Photoresist precursor composition, related product and photoresist pattern forming method

Abstract

The invention provides a photoresist precursor composition, a related product and a photoresist pattern forming method, and belongs to the technical field of photoresist. The photoresist precursor composition is composed of monomers, an initiator and a solvent, wherein the monomers are composed of A-type monomers, B-type monomers, C-type monomers and D-type monomers. New photoresist resin can be formed by adopting the monomers to carry out free radical polymerization reaction. The photoresist prepared from the photoresist resin has good photocuring performance, and can realize higher photoetching resolution.

Description

Technical Field

[0001] The invention belongs to the technical field of photoresists, and relates to a photoresist precursor composition and related products, and a photoresist pattern forming method. Background Art

[0002] Photoresist, also known as photoresist, is a material that changes its solubility or resists etching by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. Usually, photoresist is composed of three main components: photosensitive resin, sensitizer, and solvent. According to the image form, photoresist is divided into two categories: positive photoresist and negative photoresist. Photoresist in which the exposed part is dissolved and the unexposed part is retained is positive photoresist, and photoresist in which the exposed part is retained and the unexposed part is dissolved is negative photoresist. In order to make fine patterns, a method of shortening the wavelength of the exposure light source (increasing energy) is generally adopted. Specifically, although ultraviolet rays represented by g-line and i-line are used in the prior art, KrF excimer lasers or ArF excimer lasers have begun to be used to mass-produce semiconductor devices. In addition, research is also being conducted on extreme ultraviolet (EUV), X-rays, etc.

[0003] Chinese patent application 202010460924.5 provides a photoresist composition and a preparation method thereof, including a phenolic resin composition, a photosensitive compound and an organic solvent. The phenolic resin composition includes: a first linear phenolic resin, a second linear phenolic resin and a third linear phenolic resin. The first linear phenolic resin has a high sensitivity, and the second linear phenolic resin and the third linear phenolic resin have a high heat resistance temperature. The three phenolic resins cooperate with each other and work synergistically, so that the photoresist composition has a high heat resistance temperature and a high sensitivity.

[0004] Chinese patent application 200410076928.4 provides a sulfonamide compound, a polymer compound, an anti-corrosion material and a pattern forming method. The sulfonamide compound has excellent permeability at exposure of ≤300nm, excellent substrate adhesion and surface solubility. However, the photoresist components of the prior art are often relatively complex, resulting in an increased probability of introducing impurities. Summary of the invention

[0005] In view of this, an object of the present invention is to provide a photoresist with simple chemical composition and high lithography resolution.

[0006] To achieve the above-mentioned object of the invention, on the one hand, the present invention provides a photoresist precursor composition, which is composed of a monomer, an initiator and a solvent;

[0007] The monomers are composed of A-type monomers, B-type monomers, C-type monomers and D-type monomers;

[0008] The type A monomer is selected from at least one of (1,1,1,3,3,3-hexafluoroisopropyl)methacrylate, trifluoroethyl methacrylate, (3,3,4,4,4-pentafluoro-n-butyl)methacrylate, and 3,3,3-trifluoro-2-methylpropyl methacrylate;

[0009] The B-type monomer is at least one selected from 1-(methoxymethyl)cyclopentyl methacrylate, (1-(adamantan-1-yl)cyclopentyl)methacrylate, and 1-isopropylcyclopentyl methacrylate;

[0010] The C-type monomer is selected from at least one of (3-hydroxy-2,2,4,4-tetramethylcyclobutyl) methacrylate and (3,3-dimethyl-1-ethylcyclobutyl) methacrylate;

[0011] The D-type monomer is (2-(9-fluorenylmethoxycarbonylamino)ethyl)methacrylate;

[0012] The initiator is a free radical photoinitiator;

[0013] The solvent is selected from at least one of methyl ethyl ketone, cyclopentanone and cyclohexanone.

[0014] The Chinese chemical names and corresponding chemical structural formulas of the above monomers are shown in Table 1.

[0015] Table 1

[0016]

[0017]

[0018] Preferably, the molar ratio of the monomer to the initiator is 1:0.01-0.1. More preferably, the molar ratio of the monomer to the initiator is 1:0.05.

