ArF photoresist film-forming resin and preparation method thereof, and ArF photoresist composition and preparation method thereof

Abstract

The invention relates to the technical field of photoresist, and particularly discloses ArF photoresist film-forming resin, a preparation method thereof and a photoresist composition containing the resin. The ArF photoresist film-forming resin is prepared by copolymerizing a norbornene monomer, maleic anhydride and perfluoro-n-propyl vinyl ether according to a ratio of (60 to 75 mol%): (20 to 35 mol%): (5 to 10 mol%). The preparation method comprises the following steps: dissolving, heating and polymerizing, purifying and drying. The ArF photoresist composition comprises ArF photoresist film-forming resin, an alkaline additive, a photoacid generator and an organic solvent, and the specific preparation method comprises the following steps: uniformly mixing the ArF photoresist film-forming resin, the alkaline additive, the photoacid generator and the organic solvent in a nitrogen atmosphere in a dark place according to a ratio to obtain the ArF photoresist composition. The ArF photoresist composition obtained in the invention has the characteristics of high resolution and good corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of photoresist, and particularly relates to an ArF photoresist film-forming resin, a preparation method thereof, an ArF photoresist composition containing the ArF film-forming resin, and a preparation method thereof. BACKGROUND

[0002] Photoetching and etching technology is a core process system for semiconductor chip manufacturing, and the performance of photoresist as a medium carrier for pattern transfer directly determines the precision boundary of chip manufacturing. In a typical photoetching process, through the accurate projection of a specific wavelength exposure light source, a photo initiator promotes a photochemical reaction of the photoresist, and after a post-baking curing and developing process, a mask pattern with nanometer precision is formed. The pattern, as a template barrier for subsequent ion implantation or etching process, has a decisive influence on the electrical properties of the device in terms of edge steepness, line width uniformity, and interface stability.

[0003] The current mainstream photoresist system faces significant challenges in the process node below 28 nm: the resolution limit leads to a decrease in critical dimension (CD) control precision, the insufficient etching resistance causes pattern distortion, and the swelling effect in the developing process has a negative impact on line edge roughness (LER). In view of these technical bottlenecks, the industry is striving to develop new resin matrix and functional monomer systems. By introducing branched structure resins with precisely controllable molecular weight, the photo quantum efficiency of the material in the extreme ultraviolet (EUV) or deep ultraviolet (DUV) band can be effectively improved; and the etching-resistant groups containing fluorine / silicon can strengthen the structure retention of the pattern in dry etching. Most importantly, through the optimization design of the resin molecular topology structure and the synergistic effect of the photosensitive components, the resolution and etching resistance of the photoresist system can be simultaneously improved, which has strategic significance for breaking through the technical barriers of semiconductor manufacturing below 3 nm. SUMMARY

[0004] In order to solve the problems existing in the prior art, the present application aims to provide an ArF photoresist film-forming resin and a preparation method thereof, which can improve the resolution and etching resistance, so that the obtained photoresist has high transparency and good etching resistance.

[0005] Another object of the present application is to provide an ArF photoresist composition containing the ArF photoresist film-forming resin and a preparation method thereof.

[0006] To achieve the above objects, the technical solutions of the present application are as follows:

[0007] In a first aspect, the present application provides an ArF photoresist film-forming resin, which comprises the following proportions of each component:

[0008] norbornene-based monomer: 60 to 75 mol%, for example, 60 mol%, 61 mol%, 62 mol%, 63 mol%, 64 mol%, 65 mol%, 66 mol%, 67 mol%, 68 mol%, 69 mol%, 70 mol%, 71 mol%, 72 mol%, 73 mol%, 74 mol%, 75 mol%, etc.

[0009] maleic anhydride: 20 to 35 mol%, for example, 20 mol%, 21 mol%, 22 mol%, 23 mol%, 24 mol%, 25 mol%, 26 mol%, 27 mol%, 28 mol%, 29 mol%, 30 mol%, 31 mol%, 32 mol%, 33 mol%, 34 mol%, 35 mol%, etc.

[0010] perfluoro-n-propyl vinyl ether: 5 to 10 mol%, for example, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, etc.

