acetone, methanol, ethanol, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, and propylene glycol diacetate, more preferably any one or more of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate.

[0027] In this invention, the content of polymer resin in the top antireflective coating composition is preferably 1.0~5.0 wt%, such as 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, or any value between them. The content of photoacid-generating agent in the top antireflective coating composition is preferably 0.1~2.0 wt%, such as 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2.0 wt%, or any value between them.

[0028] In this invention, the photo-induced acid-producing agent can be selected from at least one of sulfonium salt-based compounds, iodine salt-based compounds, and organic sulfonic acid compounds. The sulfonium salt-based compounds, iodine salt-based compounds, and organic sulfonic acid compounds are conventional choices in the art, and specific examples include, but are not limited to: diphenyl-p-methoxyphenyl sulfonium trifluoromethanesulfonate, diphenyl-p-toluene sulfonium trifluoromethanesulfonate, diphenyl-p-tert-butylphenyl sulfonium trifluoromethanesulfonate, diphenyl-p-isobutylphenyl sulfonium trifluoromethanesulfonate, triphenyl sulfonium trifluoromethanesulfonate, tris(p-tert-butylphenyl) sulfonium trifluoromethanesulfonate, diphenyl-p-methoxyphenyl sulfonium perfluorobutyl sulfonate, diphenyl-p-toluyl sulfonium perfluorobutyl sulfonate, and diphenyl-p-tert-butylphenyl sulfonium perfluorobutyl sulfonate. The following are any one or more of the following: diphenyl-p-isobutylphenylsulfonium perfluorobutyl sulfonate, triphenylsulfonium perfluorobutyl sulfonate, tri-p-tert-butylphenylsulfonium perfluorobutyl sulfonate, triphenylsulfonium hexafluoroantimonate, dibutylnaphthylsulfonium trifluoromethanesulfonate, diphenyliodotrifluoromethanesulfonate, diphenyliodotrifluorobutyl sulfonate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, phthalimide trifluoromethanesulfonate, phthalimide trifluoromethanesulfonate, dinitrobenzyltoluenesulfonate, dinitrobenzyltoluenesulfonate, n-decyl disulfone, naphthylimide trifluoromethanesulfonate, and naphthylimide trifluoromethanesulfonate.

[0029] In this invention, the organic solvent I can be a conventional choice in the art, as long as it is a solvent that can dissolve and mix the polymer resin and the photoacid generator uniformly. Specific examples include, but are not limited to, any one or more of ethyl lactate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate (PGMEA).

[0030] The method for preparing the top anti-reflective coating composition provided by the present invention includes: mixing a polymer resin, a photoacid generator and an organic solvent I and then filtering the mixture to obtain the top anti-reflective coating composition.

[0031] This invention provides the application of a top anti-reflective coating composition in semiconductor manufacturing. The application method involves coating the aforementioned top anti-reflective coating composition onto a photoresist coating, followed by curing to form the top anti-reflective coating. The raw materials and methods used to form the photoresist coating can be adapted to the specific application.

[0032] Furthermore, the terms "Ⅰ" and "Ⅱ" are used only to distinguish the organic solvents used in different steps and do not imply any particular limitation on the organic solvents.

[0033] The present invention will be described in detail below through specific embodiments. These embodiments are intended to explain the invention and should not be construed as limiting it. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0034] Preparation Example 1 This preparation example illustrates a method for preparing a polymer resin, the specific process of which is as follows: 12.0 g (93.6 mmol) of tert-butyl acrylate, 15.0 g (63.5 mmol) of hexafluoroisopropanol methacrylate, 3.5 g (7.7 mmol) of 1H,1H-perfluorooctyl acrylate, and 5.5 g (26.9 mmol) of p-(tert-butoxycarbonyloxy)styrene were weighed and mixed thoroughly with 50.0 g of propylene glycol methyl ether acetate (PGMEA) to obtain a monomer mixture to be reacted. 0.5 g of azobisisobutyronitrile and 20.0 g of propylene glycol methyl ether acetate (PGMEA) were then mixed thoroughly to obtain an initiator solution. 200.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added to a reaction flask equipped with a stirrer, condenser, and nitrogen inlet. Nitrogen gas was continuously introduced and the temperature was raised to 85°C. Then, the above-mentioned monomer mixture and initiator solution were slowly added dropwise to the reaction flask over 3 hours using a constant-pressure dropping funnel. After the addition was complete, the reaction was continued at 85°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and n-hexane was added to precipitate a white precipitate. After filtration and vacuum drying, the resulting white solid polymer was the polymer resin, denoted as P1. GPC analysis showed that the Mw of polymer resin P1 was 15200 g / mol, and the PDI was 1.65.