[0019] Preferably, the mass of the solvent is 2.5-3.5 times the total mass of the monomer and the initiator.

[0020] Preferably, the molar ratio of the A-type monomer, the B-type monomer, the C-type monomer and the D-type monomer is 0.2-0.25: 0.25-0.32: 0.3-0.35: 0.13-0.2.

[0021] More preferably, the molar ratio of the type A monomer, the type B monomer, the type C monomer and the type D monomer is 0.23:0.3:0.32:0.15.

[0022] Preferably, the ratio of the total molar number of fluorine atoms in the class A monomer to the total molar number of the monomer is 0.12-1.2:1; more preferably 0.69-1.15:1; and even more preferably 0.8-1.09:1. As a preferred embodiment of the present invention, the ratio of the total molar number of fluorine atoms in the class A monomer to the total molar number of the monomer is 0.85:1.

[0023] Here, "the monomer" refers to the monomer in the entire photoresist precursor composition "consisting of monomers, initiators and solvents". In the present invention, "the monomer" consists of Class A monomers, Class B monomers, Class C monomers and Class D monomers.

[0024] Preferably, the Class A monomer is a mixture of (3,3,4,4,4-pentafluoro-n-butyl)methacrylate and 3,3,3-trifluoro-2-methylpropyl methacrylate; the Class B monomer is (1-(adamantan-1-yl)cyclopentyl)methacrylate; and the Class C monomer is (3-hydroxy-2,2,4,4-tetramethylcyclobutyl)methacrylate.

[0025] More preferably, the molar ratio of the (3,3,4,4,4-pentafluoro-n-butyl)methacrylate, the 3,3,3-trifluoro-2-methylpropyl methacrylate, the (1-(adamantan-1-yl)cyclopentyl)methacrylate, the (3-hydroxy-2,2,4,4-tetramethylcyclobutyl)methacrylate and the (2-(9-fluorenylmethoxycarbonylamino)ethyl)methacrylate is 0.08:0.15:0.3:0.32:0.15.

[0026] Preferably, the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate.

[0027] More preferably, and as an example of the present invention, the initiator is azobisisobutyronitrile.

[0028] Preferably, the solvent is methyl ethyl ketone.

[0029] In another aspect, the present invention provides a photoresist resin prepared from the above-mentioned photoresist precursor composition.

[0030] Preferably, the photoresist resin has a type A repeating unit, a type B repeating unit, a type C repeating unit and a type D repeating unit;

[0031] The A-type repeating unit is selected from one or more of the following structures

[0032]

[0033] The B-type repeating unit is selected from one or more of the following structures

[0034]

[0035] The C-type repeating unit is selected from one or more of the following structures

[0036]

[0037] The D-type repeating unit has the following structure

[0038]

[0039] In the photoresist resin provided by the present invention, the A-type repeating unit contained has a chain group containing fluorine elements, which functions to increase the flexibility and transmittance of the photoresist material; the B-type repeating group and the C-type repeating group contained have a five-membered ring and a four-membered ring structure with structural tension, which can generate free radicals under the excitation of light; the D-type group contained has a photobase structure, which can expose amino groups under the excitation of light, making the photoresist more uniform. The above four repeating units work synergistically in the photolithography process of the photoresist resin, and can achieve fast and high-resolution photocuring.

[0040] Preferably, the molar ratio of the type A repeating unit, the type B repeating unit, the type C repeating unit and the type D repeating unit is 1-2:6-12:6-13:2-3.

[0041] Preferably, the type A repeating unit is The B-type repeating unit is The C-type repeating unit is The D-type repeating unit is

[0042] More preferably, the Said Said

[0043] Said and stated

[0044] The molar ratio is 1:2:4:6:2.

[0045] On the other hand, the present invention provides a method for preparing the above-mentioned photoresist resin, comprising the following steps: mixing monomers, initiators and solvents, refluxing under inert gas protection overnight, precipitating and washing to obtain the photoresist resin.

[0046] Preferably, the inert gas is selected from one of nitrogen, argon and carbon dioxide.

[0047] Preferably, the precipitation is specifically performed by cooling the mixture obtained by the reaction to room temperature, mixing it with 25-50 times the mass of the organic precipitation solution, filtering it, redissolving it in 0.1-1 times the mass of methyl ethyl ketone, mixing it with the organic precipitation solution, and filtering it.