[0011] In some specific embodiments, the ArF photoresist film-forming resin has a weight average molecular weight of 3000 to 20000, for example, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, etc., and for example, preferably, a weight average molecular weight of 5000 to 15000.

[0012] In some specific embodiments, the norbornene monomer is selected from one or more of dicyclo[2,2,1]hept-2-ene, 1-methyldicyclo[2,2,1]hept-2-ene, 5-methyldicyclo[2,2,1]hept-2-ene, 7-methyldicyclo[2,2,1]hept-2-ene, 1-ethyldicyclo[2,2,1]hept-2-ene, 5-ethyldicyclo[2,2,1]hept-2-ene, 5,5-dimethyldicyclo[2,2,1]hept-2-ene, 7-oxadicyclo[2,2,1]heptane, 5-hydroxymethyldicyclo[2,2,1]hept-2-ene, 5-methoxydicyclo[2,2,1]hept-2-ene, 5-(methoxymethoxy)dicyclo[2,2,1]hept-2-ene, methyl 5-carboxylic acid dicyclo[2,2,1]hept-2-ene ester, dicyclo[2,2,1]hept-2-ene-5 carboxylic acid tert-butyl ester, 5-(tert-butoxycarbonyl)dicyclo[2,2,1]hept-2-ene, 5-(4-methylbutyrolactonyl)dicyclo[2,2,1]hept-2-ene, 1-phenyldicyclo[2,2,1]hept-2-ene, 5-phenyldicyclo[2,2,1]hept-2-ene, 5-vinyldicyclo[2,2,1]hept-2-ene, endo-oxadicyclo[3,2,1]oct-6-en-2-one, preferably selected from one or more of dicyclo[2,2,1]hept-2-ene, 1-methyldicyclo[2,2,1]hept-2-ene, 5-methyldicyclo[2,2,1]hept-2-ene, 5,5-dimethyldicyclo[2,2,1]hept-2-ene, 7-methyldicyclo[2,2,1]hept-2-ene, 1-ethyldicyclo[2,2,1]hept-2-ene, 5-hydroxymethyldicyclo[2,2,1]hept-2-ene.

[0013] In a second aspect, the present application provides a preparation method of an ArF photoresist film-forming resin, and the specific steps are as follows:

[0014] S1, dissolving norbornene monomer, maleic anhydride, perfluoro-n-propyl vinyl ether and initiator in a first solvent to obtain solution a;

[0015] S2, heating the solution a to 30-120°C (for example 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, etc.) under nitrogen protection, and reacting for 6-20h (for example 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, etc.) to obtain polymer solution b;

[0016] S3, dropping the polymer solution b into a second solvent, and extracting to obtain white precipitate;

[0017] S4, dissolving the white precipitate in a third solvent to obtain resin solution c;

[0018] S5, repeating S3 and S4 1-2 times for the resin solution c, and then performing vacuum drying at 40-80°C (for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.) to obtain a finished ArF photoresist film-forming resin powder.

[0019] In some specific embodiments, the initiator is selected from one or more of azo initiators, peroxide initiators, preferably one or more of azobisisobutyronitrile, azobisisoamyl nitrile, azobisisoheptyl nitrile, azobiscyclohexyl nitrile, dimethyl azobisbutyrate, benzoyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, t-butyl peroxybenzoate, dicumyl peroxide.

[0020] In some specific embodiments, the first solvent, the third solvent are independently selected from one or more of cyclohexanone, propylene glycol methyl ether, dipropylene glycol methyl ether, tetrahydrofuran, propylene glycol methyl ether acetate, ethyl lactate, gamma-butyrolactone.

[0021] In some specific embodiments, the second solvent is selected from one or more of methanol, ethanol, isopropanol, n-hexane, cyclohexane, heptane.

