Acrylate photoresist film-forming resin and ArF photoresist and preparation method and application thereof

Abstract

The present application belongs to the field of photoresist technology, and specifically relates to an acrylate photoresist film-forming resin and ArF photoresist and their preparation method and application. The acrylate photoresist film-forming resin has a structure shown in formula (1). The key to the present invention is to subject N-substituted maleimide, acrylate containing acid-sensitive groups and polycyclic olefins with a bridging structure to free radical polymerization, so that the obtained acrylate photoresist film-forming resin can significantly improve the etching resistance, substrate adhesion, sensitivity and resolution of the photoresist as a film-forming resin of the photoresist.

Description

Technical Field

[0001] The present application belongs to the technical field of photoresists, and specifically relates to an acrylate photoresist film-forming resin and ArF photoresist, and a preparation method and application thereof. Background Art

[0002] In photolithography, limited by Rayleigh's diffraction law, in principle, the resolution can be improved as the exposure wavelength is shortened. Currently, the G line with a wavelength of 436nm, the i line with a wavelength of 365nm, the KrF excimer laser with a wavelength of 248nm, the ArF excimer laser with a wavelength of 193nm, and the F2 excimer laser with a wavelength of 157nm have been used as exposure sources for semiconductor photolithography. Among them, the ArF excimer laser with a wavelength of 193nm is considered to be an exposure source with a wide range of application prospects, but since the exposure time of the ArF excitation laser is shorter, the sensitivity of the photoresist must be improved. The chemically amplified photoresist currently used in research contains a resin that can be decomposed by acid. Since exposure will produce the catalytic effect of acid, the resin in the photoresist is decomposed, which can reduce the energy required for the exposure of the photoresist. Therefore, the ArF photoresist currently studied is mainly a chemically amplified photoresist.

[0003] In addition, in order to ensure the transmittance of the photoresist, the ideal resin for ArF excitation laser exposure usually does not contain aromatic rings. Acrylate polymers are often used as the preferred material for ArF photoresists. Their polymer molecular chains do not have conjugated structures such as double bonds and benzene rings, so they can remain highly transparent under 193nm ArF excitation laser exposure. However, most acrylate polymer molecular chains present a simple linear structure, which makes acrylates exhibit poor plasma etching resistance, and the polymer resin has poor adhesion to the substrate and is easily peeled off from the substrate. In summary, it is of great significance to find a photoresist film-forming resin with excellent performance and to prepare an ArF photoresist with good etching resistance, substrate adhesion, high sensitivity and high resolution. Summary of the invention

[0004] One of the purposes of the present invention is to propose an acrylate photoresist film-forming resin and ArF photoresist with good etching resistance, substrate adhesion, high sensitivity and high resolution, as well as a preparation method and application thereof in response to the above-mentioned problems.

[0005] Specifically, the acrylate photoresist film-forming resin provided by the present invention has a structure shown in formula (1):

[0006]

[0007] In formula (1), R 1 , R 2 and R 3Each independently is H, F, OH, C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl or C 1 -C 5 Alkoxy, R 4 is an acid-sensitive group, R 5 is H or methyl, R 6 It is H or methyl, and p:n:m is (0.05-1):1:(0.1-1.5).

[0008] In a preferred embodiment, the number average molecular weight of the acrylate photoresist film-forming resin is 10000-25000 g / mol.

[0009] In a preferred embodiment, the PDI of the acrylate photoresist film-forming resin is 1.5-2.8.

[0010] In a preferred embodiment, the structural formula of the acid-sensitive group is selected from one of the following structures:

[0011]

[0012] The second object of the present invention is to provide a method for preparing the above-mentioned acrylate photoresist film-forming resin, which comprises subjecting a first monomer M1, a second monomer M2, and a third monomer M3 to a free radical polymerization reaction in the presence of an initiator to obtain the acrylate photoresist film-forming resin; the first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); the molar ratio n:m:p of the first monomer M1, the second monomer M2, and the third monomer M3 is 1:(0.1-1.5):(0.05-1);

[0013]

[0014] In formula (1), R 1 , R 2 and R 3 Each independently is H, F, OH, C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl or C 1 -C 5 Alkoxy;

[0015] In formula (2), R 4 is an acid-sensitive group, R 5 is H or methyl;

[0016] In formula (3), R6 It is H or methyl.