[0048] More preferably, the organic precipitating liquid is selected from at least one of methanol, n-hexane and cyclohexane.

[0049] Preferably, the washing detergent is selected from at least one of methanol, n-hexane and cyclohexane.

[0050] More preferably, the washing is followed by drying.

[0051] In another aspect, the present invention provides a photoresist composition comprising the above-mentioned photoresist resin.

[0052] Preferably, the photoresist composition comprises a photoresist resin, an acid generator and a solvent, wherein the photoresist resin is the above-mentioned photoresist resin or the photoresist resin prepared by the above-mentioned preparation method.

[0053] The acid generator includes an acid generator based on an onium salt of an iodonium salt or a sulfonium salt, and an acid generator based on an oxime sulfonate; an acid generator based on diazomethane, such as dialkyl or diaryl sulfonyl diazomethane and poly (disulfonyl) diazomethane; an acid generator based on nitrobenzyl sulfonate, an acid generator based on iminosulfonate, and an acid generator based on disulfone. Among them, an onium salt acid generator is preferably used, typically triphenylsulfur trifluoromethane sulfonate

[0054] The solvent includes polyols, such as ethylene glycol, propylene glycol, dipropylene glycol, etc.; lactones, such as γ-butyrolactone; ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, etc.; compounds with ester bonds, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, etc.; polyol derivatives, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, etc. tert-butyl ether, etc.; esters, such as methyl methoxypropionate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, ethyl ethoxypropionate, methyl lactate, ethyl lactate, etc.; aromatic organic solvents, such as anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, dimethyl sulfoxide, etc. Preferably, at least one of propylene glycol methyl ether acetate, propylene glycol dimethyl ether, γ-butyrolactone, and ethylene glycol tert-butyl ether is used.

[0055] Furthermore, the photoresist also includes auxiliary materials, and the auxiliary materials are selected from at least one of alkali, developer, leveling agent, inorganic salt, and surfactant.

[0056] Preferably, the photoresist consists of the following components:

[0057] The above-mentioned photoresist resin, solvent, acid generator and base.

[0058] Wherein, the photoresist resin has a type A repeating unit, a type B repeating unit, a type C repeating unit and a type D repeating unit;

[0059] The A-type repeating unit is selected from one or more of the following structures

[0060]

[0061] The B-type repeating unit is selected from one or more of the following structures:

[0062]

[0063] The C-type repeating unit is selected from one or more of the following structures:

[0064]

[0065] The D-type repeating unit has the following structure:

[0066]

[0067] The solvent is preferably at least one of propylene glycol methyl ether acetate, propylene glycol dimethyl ether, γ-butyrolactone, and ethylene glycol tert-butyl ether.

[0068] The acid generator is triphenylsulfonate trifluoromethanesulfonate.

[0069] The base is phosphatidylcholine.

[0070] More preferably, the mass ratio of the photoresist resin, the solvent, the acid generator and the base is 0.04-0.2: 0.8-0.99: 0.001-0.03: 0.001-0.01.

[0071] More preferably, and as an example of the present invention, the mass ratio of the photoresist resin, the solvent, the acid generator and the base is 0.05-0.15: 0.9-0.97: 0.001-0.03: 0.003-0.006.

[0072] In a final aspect, the present invention provides a method for forming a photoresist pattern, comprising the steps of preparing a photoresist film using the prepared photoresist composition, exposing the photoresist film, and developing the photoresist film to form a photoresist pattern.

[0073] Preferably, the exposure light is KrF laser, ArF laser, F2 laser, Kr2 laser, KrAr laser or Ar2 laser.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] The invention provides a photoresist precursor composition, which can be used to prepare a photoresist resin with a special structure through polymerization reaction. The photoresist prepared by using the photoresist resin has excellent resolution and line edge roughness. DETAILED DESCRIPTION

[0076] Terms and Claims of the Present Invention:

[0077] 1. The articles “a”, “an” and “the” include plural referents unless expressly limited to one or more referents otherwise.