[0022] In a third aspect, the present application provides an ArF photoresist composition, comprising the following components in mass percentage:

[0023] ArF photoresist film-forming resin: 5%-20%, for example, 5%, 8%, 10%, 12%, 15%, 18%, 20%, etc., preferably 10%-15%;

[0024] Basic additive: 0.1%-4%, for example, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc., preferably 0.5%-2%;

[0025] Photoacid generator: 1%-5%, for example, 1%, 2%, 3%, 4%, 5%, etc., preferably 2%-3%;

[0026] Organic solvent: 75%-90%, for example, 75%, 78%, 80%, 83%, 85%, 88%, 90%, etc., preferably 80%-85%;

[0027] In some specific embodiments, the ArF photoresist film-forming resin is the ArF photoresist film-forming resin as described above or prepared by the method as described above.

[0028] In some specific embodiments, the basic additive is selected from one or more of tripropylamine, tributylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxyethanolamine, trimethoxymethoxyethylamine, tetramethylammonium hydroxide.

[0029] In some specific embodiments, the photoacid generator is selected from one or more of sulfonium salts, iodonium salts, sulfonate esters, oxime sulfonate esters, preferably one or more of triphenylsulfonium triflate, triphenylsulfonium nonaflate, bis(4-tert-butylphenyl)phenylsulfonium perfluoro octylsulfonate, bis(4-tert-butylphenyl)iodonium triflate, bis(4-methoxyphenyl)iodonium nonaflate, triphenyl iodonium hexafluoroantimonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrostyryl tert-butyl sulfonate, phenyl perfluoroalkyl sulfonate, alpha-methylstyrene oxime triflate, acetophenone oxime nonaflate, bis(trifluoromethyl)acetyl oxime perfluoro octyl sulfonate.

[0030] In some specific embodiments, the organic solvent is selected from one or more of ketones, polyols, alkyl ethers, alkyl acid esters, amide solvents, preferably one or more of acetone, methyl ethyl ketone, cyclohexanone, methyl isopropyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, propylene glycol monoacetate, dipropylene glycol monoacetate, and diacetate, and mono-methyl, mono-ethyl, mono-propyl, mono-butyl, and mono-phenyl ethers thereof, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone.

[0031] In a third aspect, the present application provides a method for preparing the ArF photoresist composition as described above, comprising the steps of: mixing the ArF photoresist film-forming resin, the basic additive, the photoacid generator, and the organic solvent in a ratio under a nitrogen atmosphere, and then performing 0.22 micron or smaller pore size filtration to obtain the ArF photoresist composition.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] 1) The ArF photoresist film-forming resin of the present application comprises norbornene monomers, maleic anhydride, and perfluoro-n-propyl vinyl ether components, and in particular the perfluoro-n-propyl vinyl ether component, by introducing a strong electronegative rigid fluorine-containing group, the characteristic absorption of the material at 193 nm is significantly reduced, and at the same time a physical barrier is formed at the etching interface, so that the obtained photoresist has high transparency and good etching resistance.

[0034] 2) The ArF photoresist composition of the present application comprises ArF photoresist film-forming resin, basic additive, photoacid generator and organic solvent in a certain proportion, which can better inhibit acid diffusion after exposure, improve the pattern resolution and lithography performance in the conventional crosslinking state, and obtain high resolution and good pattern topography. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present application, the present application will be further described below in conjunction with examples. It should be understood that the following examples are only for better understanding of the present application, and do not mean that the present application is limited to the following examples only. For the process parameters not specifically mentioned, the conventional technology can be referred to.

[0036] The main raw materials of the following examples are as follows:

[0037] In the examples and comparative examples of the present application, the main raw materials are as follows, and other raw materials and reagents are purchased through ordinary market channels if not specifically mentioned.

[0038] The test methods involved in the following examples are as follows:

[0039] Weight average molecular weight and molecular weight distribution: measured by gel permeation chromatography.

[0040] Sensitivity: the minimum exposure dose is measured by an exposure dose tester.

[0041] Development resolution: the minimum feature size after development is observed by a scanning electron microscope.

[0042] Etching rate: the difference in film thickness before and after etching is measured by a step meter.

[0043] Pattern topography: observed by a scanning electron microscope.