[0017] In a preferred embodiment, the content of the first monomer M1 is 30-85 mol%, the content of the second monomer M2 is 10-40 mol%, and the content of the third monomer M3 is 5-30 mol%.

[0018] In a preferred embodiment, the third monomer M3 is prepared according to a method comprising the following steps:

[0019] (1) subjecting 5-norbornene-2-ol to an addition reaction in a first organic solvent to obtain (1R,4R,4aS,8aR)-dodecahydro-1,4:5,8-dimethylbiphenyl-diol, denoted as D1;

[0020] (2) The D1 obtained in step (1) is subjected to a condensation reaction with methacryloyl chloride in a second organic solvent to obtain a third monomer M3.

[0021] In a preferred embodiment, the molar ratio of D1 to methacryloyl chloride is (1-1.5):1.

[0022] In a preferred embodiment, the conditions of the addition reaction include a temperature of 90-120° C. and a time of 1-5 h.

[0023] In a preferred embodiment, the condensation reaction conditions include a temperature of 50-70° C. and a time of 1-5 h.

[0024] The third object of the present invention is to provide an acrylate photoresist film-forming resin prepared by the above method.

[0025] A fourth object of the present invention is to provide an ArF photoresist, which contains the above-mentioned acrylate photoresist film-forming resin, a photoacid generator, a quencher and a solvent.

[0026] In a preferred embodiment, based on the total content of the ArF photoresist, the content of the acrylate photoresist film-forming resin is 10-30wt%, the content of the photoacid generator is 0.5-45wt%, the content of the quencher is 0.001-0.1wt%, and the content of the solvent is 65-85wt%.

[0027] The fifth object of the present invention is to provide a method for preparing the above-mentioned ArF photoresist, which comprises uniformly mixing an acrylate photoresist film-forming resin, a photoacid generator, a quencher and a solvent and filtering the mixture to obtain the ArF photoresist.

[0028] The key to the present invention is to subject N-substituted maleimide (first monomer), acrylate containing acid-sensitive group (second monomer) and polycyclic olefin with bridge structure (third monomer) to free radical polymerization reaction, so that the obtained acrylate photoresist film-forming resin can be used as the film-forming resin of photoresist to significantly improve the etching resistance, substrate adhesion, sensitivity and resolution of the photoresist. DETAILED DESCRIPTION

[0029] The acrylate photoresist film-forming resin provided by the present invention has a structure shown in formula (1):

[0030]

[0031] In formula (1), R 1 , R 2 and R 3 Each independently is H, F, OH, C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl or C 1 -C 5 Alkoxy, R 4 is an acid-sensitive group, R 5 is H or methyl, R 6 is H or methyl, and p:n:m is (0.05-1):1:(0.1-1.5). 1 -C 5 The alkyl group may be at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl. 1 -C 5 The perfluoroalkyl group may be at least one of a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group and a perfluoropentyl group. 1 -C 5Alkoxy can be at least one of methoxy, ethoxy, n-propoxy, isopropoxy, butoxy and pentoxy. p, n and m represent the molar content of the corresponding structural unit respectively, which is calculated by the feeding amount. p:n is (0.05-1):1, such as 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1 or any value therebetween. n:m is 1:(0.1-1.5), such as 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5 or any value therebetween. It should be noted that the acrylate photoresist film-forming resin shown in formula (1) is only used to represent the content of the structural units contained and the respective structural units, and is not used to represent the connection relationship between the respective structural units. These three structural units can exist in the form of random copolymers, alternating copolymers or block copolymers, preferably in the form of random copolymers.