[0078] 2. Numerical range: Unless otherwise expressly stated, all ranges or ratios disclosed herein will be understood to include any and all sub-ranges or sub-ratios contained therein. For example, a range or ratio of 1 to 30 stated should be considered to be included between a minimum value of 1 and a maximum value of 30, and any sub-range or sub-ratio, integer, decimal, or sub-range or sub-ratio consisting of integers or decimals including the end points.

[0079] The following non-limiting examples can enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. The following content is merely an exemplary description of the scope of the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, which should also fall within the scope of the present invention.

[0080] The present invention is further described below by way of specific examples. The various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified. Unless otherwise specified, the contents described below are all weight contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0081] In the following examples, 3,3,4,4,4-pentafluoro-n-butyl methacrylate was obtained from Debye Scientific Co. Ltd; 1-(methoxymethyl)cyclopentyl methacrylate was obtained from Hong Kong Chemhere Co. Ltd, China; and azobisisobutyronitrile was obtained from Aldrich Chemical Co. Ltd. All other starting materials were commercially available or synthesized using known procedures.

[0082] Examples 1.1-1.3: Photoresist precursor compositions, the types and amounts of raw materials thereof are shown in Table 2.

[0083] Table 2

[0084]

[0085]

[0086] Example 2-Example 5: Photoresist precursor composition, the types and amounts of raw materials thereof are shown in Table 3.

[0087] Table 3

[0088]

[0089]

[0090] Examples 6 to 10 provide photoresist precursor compositions, the types and amounts of raw materials thereof are shown in Table 4.

[0091] Table 4

[0092]

[0093]

[0094] Comparative Examples 1-5 provide photoresist precursor compositions, and the types and amounts of raw materials thereof are shown in Table 5.

[0095] Table 5

[0096]

[0097]

[0098] Embodiment 11

[0099] A method for preparing a photoresist resin.

[0100] The photoresist precursor compositions provided in Examples 1.1, 1.2, 1.3, Examples 2-10, and Comparative Examples 1-5 were scaled down to 1 / 50 (monomer 20mmol, initiator 2.5mmol, solvent 20mL), mixed and added to a flask, sealed, and the oxygen in the system was removed three times by cleaning with a Schlenk tube connected to a nitrogen gas cylinder and a vacuum pump, and finally the internal atmosphere of the flask was nitrogen. Oil bath, heated to reflux overnight, cooled to room temperature, added 500-600mL of n-hexane to precipitate, filtered, and a solid product was obtained. The solid was taken in a flask, a small amount of methyl ethyl ketone was added to dissolve, and the steps of n-hexane precipitation-filtration were repeated twice. Vacuum drying overnight to obtain a photoresist resin.

[0101] Measured on a 400 MHz NMR spectrometer 1 HNMR, 13 CNMR and 17FNMR spectra, inversion gated in deuterated acetone using chromium acetylacetonate as relaxation agent 13 CNMR spectrum is used to determine the structure of the photoresist resin product. Size exclusion chromatography is used to determine the number average molecular weight Mn of the polymer.

[0102] The composition and molecular weight of the photoresist resins prepared by Examples 1.1, 1.2, 1.3, Examples 2-10, and Comparative Examples 1-5 according to the preparation method of Example 11 are shown in Table 6.

[0103] Table 6

[0104]

[0105]

[0106] Example 12

[0107] Preparation of photoresist

[0108] The photoresist resins prepared according to the preparation method of Example 11 in Examples 1.1, 1.2, 1.3, Examples 2-10, and Comparative Examples 1-5 were respectively configured into photoresists according to the following formulas: 5 g of photoresist resin, 0.02 g of triphenylsulfonium trifluoromethanesulfonate, 0.003 g of phosphatidylcholine, 30 g of propylene glycol methyl ether acetate, and 65 g of propylene glycol methyl ether.

[0109] Comparative Example 6

[0110] The photoresist provided in Example 1 of the prior art CN117784519A is:

[0111] A photoresist, comprising, by weight percentage:

[0112] 51% acrylate, 12% ethyl acetate, 8% isophorone, 5% calcium carbonate (particle size 0.4 μm), 15% barium sulfate (particle size 1.3 μm), 3% photoinitiator 907, 1% photosensitizer ITX and 5% dimethicone.