[0044] Example 1

[0045] In a nitrogen atmosphere, 7.35 g of bicyclo[2,2,1]hept-2-ene (CAS No. 498-66-8), 3.29 g of maleic anhydride, 1.78 g of perfluoro-n-propyl vinyl ether, 50 g of propylene glycol methyl ether were added to a 100 mL reaction bottle, then 0.42 g of azobisisobutyronitrile was added, fully stirred and dissolved, heated to 80°C, and kept for 10 hours. Then it was cooled to room temperature, precipitated by dropping into cyclohexane, filtered, dissolved in propylene glycol methyl ether, precipitated again by dropping into cyclohexane, filtered, and the filter cake was vacuum dried at 50°C to obtain the film-forming resin. The weight average molecular weight Mw of the resin was 8500 and the molecular weight distribution PDI was 1.35 measured by GPC.

[0046] Example 2

[0047] In a nitrogen atmosphere, 7.78 g of 5-methyldicyclo[2,2,1]hept-2-ene (CAS No. 16301-26-1), 3.28 g of maleic anhydride, 2.38 g of perfluoro-n-propyl vinyl ether, 56 g of propylene glycol methyl ether were added to a 100 mL reaction flask, 0.45 g of azobisisobutyronitrile was further added, dissolved by stirring, heated to 80°C, and kept for 9 hours. Then, it was lowered to room temperature, precipitated by dropping into cyclohexane, filtered; dissolved by adding propylene glycol methyl ether, precipitated again by dropping into cyclohexane, filtered, and the filter cake was vacuum dried at 45°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 8700, and the molecular weight distribution PDI was 1.39 as measured by GPC.

[0048] Example 3

[0049] In a nitrogen atmosphere, 8.93 g of 5,5-dimethyldicyclo[2,2,1]hept-2-ene (CAS No. 30561-37-0), 2.15 g of maleic anhydride, 1.33 g of perfluoro-n-propyl vinyl ether, 52 g of cyclohexanone were added to a 100 mL reaction flask, 0.68 g of benzoyl peroxide was further added, dissolved by stirring, heated to 90°C, and kept for 6 hours. Then, it was lowered to room temperature, precipitated by dropping into methanol, filtered. Dissolved by adding tetrahydrofuran, precipitated again by dropping into methanol, filtered, and the process was repeated twice, and the filter cake was vacuum dried at 50°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 6800, and the molecular weight distribution PDI was 1.22 as measured by GPC.

[0050] Example 4

[0051] In a nitrogen atmosphere, 7.42 g of 1-ethyldicyclo[2,2,1]hept-2-ene (CAS No. 1523-17-9), 2.44 g of maleic anhydride, 1.75 g of perfluoro-n-propyl vinyl ether, 48 g of γ-butyrolactone were added to a 100 mL reaction flask, 0.38 g of azobisisoheptane nitrile was further added, dissolved by stirring, heated to 70°C, and kept for 15 hours. Then, it was lowered to room temperature, precipitated by dropping into isopropyl alcohol, filtered; dissolved by adding propylene glycol methyl ether acetate, precipitated again by dropping into isopropyl alcohol, filtered, and the filter cake was vacuum dried at 40°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 12000, and the molecular weight distribution PDI was 1.45 as measured by GPC.

[0052] Example 5

[0053] In a nitrogen atmosphere, 8.05 g of 7-oxabicyclo[2,2,1]heptane (CAS No. 286-08-8), 2.94 g of maleic anhydride, 1.62 g of perfluoro-n-propyl vinyl ether, 55 g of cyclohexanone were added to a 100 mL reaction flask, and then 0.50 g of benzoyl peroxide was added, and the mixture was stirred and dissolved, and heated to 85°C, and held for 12 hours. Then, it was allowed to cool to room temperature, and precipitated by dropwise addition to methanol, and filtered; dissolved in tetrahydrofuran, and again precipitated by dropwise addition to methanol, and filtered, and the filter cake was vacuum dried at 55°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 7200, and the molecular weight distribution PDI was 1.28, as measured by GPC.