[0032] In the present invention, R 4 is an acid-sensitive group, which can be selected from one of the structures shown below;

[0033]

[0034] In the present invention, the number average molecular weight of the acrylate photoresist film-forming resin is preferably 10000-25000 g / mol, such as 10000 g / mol, 12000 g / mol, 15000 g / mol, 18000 g / mol, 20000 g / mol, 22000 g / mol, 25000 g / mol or any value therebetween. The PDI of the acrylate photoresist film-forming resin is preferably 1.5-2.8, such as 1.5, 1.8, 2.0, 2.2, 2.5, 2.8 or any value therebetween. PDI is a polymer dispersibility index, which is used to describe the molecular weight distribution of polymers. The acrylate photoresist film-forming resin provided by the present invention has a higher PDI value, and its molecular weight distribution range is wider, which is more conducive to adjusting its performance.

[0035] In the present invention, the preparation method of the acrylate photoresist film-forming resin includes subjecting a first monomer M1, a second monomer M2, and a third monomer M3 to a free radical polymerization reaction in the presence of an initiator, thereby obtaining an acrylate photoresist film-forming resin. In a specific embodiment, after subjecting the first monomer M1, the second monomer M2, and the third monomer M3 to a free radical polymerization reaction in the presence of an initiator in a third organic solvent, a precipitant may be added, and after filtering and separation, an acrylate photoresist film-forming resin is obtained. Wherein, the first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); the molar ratio n:m:p of the first monomer M1, the second monomer M2, and the third monomer M3 is 1:(0.1-1.5):(0.05-1).

[0036]

[0037] In formula (1), R 1 , R 2 and R 3 Each independently is H, F, OH, C 1 -C 5 Alkyl, C 1 -C 5 Perfluoroalkyl or C 1 -C 5 Alkoxy; in formula (2), R 4 is an acid-sensitive group, R 5 is H or methyl; in formula (3), R 6 is H or methyl. 1 , R 2 , R 3 and R 4 The specific embodiments are as described above and will not be described in detail here.

[0038] In the present invention, the polymerization temperature is preferably 60-80°C, such as 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C or any value therebetween. The polymerization time is preferably 6-10h, such as 6h, 7h, 8h, 9h, 10h or any value therebetween.

[0039] In the present invention, specific examples of the initiator include, but are not limited to, at least one of azobisisobutyronitrile, azobisisoheptylnitrile, dibenzoyl peroxide, diisopropylbenzene peroxide, di-tert-butyl peroxide, dibenzoyl peroxide, isopropylbenzene peroxide and tert-butyl peroxide.

[0040] In the present invention, specific examples of the third organic solvent include, but are not limited to: at least one of tetrahydrofuran, dioxane, acetone, acetonitrile, cyclohexanone, benzene, toluene, chlorobenzene, xylene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, ethyl acetate, butyl acetate, N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.

[0041] In the present invention, the precipitant is preferably at least one selected from isopentane, n-pentane, trimethylpentane, isooctane, deionized water, methanol, ethanol, n-hexane, cyclohexane, ether and petroleum ether. More preferably, the precipitant is selected from at least one selected from petroleum ether, n-hexane and cyclohexane, and the precipitation effect of a low-polarity solvent is better.

[0042] In the present invention, the content of the first monomer M1 is preferably 30-85 mol%, such as 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol% or any value therebetween. The content of the second monomer M2 is preferably 10-40 mol%, such as 10 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%, 28 mol%, 30 mol%, 32 mol%, 35 mol%, 38 mol%, 40 mol% or any value therebetween. The content of the third monomer M3 is preferably 5-30 mol%, such as 5 mol%, 8 mol%, 10 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%, 28 mol%, 30 mol% or any value therebetween.