[0113] Comparative Example 7

[0114] The photoresist provided in the first embodiment of the prior art CN1611490A:

[0115] Base resin: Resin formed by polymerization of the first unit and the second unit.

[0116] Unit 1:

[0117]

[0118] Unit 2:

[0119]

[0120] Acid generator: triphenylsulfonium trifluoromethanesulfonate (2% by weight of the base resin).

[0121] Solvent: Propylene glycol monomethyl ether acetate.

[0122] Effect evaluation

[0123] The post-lithography resolution and other properties of the photoresists in Example 12, Comparative Example 6, and Comparative Example 7 were evaluated.

[0124] (1) The photoresists prepared in Example 12, Comparative Example 6 and Comparative Example 7 were uniformly coated on a silicon wafer by spin coating to form thin films of different thicknesses (100 nm, 500 nm).

[0125] (2) Thereafter, pre-baking (PAB) is performed at 90-130° C. (the actual baking temperature is 110° C.) for 1-2 minutes (the actual baking time is 1.5 minutes), thereby forming a resist film.

[0126] (3) The exposure method of the resist film can be dry exposure in the atmosphere or in an inert gas such as nitrogen, or can be liquid immersion lithography. The exposure apparatus used includes a KrF exposure apparatus, an ArF exposure apparatus, an electron beam lithography apparatus, an EUV exposure apparatus, etc. The wavelength of exposure is not particularly limited, and KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV) and electron beam (EB) can be used.

[0127] The experiment used an immersion ArF exposure device, ASML XT1900Gi; NA = 1.35, and the immersion medium was ultrapure water.

[0128] (4) Then, the product is baked at 80-130° C. (the actual baking temperature is 105° C.) for 40 seconds to 5 minutes (the actual baking time is 1.5 minutes) in a post-exposure baking (PEB) process.

[0129] (5) Developing in a 35% (v / v) acetone aqueous solution of tetraethylammonium hydroxide (the mass percentage concentration of tetraethylammonium hydroxide in the entire solution is 1.9%) for 0.5-3 minutes (the actual development time is 2 minutes) to form a resist pattern

[0130] Finally, the patterned wafer was observed in a top-down scanning electron microscope (TD-SEM).

[0131] The optimal exposure is defined as the exposure (μC / cm 2), which provides 1:1 resolution at the top and bottom of the 200nm, 1:1 line and space pattern. The maximum resolution of the photoresist is defined as the minimum line width of the L / S pattern that can be distinguished and separated under optimal exposure. The line edge roughness (LER) of the 100nm L / S pattern was evaluated by SEM. The pattern outline was judged to be rectangular by visual observation.

[0132] The experimental results for the 100 nm thick film are shown in Table 7.

[0133] Table 7

[0134]

[0135]

[0136] The experimental results of the 500nm thick film are shown in Table 8:

[0137] Table 8

[0138] Group Maximum resolution (nm) Line edge roughness (nm) Pattern outline Example 1.1 51 4.9 rectangle Example 1.2 51 4.9 rectangle Example 1.3 51 4.8 rectangle Example 2 52 5.2 rectangle Example 3 53 5.1 rectangle Example 4 53 5.1 rectangle Example 5 53 5.1 rectangle Example 6 55 5.1 rectangle Example 7 54 5.2 rectangle Example 8 54 5.3 rectangle Example 9 54 5.3 rectangle Example 10 55 5.6 rectangle Comparative Example 1 99 8.5 Incomplete Comparative Example 2 94 8.8 Incomplete Comparative Example 3 98 9.7 Incomplete Comparative Example 4 140 9.4 Incomplete Comparative Example 5 96 9.6 Incomplete Comparative Example 6 90 9.9 Incomplete Comparative Example 7 162 9.8 Incomplete

[0139] It can be seen that, compared with the comparative examples, the resolution and line edge roughness of the photoresist after photosensitization in each embodiment are significantly improved.