[0054] Example 6

[0055] In a nitrogen atmosphere, 9.30 g of 5-hydroxymethylbicyclo[2,2,1]hept-2-ene (CAS No. 33978-25-9), 2.45 g of maleic anhydride, 1.50 g of perfluoro-n-propyl vinyl ether, 48 g of γ-butyrolactone were added to a 100 mL reaction flask, and then 0.35 g of azobisisoheptane nitrile was added, and the mixture was stirred and dissolved, and heated to 75°C, and held for 14 hours. Then, it was allowed to cool to room temperature, and precipitated by dropwise addition to isopropanol, and filtered; dissolved in propylene glycol methyl ether acetate, and again precipitated by dropwise addition to isopropanol, and filtered, and the filter cake was vacuum dried at 45°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 10500, and the molecular weight distribution PDI was 1.42, as measured by GPC.

[0056] Example 7

[0057] In a nitrogen atmosphere, 12.30 g of methyl 5-carboxylic acid bicyclo[2,2,1]hept-2-ene (CAS No. 6203-13-0), 2.55 g of maleic anhydride, 1.45 g of perfluoro-n-propyl vinyl ether, 60 g of tetrahydrofuran were added to a 100 mL reaction flask, and then 0.55 g of azobisisobutyronitrile was added, and the mixture was stirred and dissolved, and heated to 95°C, and held for 8 hours. Then, it was allowed to cool to room temperature, and precipitated by dropwise addition to n-hexane, and filtered; dissolved in ethyl lactate, and again precipitated by dropwise addition to n-hexane, and filtered, and the filter cake was vacuum dried at 60°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 7800, and the molecular weight distribution PDI was 1.31, as measured by GPC.

[0058] Example 8

[0059] In a nitrogen atmosphere, 12.10 g of 2-(trifluoromethyl)dicyclo[2,2,1]hept-2-ene (CAS No. 1686-38-0), 3.14 g of maleic anhydride, 1.52 g of perfluoro-n-propyl vinyl ether, 52 g of propylene glycol methyl ether acetate were added to a 100 mL reaction bottle, and then 0.48 g of diisopropyl peroxydicarbonate was added, dissolved by stirring, heated to 70°C, and incubated for 16 hours. Then, it was lowered to room temperature, precipitated by dropping into ethanol, filtered; dissolved by adding cyclohexanone, precipitated again by dropping into ethanol, filtered, and the filter cake was vacuum dried at 65°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 11500, and the molecular weight distribution PDI was 1.38, as measured by GPC.

[0060] Example 9

[0061] In a nitrogen atmosphere, 12.75 g of 5-phenyl dicyclo[2,2,1]hept-2-ene (CAS No. 15185-21-2), 2.84 g of maleic anhydride, 1.60 g of perfluoro-n-propyl vinyl ether, 58 g of propylene glycol methyl ether were added to a 100 mL reaction bottle, and then 0.52 g of dimethyl azobis isobutyrate was added, dissolved by stirring, heated to 100°C, and incubated for 7 hours. Then, it was lowered to room temperature, precipitated by dropping into heptane, filtered; dissolved by adding dipropylene glycol methyl ether, precipitated again by dropping into heptane, filtered, and the filter cake was vacuum dried at 70°C to obtain a film-forming resin. The weight average molecular weight Mw of the resin was 9400, and the molecular weight distribution PDI was 1.25, as measured by GPC.

[0062] Example 10

[0063] An ArF photoresist composition, the composition comprising:

[0064] ArF photoresist film-forming resin: 12 wt% of the resin prepared in Example 1;

[0065] Basic additive: 1.0 wt% of tributylamine;

[0066] Photoacid generator: 2.5 wt% of bis(4-tert-butylphenyl) iodonium triflate;

[0067] Organic solvent: 84.5 wt% of propylene glycol methyl ether acetate.

[0068] The preparation method steps are: under a nitrogen atmosphere, the ArF photoresist film-forming resin, the basic additive, the surfactant, the photoacid generator, and the organic solvent are mixed by one-pot method under light-proof conditions, and the mixture is shaken for 24 hours at room temperature, and then filtered using a 0.22 μm organic filter device (filter core material: nylon) to obtain the ArF photoresist composition.

