KR20060056237A - Chemical amplification positive type resist composition - Google Patents

Abstract

The present invention has a super random copolymer structure in which the 2-alkyl-2-adamantyl (meth) acrylate polymerized units and hydroxystyrene polymerized units represented by the following general formula (1) are alternately connected in an alternating manner. Is one or more resins which are insoluble or poorly soluble in an aqueous alkali solution, but which are unstable for an acid and are converted to soluble in an aqueous alkali solution after dissociation by the action of an acid, and a photoacid generator represented by the following Chemical Formulas 2 and 3 It relates to a chemically amplified positive type resist composition comprising a. The chemically amplified positive type resist composition of the present invention is suitable for the lithography method of KrF-eximer laser and ArF-eximer laser, and is excellent in various performances such as heat resistance, residual film rate, coating property, dry corrosion resistance, exposure latitude, and especially a substrate. In the case of forming the pattern under the condition of specificity of, the resolution, sensitivity, profile and depth of focus can be further improved to form a more precise resist pattern.

(Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

Wherein R ₃ or R ₄ Represents a straight, branched or cyclic alkyl group having 3 to 8 carbon atoms.)

In which R ₅ , R ₆ or R ₇ Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

 Chemically Amplified Positive Type Resist Compositions, Super Random Type Copolymers

Description

Chemically Amplified Positive Type Resist Composition {CHEMICAL AMPLIFICATION POSITIVE TYPE RESIST COMPOSITION}

1 is a pattern photograph of a resist composition containing a resin component (A-1) having a copolymer structure of the super random type of the present invention.

2 is a pattern photograph of a resist composition containing a resin synthesized by a conventional method.

The present invention relates to a chemically amplified positive type resist composition suitable for photolithography or the like acting by high energy radiation such as far ultraviolet rays, electron beams, X-rays or radiant light including an excimer laser or the like. Specifically, the present invention is suitable for the lithography method of KrF-eximer laser and ArF-eximer laser, including a resin component having a copolymer structure of super random type and a photoacid generator which generates an acid when irradiated with high energy radiation. Excellent performance, such as heat resistance, residual film ratio, coating property, dry corrosion resistance, exposure latitude, and resolution, sensitivity, profile and depth of focus, especially when forming patterns under specific substrate conditions The focus is on an improved chemically amplified positive type resist composition.

In general, microfabrication in semiconductor fabrication is commonly carried out in lithographic processes using resist compositions. In a lithography process, the resolution can be improved primarily by shortening the exposure wavelength, as indicated by Rayleigh's formula regarding the diffraction limit. Therefore, the wavelength of the light source for the lithography process used in semiconductor manufacturing is g-ray (wavelength 436 nm), i-ray (wavelength 365 nm), KrF-excimer laser (wavelength 248 nm), ArF-excimer laser (wavelength 193). Increasingly shorter wavelengths of light have been adopted in the order of nm). Recently, as the degree of integration of integrated circuits increases, the formation of submicron patterns is required. In particular, photolithography using a KrF-eximer laser or an ArF-eximer laser has attracted attention in that it enables the production of 64M DRAM to 1G DRAM. However, since a lens of an exposure apparatus using a short wavelength excimer laser has a shorter lifetime than a lens used for a conventional exposure light source, it is preferable to expose the lens to the excimer laser for a short time. In the lithography process using the excimer laser, the sensitivity of the resist must be increased to reduce the exposure time, and in order to achieve the object, a group decomposable by the action of acid using the catalysis and chemical amplification effect of the acid generated by exposure is achieved. A so-called chemically amplified resist containing a resin having a resin is used.