[0043] In the present invention, the third monomer M3 is prepared according to a method comprising the following steps:

[0044] (1) subjecting 5-norbornene-2-ol to an addition reaction in a first organic solvent to obtain (1R,4R,4aS,8aR)-dodecahydro-1,4:5,8-dimethylbiphenyl-diol, denoted as D1;

[0045] (2) The D1 obtained in step (1) is subjected to a condensation reaction with methacryloyl chloride in a second organic solvent to obtain a third monomer M3.

[0046] In the preparation process of the third monomer M3, the molar ratio of D1 to methacryloyl chloride is (1-1.5):1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1 or any value therebetween.

[0047] In the preparation process of the third monomer M3, in step (1), the temperature of the addition reaction is preferably 90-120° C., such as 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C. or any value therebetween. The time of the addition reaction is preferably 1-5 h, such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h or any value therebetween.

[0048] In the preparation process of the third monomer M3, in step (2), the temperature of the condensation reaction is preferably 50-70° C., such as 50° C., 55° C., 60° C., 65° C., 70° C. or any value therebetween. The time of the condensation reaction is preferably 1-5 h, such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h or any value therebetween.

[0049] In the present invention, the first organic solvent and the second organic solvent are each independently preferably at least one selected from toluene, chlorobenzene, xylene, dichloromethane, ethyl acetate, diethylene glycol dimethyl ether, tetrahydrofuran, acetone and N,N-dimethylformamide.

[0050] In the present invention, the ArF photoresist comprises an acrylate photoresist film-forming resin, a photoacid generator, a quencher and a solvent. The content of the acrylate photoresist film-forming resin is preferably 10-30wt%, such as 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt% or any value therebetween. The content of the photoacid generator is preferably 0.5-5wt%, such as 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt% or any value therebetween. The content of the quencher is preferably 0.001-0.1wt%, such as 0.001wt%, 0.005wt%, 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%, 0.1wt% or any value therebetween. The content of the solvent is preferably 65-85wt%, such as 65wt%, 68wt%, 70wt%, 72wt%, 75wt%, 78wt%, 80wt%, 82wt%, 85wt% or any value therebetween.

[0051] In the present invention, the photoacid generator is preferably an ionic photoacid generator and / or a non-ionic photoacid generator. Among them, the ionic photoacid generator is preferably an iodonium salt and / or a sulfonium salt. The non-ionic photoacid generator is preferably at least one selected from an organic halogen compound, a diazosulfone and an imide sulfonate.

[0052] In the present invention, the quencher is preferably an organic amine, and specific examples thereof include but are not limited to at least one of trioctylamine, diethylamine, triethylamine, di-n-propylamine and tri-2-(2-methoxy(ethoxy)ethylamine).

[0053] In the present invention, the solvent is preferably at least one selected from cyclohexanone, diacetone alcohol, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.

[0054] In the present invention, the ArF photoresist preparation method comprises mixing an acrylate photoresist film-forming resin, a photoacid generator, a quencher and a solvent uniformly and filtering to obtain the ArF photoresist. In a specific embodiment, after the acrylate photoresist film-forming resin, the photoacid generator and the quencher are mixed in a solvent, a container containing the mixed solution is fixed on a mechanical oscillator and oscillated at room temperature for 10-24 hours to fully dissolve each component, and then filtered using a filter with a pore size of 20-50 nm to obtain the ArF photoresist.

[0055] In the present invention, the application of the ArF photoresist in the photolithography process can be specifically as follows: coating the ArF photoresist on a pretreated substrate, followed by drying, exposure, baking and development, wherein a 2.38 wt % tetramethylammonium hydroxide aqueous solution is used as a developer.

[0056] In addition, in the present invention, the terms "first", "second" and "third" are only used to refer to the same type of chemical substances with the same function in different orders of appearance for the convenience of distinction and description, and have no special meaning.

[0057] The present invention will be described in detail below through specific embodiments.