[0035] Preparation Example 2 This preparation example illustrates a method for preparing a polymer resin, the specific process of which is as follows: 9.4 g (93.6 mmol) of methyl methacrylate, 15.0 g (63.5 mmol) of hexafluoroisopropanol methacrylate, 4.1 g (7.7 mmol) of perfluorooctylpropyl acrylate (CAS No.: 1652-60-4), 4.7 g (26.7 mmol) of p-tert-butoxystyrene, and 50.0 g of propylene glycol methyl ether acetate (PGMEA) were weighed and mixed thoroughly to obtain a monomer mixture to be reacted. 0.5 g of azobisisobutyronitrile and 20.0 g of propylene glycol methyl ether acetate (PGMEA) were then mixed thoroughly to obtain an initiator solution. 200.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added to a reaction flask equipped with a stirrer, condenser, and nitrogen inlet. Nitrogen gas was continuously introduced and the temperature was raised to 85°C. Then, the above-mentioned monomer mixture and initiator solution were slowly added dropwise to the reaction flask over 3 hours using a constant-pressure dropping funnel. After the addition was complete, the reaction was continued at 85°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and n-hexane was added to precipitate a white precipitate. After filtration and vacuum drying, the resulting white solid polymer was the polymer resin, denoted as P2. GPC analysis showed that the Mw of polymer resin P2 was 15500 g / mol, and the PDI was 1.67.

[0036] Preparation Example 3 This preparation example illustrates a method for preparing a polymer resin, the specific process of which is as follows: 9.5 g (74 mmol) of tert-butyl acrylate, 22.7 g (96 mmol) of hexafluoroisopropanol methacrylate, 9.1 g (20 mmol) of 1H,1H-perfluorooctyl acrylate, 2.0 g (10 mmol) of p-(tert-butoxycarbonyloxy)styrene, and 50.0 g of propylene glycol methyl ether acetate (PGMEA) were weighed and mixed thoroughly to obtain the monomer mixture to be reacted. 0.5 g of azobisisobutyronitrile and 20.0 g of propylene glycol methyl ether acetate (PGMEA) were then mixed thoroughly to obtain the initiator solution. 200.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added to a reaction flask equipped with a stirrer, condenser, and nitrogen inlet. Nitrogen gas was continuously introduced and the temperature was raised to 85°C. Then, the above-mentioned monomer mixture and initiator solution were slowly added dropwise to the reaction flask over 3 hours using a constant-pressure dropping funnel. After the addition was complete, the reaction was continued at 85°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and n-hexane was added to precipitate a white precipitate. After filtration and vacuum drying, the resulting white solid polymer was the polymer resin, denoted as P3. GPC analysis showed that the Mw of polymer resin P3 was 16000 g / mol, and the PDI was 1.70.

[0037] Preparation Example 4 This preparation example illustrates a method for preparing a polymer resin, the specific process of which is as follows: 13.6 g (106 mmol) of tert-butyl acrylate, 14.2 g (60 mmol) of hexafluoroisopropanol methacrylate, 10.2 g (14 mmol) of 1H,1H,11H-perfluoroundecyl methacrylate, 4.0 g (20 mmol) of p-(tert-butoxycarbonyloxy)styrene, and 50.0 g of propylene glycol methyl ether acetate (PGMEA) were weighed and mixed thoroughly to obtain a monomer mixture to be reacted. 0.5 g of azobisisobutyronitrile and 20.0 g of propylene glycol methyl ether acetate (PGMEA) were then mixed thoroughly to obtain an initiator solution. 200.0 g of propylene glycol monomethyl ether acetate (PGMEA) was added to a reaction flask equipped with a stirrer, condenser, and nitrogen inlet. Nitrogen gas was continuously introduced and the temperature was raised to 85°C. Then, the above-mentioned monomer mixture and initiator solution were slowly added dropwise to the reaction flask over 3 hours using a constant-pressure dropping funnel. After the addition was complete, the reaction was continued at 85°C for 6 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and n-hexane was added to precipitate a white precipitate. After filtration and vacuum drying, the resulting white solid polymer was the polymer resin, denoted as P4. GPC analysis showed that the Mw of polymer resin P4 was 16500 g / mol, and the PDI was 1.71.