When a chemically amplified resist is used, the acid generated from the photoacid generator in the irradiation section of the radiation is diffused by subsequent heat treatment, and the solubility in the alkaline developer of the irradiation section is changed by a reaction using the generated acid as a catalyst. Obtain a positive type or negative type pattern. On the other hand, because the chemically amplified resist uses an acid catalysis, there is a problem in that the lower tailing of the profile appears due to the inactivation of the acid when the substrate is basic. This problem can be solved by adding much higher amounts of basic removing material. However, the addition of a large amount of basic removing material lowers the sensitivity. When an excimer laser is used as the exposure light source, a low reflection substrate is usually used, but in general, the resist profile deteriorates to a tapered shape, although the dimensional uniformity is efficiently improved. Therefore, chemically amplified resists have a problem that their performance, in particular their profile, varies with the type of substrate. In the above, Japanese Patent Laid-Open No. 9-73173 discloses that when a polymer or copolymer of 2-methyl-2-adamantyl methacrylate is used as the resin of a chemically amplified resist, 2-methyl- It has been described that positive action appears as the 2-adamantyl group decomposes, and high dry etch resistance, high resolution and high adhesion to the substrate are obtained. In addition, Japanese Patent Application Laid-Open Nos. Hei 10-12406 and Hei 10-191559 show that the adhesion to the substrate includes a resin having a butyrolactone moiety as part of the polymer unit or polymerized unit 2-alkyl. It has been found that improvements can be made using chemically amplified positive resist compositions comprising 2-adamantyl (meth) acrylate and a resin having polymerized unit maleic anhydride. It has also been found that resins having adamantane-based polymerized units and specific high-polarity polymerized units of particular structure are effective in improving adhesion to substrates. However, even if a resin having a polymerized unit such as 2-alkyl-2-adamantyl (meth) acrylate in the above-mentioned document is used, a resin having a general structure such as the following general formula (4) is separated from each other in hydrophilic and hydrophobic groups in a molecular unit. When the pattern is formed under the condition of the specificity of the substrate, it has a structure that is separated from each other according to each characteristic, and thus there is a limit in resolution, sensitivity, profile, depth of focus and the like.

(Wherein R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

In addition, in the pattern formation by photolithography in the case where there is a specificity of the substrate, in general, variations in the depth of focus tend to cause variation in the finished pattern of the resist pattern and the depth of focus is small. As described above, conventionally known resist compositions have limitations in resolution, sensitivity, profile, depth of focus, and the like.

The present invention has been proposed in order to solve the problems of the prior art, which is separated into hydrophilic and hydrophobic at the molecular unit when synthesizing a resin having a polymerized unit of conventional 2-alkyl-2-adamantyl (meth) acrylate. In order to solve the problem caused by the phenomena, a resin having a super random copolymer structure in which the 2-alkyl-2-adamantyl (meth) acrylate polymer unit and the hydroxy styrene polymer unit are alternately connected alternately. It is used more effectively to improve resolution, sensitivity, profile and depth of focus. An object of the present invention is suitable for the lithography method of KrF-eximer laser and ArF-eximer laser, including resin component and photoacid generator, and excellent in various performances such as heat resistance, residual film ratio, coating property, dry corrosion resistance, exposure latitude, In particular, the present invention provides a chemically amplified positive type resist composition having a further improved resolution, sensitivity, profile, and depth of focus, when the pattern is formed under specific substrate conditions.

In order to achieve the object of the present invention, the present invention includes a resin component having a super random type copolymer structure and a photoacid generator that generates an acid when irradiated with high energy radiation, KrF-eximer laser and ArF-eximer It is suitable for laser lithography, and has excellent performances such as heat resistance, residual film rate, coating property, dry corrosion resistance, exposure latitude, and resolution, sensitivity, profile, and focus, especially when forming patterns under conditions specific to the substrate. A chemically amplified positive type resist composition with further improved depth is provided.

In the resist composition of the present invention, the resin component is insoluble or poorly insoluble in aqueous alkali solution, but becomes soluble in aqueous alkali solution after the group unstable to acid is dissociated by the action of acid. Such a resin has a super random copolymer structure in which 2-alkyl-2-adamantyl (meth) acrylate polymerized units and hydroxystyrene polymerized units are alternately connected alternately, and synthesized by conventional methods. Unlike the structure in which the hydrophilic and hydrophobic groups are separated in the molecular unit and separated according to their respective properties, the resin has an important role in improving various properties of the resist since the polymerized units are uniformly distributed from the molecular unit. Doing Examples of such a resin include a copolymer represented by the following formula (1).

[Formula 1]

(Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

The 2-alkyl-2-adamantyl (meth) acrylate polymerized units mentioned herein are formed by polymerizing 2-alkyl-2-adamantyl acrylate or 2-alkyl-2-adamantyl methacrylate. Means one unit in a polymer.

The photoacid generator in the resist composition of the present invention is a substance that generates an acid by irradiating the material itself or a resist composition containing such material with high energy radiation such as far ultraviolet rays, electron beams, X-rays, or radiant light. In a chemically amplified positive type resist composition, the acid generated from the photoacid generator acts on the above-mentioned resin to dissociate the group that is unstable in the acid present in the resin. In the present invention, the compounds of formulas (2) and (3) exhibiting high absorbance near 248 nm (KrF) are used as photoacid generator components.