[0069] Example 11

[0070] An ArF photoresist composition, the composition comprising:

[0071] ArF photoresist film-forming resin: 10 wt% of the resin prepared in Example 2;

[0072] Basic additive: 0.5 wt% of trioctylamine;

[0073] Photoacid generator: 2 wt% of triphenylsulfonium triflate;

[0074] Organic solvent: 47.5 wt% of propylene glycol methyl ether, 40 wt% of ethyl lactate. The preparation method is the same as that of Example 10.

[0075] Example 12

[0076] An ArF photoresist composition, the composition comprising:

[0077] ArF photoresist film-forming resin: 15 wt% of the resin prepared in Example 3;

[0078] Basic additive: 0.3 wt% of tripropylamine, 0.3 wt% of triethanolamine;

[0079] Photoacid generator: 2.5 wt% of bis(4-tert-butylphenyl) iodonium triflate;

[0080] Organic solvent: 50 wt% of propylene glycol monomethyl ether acetate, 31.9 wt% of propylene glycol methyl ether. The preparation method is the same as that of Example 10.

[0081] Example 13

[0082] An ArF photoresist composition, the composition comprising:

[0083] ArF photoresist film-forming resin: 15 wt% of the resin prepared in Example 4;

[0084] Basic additive: 1 wt% of triisobutylamine;

[0085] Photoacid generator: 3 wt% of perfluoroalkylsulfonic acid phenyl ester;

[0086] Organic solvent: 81 wt% of propylene glycol methyl ether acetate.

[0087] The preparation method is the same as that of Example 10.

[0088] Example 14

[0089] An ArF photoresist composition, the composition comprising:

[0090] ArF photoresist film-forming resin: 10 wt% of the resin prepared in Example 5;

[0091] Basic additive: 0.8 wt% of triethoxyethanolamine;

[0092] Photoacid generator: 2.2 wt% of triphenylsulfonium nonafluorobutane sulfonate;

[0093] Organic solvent: 87.0 wt% of propylene glycol methyl ether acetate.

[0094] The preparation method is the same as that of Example 10.

[0095] Example 15

[0096] An ArF photoresist composition, the composition comprising:

[0097] ArF photoresist film-forming resin: 15 wt% of the resin prepared in Example 6;

[0098] Basic additive: 1.5 wt% of tetramethylammonium hydroxide;

[0099] Photoacid generator: 3.0 wt% of α-methylstyrene oxime triflate; Organic solvent: 80.5 wt% of ethyl lactate.

[0100] The preparation method is the same as that of Example 10.

[0101] Example 16

[0102] An ArF photoresist composition, the composition comprising:

[0103] ArF photoresist film-forming resin: 12 wt% of the resin prepared in Example 7;

[0104] Basic additive: 0.6 wt% of trioctylamine;

[0105] Photoacid generator: 1.8 wt% of bis(4-methoxyphenyl) iodonium nonafluorobutane sulfonate; Organic solvent: 85.6 wt% of γ-butyrolactone.

[0106] The preparation method is the same as that of Example 10.

[0107] Example 17

[0108] An ArF photoresist composition, the composition comprising:

[0109] ArF photoresist film-forming resin: 18 wt% of the resin prepared in Example 8;

[0110] Basic additive: 1.2 wt% of triisobutylamine;

[0111] Photoacid generator: 4.0 wt% of perfluoroalkylsulfonic acid phenyl ester;

[0112] Organic solvent: 76.8 wt% of cyclohexanone.

[0113] The preparation method is the same as that of Example 10.

[0114] Example 18

[0115] An ArF photoresist composition, the composition comprising:

[0116] ArF photoresist film-forming resin: 8 wt% of the resin prepared in Example 9;

[0117] Basic additive: 0.4 wt% of tripropylamine;

[0118] Photoacid generator: 1.6 wt% of phenacyl oxime nonafluorobutane sulfonate;

[0119] Organic solvent: 90 wt% of propylene glycol methyl ether.

[0120] The preparation method is the same as that of Example 10.

[0121] Comparative Example 1

[0122] Referring to the ArF photoresist film-forming resin of Example 1, the only difference is that the perfluoro-n-propyl vinyl ether monomer is replaced by an equal mass of solvent, and other conditions remain unchanged; the ArF photoresist composition is prepared according to Example 10.