[0058] Preparation Example 1 Preparation of the third monomer M3

[0059] 40g of 5-norbornene-2-ol and 200mL of toluene were mixed, heated under reflux at 100°C for 2h and then cooled. The precipitated white crystals were filtered and dried in a vacuum to obtain 28.4g of (1R,4R,4aS,8aR)-dodecahydro-1,4:5,8-dimethylbiphenyl-diol with a yield of 71%, which was recorded as D1; ​​26.4g of D1 and 10.4g of 2-methacryloyl chloride were dissolved in 130mL of diethylene glycol dimethyl ether, reacted at 60°C for 2h and then cooled. A white solid precipitated, which was the esterification product of D1 and 2-methacrylic acid, the third monomer M3, which was filtered and dried to obtain 17.6g with a yield of 61%. Its synthesis route is as follows:

[0060]

[0061] Example 1 Preparation of Acrylate Photoresist Film-forming Resin

[0062] Under room temperature conditions, 18.9 g of 1-(tris(trifluoromethyl)-tert-butyl)-1H-pyrrole-2,5-dione (first monomer M1, 0.06 mol), 5.9 g of 3-hydroxy-1-adamantyl methacrylate (second monomer M2, 0.025 mol), 4.3 g of third monomer M3 (0.015 mol) and 0.29 g of azobisisobutyronitrile were dissolved in 87 g of tetrahydrofuran, heated to 70° C. under the protection of a nitrogen atmosphere for reaction for 8 h, and then cooled to room temperature; the mixture solution obtained by the reaction was sunk into 800 g of petroleum ether, and a precipitate was generated and then filtered, and the obtained solid was placed under vacuum conditions at 80° C. and dried for 48 h, and the dried solid was placed in a brown reagent bottle and stored away from light, thereby obtaining an acrylate photoresist film-forming resin, which was recorded as P1, and had a number average molecular weight of 14370 g / mol and a PDI of 2.67.

[0063] The structure of the first monomer M1 is shown in formula (1-1), and the structure of the second monomer M2 is shown in formula (1-2).

[0064]

[0065] Example 2 Preparation of Acrylate Photoresist Film-forming Resin

[0066] At room temperature, 10.7 g of 1-(trifluoroethyl)-1H-pyrrole-2,5-dione (first monomer M1, 0.06 mol), 6.6 g of 1-adamantyl methacrylate (second monomer M2, 0.03 mol), 2.9 g of third monomer M3 (0.01 mol) and 0.2 g of azobisisobutyronitrile were dissolved in 60.1 g of tetrahydrofuran, and the mixture was heated to 70° C. for reaction for 8 h under the protection of nitrogen atmosphere, and then cooled to room temperature; the mixture solution obtained by the reaction was precipitated into 600 g of petroleum ether, filtered after precipitation, and the obtained solid was placed under vacuum at 80° C. and dried for 48 h. The dried solid was placed in a brown reagent bottle and stored away from light to obtain an acrylate photoresist film-forming resin, which was recorded as P2, and had a number average molecular weight of 16882 g / mol and a PDI of 2.78.

[0067] The structure of the first monomer M1 is shown in formula (2-1), and the structure of the second monomer M2 is shown in formula (2-2).

[0068]

[0069] Example 3 Preparation of Acrylate Photoresist Film-forming Resin

[0070] At room temperature, 8.3 g of 1-(hydroxymethyl)-1H-pyrrole-2,5-dione (first monomer M1, 0.065 mol), 5.8 g of 2-methyl-2-adamantyl methacrylate (second monomer M2, 0.025 mol), 2.9 g of third monomer M3 (0.01 mol) and 0.17 g of azobisisobutyronitrile were dissolved in 51 g of tetrahydrofuran, heated to 70° C. under the protection of nitrogen atmosphere for reaction for 8 h, and then cooled to room temperature; the reaction mixture solution was sunk into 500 g of petroleum ether, filtered after precipitation, and the obtained solid was placed under vacuum at 80° C. and dried for 48 h. The dried solid was placed in a brown reagent bottle and stored away from light to obtain an acrylate photoresist film-forming resin, denoted as P3, with a number average molecular weight of 12372 g / mol and a PDI of 2.32.