[Formula 2]

Wherein R ₃ or R ₄ Represents a straight, branched or cyclic alkyl group having 3 to 8 carbon atoms.)

[Formula 3]

In which R ₅ , R ₆ or R ₇ Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

Hydrocarbon group of Formula 2 R ₃ or R ₄ Is an alkyl group or cycloalkyl group having 3 to 8 carbon atoms, wherein the alkyl or cycloalkyl may be each independently substituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms. R ₃ or R ₄ of Formula 2 Is n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group , 2-naphthyl group, benzyl group.

Hydrocarbon group R ₅ , R ₆ or R ₇ in formula (3) is an alkyl group or cycloalkyl group having 1 to 10 carbon atoms, wherein the alkyl or cycloalkyl may each independently be substituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms. have. R ₅ , R ₆ or R ₇ of Formula 3 Is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4 -Methoxyphenyl group, 2-naphthyl group, benzyl group.

In the resist composition of the present invention, photoacid generators other than the photoacid generators of Formula 2 and Formula 3 may be used together. Examples of such other photoacid generators include onium salt compounds, s-triazine-based organic halogen compounds, sulfone compounds, sulfonate compounds and the like. Specifically, the following compounds may be listed:

Diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl Iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert -Butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsul Phosphium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoro Methanesulfonate, p-tolyldiphenylsulfo Trifluoromethanesulfonate, triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl Diphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) Thiolanium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4- Hydroxy-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloro Rhomethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6- Bis (trichloromethyl) -1,3-5- Lysine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxy Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-tri Azine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (usually benzo Called intosylate), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesul Nate (commonly referred to as α-methylol benzoin tosylate), 1,2,3-benzenetolyl trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfo Nate, 4-nitrobenzyl p-toluenesulfonate, diphenyl disulfone, di-p-tolyl disulfone, dis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis ( p-tolylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazo Methane, (benzoyl) (phenylsulfonyl) diazomethane, N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyl Oxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N -(10-camphorsulfonyloxy) naphthalimide, 4-methoxy-α-[[[(4-methylphenyl) sulfonyl] oxy] imino] benzeneacetonitrile and the like.

It is preferable that the photo-acid generator of the resist composition of this invention contains 0.1-20 weight part with respect to 100 weight part of resin which becomes soluble with respect to aqueous alkali solution by the action of an acid.

The resist composition of the present invention may contain other organic base compounds, especially nitrogen-containing basic organic compounds synthesized as quenchers in an amount that does not adversely affect the effects of the present invention. Specific examples of the quencher component include tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n-octylammonium hydroxide, phenyltrimethylammonium hydroxide , 3- (trifluoromethyl) -phenyltrimethylammonium hydroxide, and (2-hydroxyethyl) trimethylammonium hydroxide, dicyclohexylmethylamine, 2,6-diisopropylaniline, tris (2- (2-methoxyethoxy) ethyl) amine and the like. In addition, hindered amine compounds having a piperidine backbone as described in JP-A-11-52575 can also be used as quencher.

It is preferable that the quencher of the resist composition of this invention contains 0.001-10 weight part based on 100 weight part of resin which becomes soluble with respect to aqueous alkali solution by the action of an acid.

In addition, the compositions may also contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes, and the like.

Such a resist composition is usually in the form of a resist liquid composition containing components dissolved in a solvent, and is applied onto a substrate such as a silicon wafer by a conventional method. The solvent used in the present invention may be one that dissolves the components, exhibits a suitable drying rate and provides a uniform and smooth coating after solvent evaporation. What is normally used in this field can be used. Examples thereof include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; Esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Alcohols such as 3-methoxy-1-butanol and the like. These solvents may each be used alone or as a mixture of two or more.

The resist applied to the substrate and dried is subjected to an exposure treatment for pattern formation, followed by heat treatment to promote the protecting group removal reaction, followed by development with an alkali developer. The alkali developer used in the present invention can be selected from various aqueous alkali solutions, and usually tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly referred to as choline) are frequently used. .

Hereinafter, the present invention will be described in detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto, and those skilled in the art can variously change the present invention without departing from the spirit and scope of the invention described in the following claims. It may be modified or modified. In the examples, parts means parts by weight unless otherwise indicated.