[0123] Comparative Example 2

[0124] Referring to the ArF photoresist film-forming resin of Example 1, the only difference is that the perfluoro-n-propyl vinyl ether monomer is replaced by an equal molar proportion of n-propyl vinyl ether, and other conditions remain unchanged; the ArF photoresist composition is prepared according to Example 10.

[0125] Comparative Example 3

[0126] Referring to the ArF photoresist film-forming resin of Example 1, the only difference is that the amount of perfluoro-n-propyl vinyl ether monomer is doubled, and an equal mass of solvent is deducted, and other conditions remain unchanged; the ArF photoresist composition is prepared according to Example 10.

[0127] Test Example

[0128] The ArF photoresist compositions of the above examples and comparative examples are subjected to photoresist spin coating (spin coating speed 1200 rpm, uniform thickness 300 nm) using a silicon wafer treated with hexamethyldisilazane, pre-baked at 110°C for 60 s, exposed under an exposure machine (exposure wavelength 193 nm), and the exposed silicon wafer is post-baked at 120°C for 60 s, and then developed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) developer, to obtain a photoetching pattern. The sensitivity, development resolution and etching rate at the same resolution are tested, and the results are shown in the following table.

[0129]

[0130]

[0131] From the above table, it can be seen that the ArF photoresist compositions prepared in the examples exhibit significantly superior comprehensive performance. Specifically, in terms of resolution, the examples 10-18 all achieve finer patterning ability compared to the comparative examples, and the resolution is significantly lower than that of the comparative examples, indicating that the compositions can effectively form smaller size microstructure features. In terms of etching resistance, the relative etching rates of the examples 10-18 are overall lower than those of the comparative examples, showing more excellent etching resistance stability. In addition, the sensitivity of the examples is simultaneously optimized, further improving the efficiency of the exposure process. In summary, the ArF photoresist compositions provided by the present application have high resolution and good etching resistance.

[0132] It is easily understood that the above examples are only examples for clearly illustrating the present application, and do not mean that the present application is limited to this. For ordinary skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. An ArF photoresist film-forming resin, characterized in that, comprise the following proportions of each component: norbornene-based monomer: 60-75 mol%; maleic anhydride: 20-35 mol%; perfluoro-n-propyl vinyl ether: 5-10 mol%.

2. The ArF photoresist film-forming resin according to claim 1, wherein The molecular weight of the ArF photoresist film-forming resin is 3000-20000, preferably 5000-15000.

3. The ArF photoresist film-forming resin according to claim 1, wherein The norbornene-based monomer is selected from one or more of dicyclo[2,2,1]hept-2-ene, 1-methyldicyclo[2,2,1]hept-2-ene, 5-methyldicyclo[2,2,1]hept-2-ene, 7-methyldicyclo[2,2,1]hept-2-ene, 1-ethyldicyclo[2,2,1]hept-2-ene, 5-ethyldicyclo[2,2,1]hept-2-ene, 5,5-dimethyldicyclo[2,2,1]hept-2-ene, 7-oxadicyclo[2,2,1]heptane, 5-hydroxymethyldicyclo[2,2,1]hept-2-ene, 5-methoxydicyclo[2,2,1]hept-2-ene, 5-(methoxymethoxy)dicyclo[2,2,1]hept-2-ene, methyl 5-carboxylic acid dicyclo[2,2,1]hept-2-ene ester, dicyclo[2,2,1]hept-2-ene-5 carboxylic acid tert-butyl ester, 5-(tert-butoxycarbonyl)dicyclo[2,2,1]hept-2-ene, 5-(4-methylbutyrolactonyl)dicyclo[2,2,1]hept-2-ene, 1-phenyldicyclo[2,2,1]hept-2-ene, 5-phenyldicyclo[2,2,1]hept-2-ene, 5-vinyldicyclo[2,2,1]hept-2-ene, endo-oxadicyclo[3,2,1]oct-6-ene-2-one, preferably selected from one or more of dicyclo[2,2,1]hept-2-ene, 1-methyldicyclo[2,2,1]hept-2-ene, 5-methyldicyclo[2,2,1]hept-2-ene, 5,5-dimethyldicyclo[2,2,1]hept-2-ene, 7-methyldicyclo[2,2,1]hept-2-ene, 1-ethyldicyclo[2,2,1]hept-2-ene, 5-hydroxymethyldicyclo[2,2,1]hept-2-ene.