[0071] The structure of the first monomer M1 is shown in formula (3-1), and the structure of the second monomer M2 is shown in formula (3-2).

[0072]

[0073] Example 4 Preparation of Acrylate Photoresist Film-forming Resin

[0074] At room temperature, 10.7 g of 1-(trifluoroethyl)-1H-pyrrole-2,5-dione (first monomer M1, 0.06 mol), 1.3 g of 1-adamantyl methacrylate (second monomer M2, 0.006 mol), 8.6 g of third monomer M3 (0.03 mol) and 0.15 g of azobisisobutyronitrile were dissolved in 68 g of tetrahydrofuran, heated to 70° C. under the protection of nitrogen atmosphere for reaction for 8 h, and then cooled to room temperature; the reaction mixture solution was sunk into 500 g of petroleum ether, filtered after precipitation, and the obtained solid was placed under vacuum at 80° C. and dried for 48 h. The dried solid was placed in a brown reagent bottle and stored away from light to obtain an acrylate photoresist film-forming resin, denoted as P4, with a number average molecular weight of 20,000 g / mol and a PDI of 2.78.

[0075] Example 5 Preparation of Acrylate Photoresist Film-forming Resin

[0076] At room temperature, 3.8 g of 1-(hydroxymethyl)-1H-pyrrole-2,5-dione (first monomer M1, 0.03 mol), 10.4 g of 2-methyl-2-adamantyl methacrylate (second monomer M2, 0.045 mol), 8.6 g of third monomer M3 (0.03 mol) and 0.15 g of azobisisobutyronitrile were dissolved in 62 g of tetrahydrofuran, heated to 70° C. under the protection of nitrogen atmosphere for reaction for 8 h, and then cooled to room temperature; the mixture solution obtained by the reaction was precipitated into 600 g of petroleum ether, filtered after precipitation, and the obtained solid was placed under vacuum at 80° C. and dried for 48 h. The dried solid was placed in a brown reagent bottle and stored away from light to obtain an acrylate photoresist film-forming resin, denoted as P5, with a number average molecular weight of 18372 g / mol and a PDI of 2.32.

[0077] Example 6 Preparation of ArF Photoresist

[0078] 25wt% of acrylate photoresist film-forming resin P1, 2.0wt% of photoacid generator (4-methoxyphenyldiphenyl trifluoromethanesulfonate), 0.02wt% of quencher (triethylamine) and 73wt% of solvent (cyclohexanone) are added to a clean plastic container, and the plastic container is fixed on a mechanical oscillator and shaken at room temperature for 18h to allow each component to be fully dissolved, and then filtered using a filter with a pore size of 50nm to obtain ArF photoresist F1.

[0079] Example 7 Preparation of ArF Photoresist

[0080] ArF photoresist was prepared according to the method of Example 6, except that acrylate photoresist film-forming resin P2 with the same mass fraction was used instead of acrylate photoresist film-forming resin P1, and other conditions were the same, to obtain ArF photoresist F2.

[0081] Example 8 Preparation of ArF Photoresist

[0082] ArF photoresist was prepared according to the method of Example 6, except that acrylate photoresist film-forming resin P3 with the same mass fraction was used instead of acrylate photoresist film-forming resin P1, and other conditions were the same, to obtain ArF photoresist F3.

[0083] Example 9 Preparation of ArF Photoresist

[0084] ArF photoresist was prepared according to the method of Example 6, except that acrylate photoresist film-forming resin P4 with the same mass fraction was used instead of acrylate photoresist film-forming resin P1, and other conditions were the same, to obtain ArF photoresist F4.