[0140] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A photoresist precursor composition, characterized in that It is composed of monomers, initiators and solvents; The monomers are composed of A-type monomers, B-type monomers, C-type monomers and D-type monomers; The type A monomer is selected from at least one of (1,1,1,3,3,3-hexafluoroisopropyl)methacrylate, trifluoroethyl methacrylate, (3,3,4,4,4-pentafluoro-n-butyl)methacrylate, and 3,3,3-trifluoro-2-methylpropyl methacrylate; The B-type monomer is at least one selected from 1-(methoxymethyl)cyclopentyl methacrylate, (1-(adamantan-1-yl)cyclopentyl)methacrylate, and 1-isopropylcyclopentyl methacrylate; The C-type monomer is selected from at least one of (3-hydroxy-2,2,4,4-tetramethylcyclobutyl) methacrylate and (3,3-dimethyl-1-ethylcyclobutyl) methacrylate; The D-type monomer (2-(9-fluorenylmethoxycarbonylamino)ethyl) methacrylate; The initiator is a free radical photoinitiator; The solvent is selected from at least one of methyl ethyl ketone, cyclopentanone and cyclohexanone.

2. The photoresist precursor composition according to claim 1, characterized in that The molar ratio of the monomer to the initiator is 1:0.01-0.1, and the mass of the solvent is 2.5-3.5 times the total mass of the monomer and the initiator.

3. The photoresist precursor composition according to claim 1, characterized in that The molar ratio of the class A monomer, the class B monomer, the class C monomer and the class D monomer is 0.2-0.25:0.25-0.32:0.3-0.35:0.13-0.2; the ratio of the total molar number of fluorine atoms in the class A monomer to the total molar number of the monomers is 0.12-1.2:

1.

4. The photoresist precursor composition according to claim 1, characterized in that The class A monomer is a mixture of (3,3,4,4,4-pentafluoro-n-butyl) methacrylate and 3,3,3-trifluoro-2-methylpropyl methacrylate; the class B monomer is (1-(adamantan-1-yl) cyclopentyl) methacrylate; and the class C monomer is (3-hydroxy-2,2,4,4-tetramethylcyclobutyl) methacrylate.

5. The photoresist precursor composition according to claim 4, characterized in that The molar ratio of the (3,3,4,4,4-pentafluoro-n-butyl)methacrylate, the 3,3,3-trifluoro-2-methylpropyl methacrylate, the (1-(adamantan-1-yl)cyclopentyl)methacrylate, the (3-hydroxy-2,2,4,4-tetramethylcyclobutyl)methacrylate and the (2-(9-fluorenylmethoxycarbonylamino)ethyl)methacrylate is 0.08:0.15:0.3:0.32:0.

15.

6. The photoresist precursor composition according to claim 1, characterized in that The initiator is at least one of azobisisobutyronitrile, azobisisoheptanenitrile and dimethyl azobisisobutyrate; and the solvent is methyl ethyl ketone.

7. A photoresist resin, characterized in that: Made from the photoresist precursor composition according to any one of claims 1 to 6.

8. The photoresist resin according to claim 7, characterized in that: The photoresist resin has a type A repeating unit, a type B repeating unit, a type C repeating unit and a type D repeating unit; The A-type repeating unit is selected from one or more of the following structures The B-type repeating unit is selected from one or more of the following structures The C-type repeating unit is selected from one or more of the following structures The D-type repeating unit has the following structure 9. The photoresist resin according to any one of claims 7 to 8, characterized in that: The molar ratio of the type A repeating unit, the type B repeating unit, the type C repeating unit and the type D repeating unit is 1-2:6-12:6-13:2-3.

10. The photoresist resin according to claim 9, characterized in that: The A-type repeating unit is The B-type repeating unit is The C-type repeating unit is The D-type repeating unit is 11. The photoresist resin according to claim 10, characterized in that: Said Said Said Said and stated The molar ratio is 1:2:4:6:

2.

12. A photoresist composition, characterized in that: The photoresist resin comprises any one of claims 6 to 10.

13. A method for forming a photoresist pattern, characterized in that: The method comprises the steps of preparing a photoresist film using the photoresist composition prepared according to claim 12, exposing the photoresist film to light, and developing the photoresist film to form a photolithography pattern.

14. The method for forming a photoresist pattern according to claim 13, wherein: The exposure light is KrF laser, ArF laser, F2 laser, Kr2 laser, KrAr laser or Ar2 laser.

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