4. The method for producing an ArF photoresist film-forming resin according to any one of claims 1 to 3, characterized by, The preparation steps include: S1, dissolving the norbornene-based monomer, maleic anhydride, perfluoro-n-propyl vinyl ether and initiator in a first solvent to obtain solution a; S2, heating the solution a to 30-120°C under nitrogen protection for 6-20h to obtain polymer solution b; S3, adding the polymer solution b dropwise to a second solvent, and filtering to obtain white precipitate; S4, dissolving the white precipitate in a third solvent to obtain resin solution c; S5, repeating the steps S3 and S4 1-5 times, and then filtering and drying under vacuum at 40-80°C to obtain the finished ArF photoresist film-forming resin powder.

5. The preparation method according to claim 4, characterized in that, The initiator is selected from one or more of azo initiators and peroxide initiators, preferably selected from one or more of azobisisobutyronitrile, azobisisopentanitrile, azobisisoheptylnitrile, azobiscyclohexylcarbonitrile, dimethyl azodicarboxylate, benzoyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, diisopropyl peroxybenzene; and / or The first solvent, the third solvent are independently selected from one or more of cyclohexanone, propylene glycol methyl ether, dipropylene glycol methyl ether, tetrahydrofuran, propylene glycol methyl ether acetate, ethyl lactate, gamma-butyrolactone; and / or The second solvent is selected from one or more of methanol, ethanol, isopropanol, n-hexane, cyclohexane, heptane.

6. An ArF photoresist composition, characterized by comprising: The components include the following mass percentages: The ArF photoresist film-forming resin is 5% to 20%, preferably 10% to 15%; The basic additive is 0.1% to 4%, preferably 0.5% to 2%; The photoacid generator is 1% to 5%, preferably 2% to 3%; The organic solvent is 75% to 90%, preferably 80% to 85%; The ArF photoresist film-forming resin is the ArF photoresist film-forming resin of any one of claims 1 to 3 or the ArF photoresist film-forming resin prepared by the preparation method of claim 4 or 5.

7. The ArF photoresist composition according to claim 6, wherein The basic additive is selected from one or more of tripropylamine, tributylamine, triisobutylamine, trioctylamine, triethanolamine, triethoxyethanolamine, trimethoxy-methoxyethylamine, tetramethylammonium hydroxide.

8. The ArF photoresist composition according to claim 6, wherein The photoacid generator is selected from one or more of sulfonium salts, iodonium salts, sulfonate esters, oxime sulfonate esters, preferably selected from one or more of triphenylsulfonium triflate, triphenylsulfonium nonaflate, bis(4-tert-butylphenyl)phenylsulfonium perfluoroalkylsulfonate, bis(4-tert-butylphenyl)iodonium triflate, bis(4-methoxyphenyl)iodonium nonaflate, triphenylphosphonium hexafluoroantimonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrostyryl sulfonic acid tert-butyl ester, perfluoroalkylsulfonic acid phenyl ester, alpha-methylstyrene oxime triflate, acetophenone oxime nonaflate, bis(trifluoromethyl)acetyl oxime perfluoroalkylsulfonate.

9. The ArF photoresist composition according to claim 6, wherein The organic solvent is selected from one or more of ketones, polyols, alkyl ethers, alkyl acid esters, amide solvents, preferably selected from one or more of acetone, methyl ethyl ketone, cyclohexanone, methyl isopropyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, ethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, and mono-methyl, mono-ethyl, mono-propyl, mono-butyl, and mono-phenyl ethers thereof, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone.

10. A method for producing the ArF photoresist composition according to any one of claims 6 to 9, characterized by, The preparation steps are: under a nitrogen atmosphere, the ArF photoresist film-forming resin, the basic additive, the photoacid generator, and the organic solvent are mixed uniformly in proportion in the dark, then filtered through a 0.22 micron or smaller pore size filter to obtain a photoresist mixture.

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