[0085] Example 10 Preparation of ArF Photoresist

[0086] ArF photoresist was prepared according to the method of Example 6, except that acrylate photoresist film-forming resin P5 with the same mass fraction was used instead of acrylate photoresist film-forming resin P1, and other conditions were the same, to obtain ArF photoresist F5.

[0087] Comparative Example 1 Preparation of Reference ArF Photoresist

[0088] A reference acrylate photoresist film-forming resin was prepared according to the method of Example 1, except that 3-hydroxypropyl methacrylate was used in place of the third monomer M3 at the same mass fraction, and other conditions were the same to obtain a reference acrylate photoresist film-forming resin, which was recorded as DP1.

[0089] A reference ArF photoresist was prepared according to the method of Example 6, except that the reference acrylate photoresist film-forming resin DP1 with the same mass fraction was used instead of the acrylate photoresist film-forming resin P1, and the other conditions were the same to obtain a reference ArF photoresist, which was recorded as DF1.

[0090] Comparative Example 2 Preparation of Reference ArF Photoresist

[0091] A reference acrylate photoresist film-forming resin was prepared according to the method of Example 1, except that the third monomer M3 was replaced by cyclohexanol methacrylate with the same mass fraction. Other conditions were the same to obtain a reference acrylate photoresist film-forming resin, which was recorded as DP2.

[0092] A reference ArF photoresist was prepared according to the method of Example 6, except that the reference acrylate photoresist film-forming resin DP2 with the same mass fraction was used instead of the acrylate photoresist film-forming resin P1. Other conditions were the same, and a reference ArF photoresist was obtained, which was recorded as DF2.

[0093] Test Example 1

[0094] The ArF photoresist obtained in the above-mentioned embodiment and comparative example was applied in the photoresist process. The specific operation steps were as follows: first, a "DUV-30J-14" composition (a composition for forming an organic reflective film, produced by Brewer Co., Ltd.) was coated on a silicon wafer treated with hexamethyldisilazide, and then baked at 200° C. for 60 seconds to form a reflective film on the silicon wafer. an organic anti-reflection film; the ArF photoresist solution obtained in the above embodiments and comparative examples is then spin-coated onto the silicon wafer at a spin coating speed of 1000 r / min, and the thickness of the film is measured after drying. After coating the photoresist solution, the silicon wafer is pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 1; the silicon wafer with the photoresist film formed is irradiated under an ArF laser to form a pattern, the exposure amount is gradually changed, and the exposed silicon wafer is baked for 60 seconds at the temperature shown in the "PEB" column of Table 1, and finally developed for 60 seconds using a 2.38wt% tetramethylammonium hydroxide aqueous solution to obtain a photoresist pattern.

[0095] (1) Effective sensitivity: It is expressed as the minimum exposure amount to obtain a pattern of 0.18 μm. The results are shown in Table 1.

[0096] (2) Resolution: It is expressed as the minimum size of the pattern obtained at the effective sensitivity exposure. The results are shown in Table 1.

[0097] (3) Evaluation of substrate adhesion performance: The photoresist pattern formed on the silicon wafer was observed by an optical microscope, where: ◎ indicates good peeling resistance during development (even at high exposure light, the fine pattern hardly peels off), ○ indicates that no peeling of the large pattern was observed, although some peeling of the fine pattern was observed at high exposure, and X indicates that the photoresist pattern including the large pattern completely peeled off. The results are shown in Table 1.

[0098] Test Example 2

[0099] The ArF photoresist obtained in the embodiment and the comparative example was spin-coated on different test pieces with anti-reflection layers using an ACT-8 spin coater at a spin coating speed of 1000 r / min, and then baked at 110°C for 150s. The thickness of the photoresist film was measured after cooling to room temperature. The test pieces were then placed in a LAM EXELAN HPT etching machine and etched for 20s under the process conditions of 60Mt / 1000W / 500W / 45CF4 / 180Ar / 10002. The thickness of the remaining photoresist film was measured and the etching rate of the film was calculated. The results are shown in Table 2.