[0038] Comparative Preparation Example 1 This comparative preparation example illustrates a method for preparing a reference polymer resin, the specific process of which is as follows: The polymer resin was prepared according to the method of Preparation Example 1, except that the same molar amount of tert-butyl acrylate was used instead of p-(tert-butoxycarbonyloxy)styrene, and the same molar amount of hexafluoroisopropanol methacrylate was used instead of 1H,1H-perfluorooctyl acrylate. All other conditions were the same as in Preparation Example 1. The resulting reference polymer resin was denoted as DP1. GPC analysis showed that the Mw of reference polymer resin DP1 was 15500 g / mol, and the PDI was 1.65.

[0039] Comparative Preparation Example 2 This comparative preparation example illustrates a method for preparing a reference polymer resin, the specific process of which is as follows: The polymer resin was prepared according to the method of Preparation Example 1, except that the same molar amount of tert-butyl acrylate was used instead of p-(tert-butoxycarbonyloxy)styrene, and all other conditions were the same as in Preparation Example 1. The reference polymer resin prepared in this way was denoted as DP2. According to GPC determination, the Mw of the reference polymer resin DP2 was 15800 g / mol, and the PDI was 1.70.

[0040] Comparative preparation example 3 This comparative preparation example illustrates a method for preparing a reference polymer resin, the specific process of which is as follows: The polymer resin was prepared according to the method of Preparation Example 1, except that the same molar amount of hexafluoroisopropanol methacrylate was used instead of 1H,1H-perfluorooctyl acrylate, and all other conditions were the same as in Preparation Example 1. The reference polymer resin prepared in this way was denoted as DP3. According to GPC determination, the Mw of the reference polymer resin DP3 was 16200 g / mol, and the PDI was 1.71.

[0041] Comparative preparation example 4 This comparative preparation example illustrates a method for preparing a reference polymer resin, the specific process of which is as follows: The polymer resin was prepared according to the method of Preparation Example 1, except that 30 mmol of tert-butyl acrylate, 30 mmol of hexafluoroisopropanol methacrylate, 60 mmol of 1H,1H-perfluorooctyl acrylate, 80 mmol of p-(tert-butoxycarbonyloxy)styrene, and 50.0 g of propylene glycol methyl ether acetate (PGMEA) were weighed and mixed thoroughly. All other conditions were the same as in Preparation Example 1. The reference polymer resin prepared in this way was designated DP4. GPC analysis showed that the Mw of the reference polymer resin DP4 was 15800 g / mol, and the PDI was 1.68.

[0042] Examples 1-5 and Comparative Examples 1-4 The polymer resins obtained in the above preparation examples and comparative preparation examples were formulated with a photoacid-generating agent and an organic solvent to prepare a top anti-reflective coating composition (based on a total mass of 100 parts by weight). After filtration through a 0.1 μm polytetrafluoroethylene filter, the top anti-reflective coating composition was obtained. The amounts of each component are shown in Table 1. The photoacid-generating agent was triphenylsulfonate perfluorobutyl sulfonate, and the solvent was ethyl lactate.

[0043] Table 1

[0044] Test case (1) The top anti-reflective coating compositions obtained in the above examples and comparative examples were spin-coated onto silicon wafers coated with EUV photoresist (EUV photoresist purchased from JSR Corporation, item number EUV-001), and soft-baked at 110°C for 60 s to form a TARC film with a thickness of approximately 50 nm. The refractive index n and extinction coefficient k of the TARC film at 50 nm were measured using an elliptic meter (manufacturer: JAWoolam, equipment name: VUV-303). The static water contact angle (SCA) of the top antireflective coating was tested using a contact angle meter (KRUSS, DSA100L). The advancing contact angle (ACA) was tested using the pendant drop / increase method: the contact angle at which the leading edge of the droplet just begins to move when deionized water is slowly added to the surface of the silicon wafer coated with the top antireflective coating. The receding contact angle (RCA) was tested using the liquid absorption / reduction method: the contact angle at which the trailing edge of the droplet just begins to retract when the droplet volume is slowly reduced on the surface of the silicon wafer coated with the top antireflective coating. The tilt angle (TCA) was tested using the tilting platform method: the sample was placed on a tiltable platform, and the tilt angle was gradually increased until the droplet began to slide; the tilt angle of the platform at this point was recorded as the sliding tilt angle. The average value of three points was taken for each test group. The results are shown in Table 2.

[0045] (2) Expose the silicon wafer prepared in (1) under the same conditions using an EUV laser (using a design pattern with a linewidth of 190nm). After exposure, bake it on a hot plate at a temperature of 110℃ for 60s, and then develop it in 2.38% TMAH developer for 60s. Quickly remove it and place it in pure water for rinsing to obtain the photoresist pattern.