[0100] Table 1

[0101]

[0102] Table 2

[0103]

[0104] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. An acrylate photoresist film-forming resin, characterized in that: The acrylate photoresist film-forming resin has a structure shown in formula (1): Formula (1), R1, R2 and R3 are each independently H, F, OH, C1-C5 alkyl, C1-C5 perfluoroalkyl or C1-C5 alkoxy, R4 is an acid-sensitive group, R5 is H or methyl, R6 is H or methyl, p:n:m is (0.05-1):1:(0.1-1.5); the structural formula of the acid-sensitive group is selected from one of the following structures: The number average molecular weight of the acrylate photoresist film-forming resin is 10000-25000 g / mol; the PDI of the acrylate photoresist film-forming resin is 1.5-2.

8.

2. A method for preparing an acrylic ester photoresist film-forming resin, characterized in that: The method comprises subjecting a first monomer M1, a second monomer M2 and a third monomer M3 to a free radical polymerization reaction in the presence of an initiator, so as to obtain an acrylate photoresist film-forming resin; the first monomer M1 has a structure shown in formula (2); the second monomer M2 has a structure shown in formula (3); the third monomer M3 has a structure shown in formula (4); the molar ratio n:m:p of the first monomer M1, the second monomer M2 and the third monomer M3 is 1:(0.1-1.5):(0.05-1); In formula (1), R1, R2 and R3 are each independently H, F, OH, C1-C5 alkyl, C1-C5 perfluoroalkyl or C1-C5 alkoxy; In formula (2), R4 is an acid-sensitive group, R5 is H or methyl, and the structural formula of the acid-sensitive group is selected from one of the following structures: In formula (3), R6 is H or methyl.

3. The method for preparing the acrylic ester photoresist film-forming resin according to claim 2, characterized in that: The content of the first monomer M1 is 30-85 mol %, the content of the second monomer M2 is 10-40 mol %, and the content of the third monomer M3 is 5-30 mol %.

4. The method for preparing the acrylic ester photoresist film-forming resin according to claim 2, characterized in that: The third monomer M3 is prepared according to a method comprising the following steps: (1) subjecting 5-norbornene-2-ol to an addition reaction in a first organic solvent to obtain (1R,4R,4aS,8aR)-dodecahydro-1,4:5,8-dimethylbiphenyl-diol, denoted as D1; (2) The D1 obtained in step (1) is subjected to a condensation reaction with methacryloyl chloride in a second organic solvent to obtain a third monomer M3.

5. The method for preparing the acrylic ester photoresist film-forming resin according to claim 4, characterized in that: The molar ratio of D1 to methacryloyl chloride is (1-1.5):

1.

6. The method for preparing the acrylic ester photoresist film-forming resin according to claim 4, characterized in that: The conditions of the addition reaction include a temperature of 90-120° C. and a time of 1-5 h.

7. The method for preparing the acrylic ester photoresist film-forming resin according to claim 4, characterized in that: The conditions of the condensation reaction include a temperature of 50-70° C. and a time of 1-5 h.

8. Acrylate photoresist film-forming resin prepared by the method according to any one of claims 2 to 7.

9. An ArF photoresist, characterized in that: The ArF photoresist contains the acrylate photoresist film-forming resin according to claim 1 or 8, a photoacid generator, a quencher and a solvent.

10. The ArF photoresist according to claim 9, characterized in that: Based on the total content of the ArF photoresist, the content of the acrylate photoresist film-forming resin is 10-30wt%, the content of the photoacid generator is 0.5-5wt%, the content of the quencher is 0.001-0.1wt%, and the content of the solvent is 65-85wt%.

11. The method for preparing ArF photoresist according to claim 9 or 10, characterized in that: The method comprises the steps of uniformly mixing an acrylic ester photoresist film-forming resin, a photoacid generator, a quencher and a solvent and filtering the mixture to obtain the ArF photoresist.

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