[0046] The development effect and line edge roughness (LER) of the photoresist pattern were observed using CD-SEM (scanning electron microscopy). The formed photoresist pattern was observed using a scanning electron microscope, and the boundary position of the photoresist pattern was determined by scanning. The deviation of the boundary from the average boundary was determined, and the standard deviation of the measured photoresist pattern boundary was obtained. In the field of photolithography, three times the boundary standard deviation is used to quantitatively describe the line edge roughness. The test results are shown in Table 2; a smaller line edge roughness is better.

[0047] Table 2

[0048] As shown in Table 2, compared with the comparative example, the antireflective coating prepared by the embodiment of the present invention has higher static water contact angle (SCA), forward contact angle (ACA), and backward contact angle (RCA), better surface hydrophobicity, and a lower tilt angle (TCA), indicating that the coating surface is more uniform, has low adhesion, and has stable low surface energy characteristics. At the same time, it has a lower refractive index n and extinction coefficient k, has good optical performance, and the obtained photoresist pattern has less line edge roughness and better development effect.

[0049] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. A top anti-reflective coating composition, characterized in that, The top antireflective coating composition comprises a polymer resin, a photoacid generator, and an organic solvent I; the polymer resin has the structure shown in formula (1): Equation (1), In equation (1), R 11 R 12 R 13 Each is independently a hydrogen atom or a C1~C3 alkyl group, R2 is a C1~C5 alkyl group, R3 is a single bond or a C1~C3 alkylene group, R4 is a C8~C16 perfluoroalkyl group, R5 is an acid-sensitive group, and a:b:c:d=(35~55%):(30~50%):(2~10%):(5~20%).

2. The top anti-reflective coating composition according to claim 1, characterized in that, The polymer resin has a weight-average molecular weight of 5000~30000 g / mol and a PDI of 0.80~2.

00.

3. The top anti-reflective coating composition according to claim 1, characterized in that, The acid-sensitive group is selected from at least one of the following structures: 。 4. The top anti-reflective coating composition according to claim 1, characterized in that, The preparation method of the polymer resin is as follows: the acrylate monomer I shown in formula (2), the acrylate monomer II shown in formula (3), the acrylate monomer III shown in formula (4) and the styrene monomer shown in formula (5) are subjected to free radical copolymerization under the action of an initiator, and the resulting reaction product is the polymer resin with the structure shown in formula (1). Equation (2), Equation (3), Equation (4), Equation (5), In equation (2), R 11 R1 is a hydrogen atom or a C1-C3 alkyl group, and R2 is a C1-C5 alkyl group; In equation (3), R 12 It consists of hydrogen atoms or C1-C3 alkyl groups; In equation (4), R 13 R3 is a hydrogen atom or a C1~C3 alkyl group, R4 is a single bond or a C1~C3 alkylene group, and R5 is a C8~C16 perfluoroalkyl group. In formula (5), R5 is an acid-sensitive group.

5. The top anti-reflective coating composition according to claim 4, characterized in that, The molar ratio of acrylate monomer one, acrylate monomer two, acrylate monomer three and styrene monomer is (35~55%):(30~50%):(2~10%):(5~20%). Preferably, the conditions for the free radical copolymerization reaction include: being carried out in an inert gas atmosphere, at a temperature of 70~100℃, and for a time of 6~12h.

6. The top antireflective coating composition according to claim 4, characterized in that, The initiator is selected from at least one of peroxide initiators, azo initiators, and redox initiators.

7. The top antireflective coating composition according to claim 1, characterized in that, The content of polymer resin in the top antireflective coating composition is 1.0~5.0wt%; the content of photoacid generator in the top antireflective coating composition is 0.1~2.0wt%.

8. The top antireflective coating composition according to claim 1, characterized in that, The photo-induced acid-producing agent is selected from at least one of sulfonate-based compounds, iodide-based compounds, and organic sulfonic acid compounds; the organic solvent I is selected from at least one of ethyl lactate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

9. A method for preparing the top anti-reflective coating composition according to any one of claims 1 to 8, characterized in that, The preparation method includes: mixing polymer resin, photoacid generator and organic solvent I and then filtering to obtain the top anti-reflective coating composition.

10. The application of the top antireflective coating composition according to any one of claims 1 to 8 in semiconductor manufacturing, characterized in that, The application method is as follows: coating the top anti-reflective coating composition according to any one of claims 1 to 8 onto the photoresist coating, and then curing it to form the top anti-reflective coating.

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