EXAMPLE

Example  1 to 10 and Comparative example  1 to 10

Photoacid generator (7 parts by weight) based on 100 parts by weight (in terms of solids) of the resin component mixed in the ratio (in terms of solids) shown in Table 1, the quencher according to the amounts and types shown in Table 1 As ammonium salt was dissolved in 900 parts by weight of propylene glycol monomethyl ether acetate and then filtered through a fluorine resin filter having a pore diameter of 0.1 μm to prepare a resist solution. The resist solution prepared here comprises a resin containing a protection rate on the order of 25% to 40%.

The resist solution described above was applied to a silicon wafer treated with hexamethyldisilazane such that the film thickness after drying was 0.274 µm using a spin coater. After the resist solution was applied, preliminary heat treatment was performed for 60 seconds on a hotplate at 110 ° C. The wafer having the resist film thus formed was gradually exposed to light using a scanning exposure apparatus ['NSR-S203B', manufactured by Nikon Corp., NA = 0.55, sigma = 0.55] having an exposure wavelength of 248 nm (KrF). Exposure was performed to form line and space patterns. Subsequently, in the hot plate, post-exposure heat treatment was performed at 110 ° C. for 60 seconds. In addition, paddle development was performed for 60 seconds using 2.38% aqueous tetramethylammonium hydroxide solution. The pattern after development was measured using a scanning electron microscope in resolution, sensitivity, depth of focus and profile in 0.12 탆 line and space patterns and 0.18 탆 independent line patterns. The results are shown in Table 2.

number Resin (protection rate) Photoacid Generator (Copies) Kencher (collapse) Solvent (incident) Example 1 A-1 (25.0%) B-1 (0.1 copies) C-1 (0.001 copies) D-1 (900 copies) Example 2 A-1 (27.0%) B-1 (0.1 copies) / B-2 (0.1 copies) C-1 (0.001 copies) / C-2 (0.001 copies) D-1 (900 copies) Example 3 A-1 (30.0%) B-1 (1.0 copies) / B-2 (1.0 copies) C-1 (0.1 copies) / C-2 (0.1 copies) D-1 (900 copies) Example 4 A-1 (25.0%) B-1 (1.0 parts) / B-2 (3.0 parts) C-1 (2.0 parts) / C-2 (0.5 parts) D-1 (900 copies) Example 5 A-1 (30.0%) B-1 (3.5 parts) / B-2 (3.5 parts) C-1 (1.5 copies) / C-2 (1.5 copies) D-1 (900 copies) Example 6 A-1 (35.0%) B-1 (5.0 parts) / B-2 (5.0 parts) C-1 (1.0 parts) / C-2 (5.0 parts) D-1 (900 copies) Example 7 A-1 (40.0%) B-1 (7.0 parts) / B-2 (3.0 parts) C-1 (3.0 parts) / C-2 (2.0 parts) D-1 (900 copies) Example 8 A-1 (30.0%) B-1 (10.0 parts) C-1 (3.0 parts) D-1 (900 copies) Example 9 A-1 (35.0%) B-2 (20.0 parts) C-2 (10.0 parts) D-1 (900 copies) Example 10 A-1 (40.0%) B-1 (10.0 parts) / B-2 (10.0 parts) C-1 (5.0 parts) / C-2 (5.0 parts) D-1 (900 copies) Comparative Example 1 A-2 (25.0%) B-1 (0.1 copies) C-1 (0.001 copies) D-1 (900 copies) Comparative Example 2 A-2 (27.0%) B-1 (0.1 copies) / B-2 (0.1 copies) C-1 (0.001 copies) / C-2 (0.001 copies) D-1 (900 copies) Comparative Example 3 A-2 (30.0%) B-1 (1.0 copies) / B-2 (1.0 copies) C-1 (0.1 copies) / C-2 (0.1 copies) D-1 (900 copies) Comparative Example 4 A-2 (25.0%) B-1 (1.0 parts) / B-2 (3.0 parts) C-1 (2.0 parts) / C-2 (0.5 parts) D-1 (900 copies) Comparative Example 5 A-2 (30.0%) B-1 (3.5 parts) / B-2 (3.5 parts) C-1 (1.5 copies) / C-2 (1.5 copies) D-1 (900 copies) Comparative Example 6 A-2 (35.0%) B-1 (5.0 parts) / B-2 (5.0 parts) C-1 (1.0 parts) / C-2 (5.0 parts) D-1 (900 copies) Comparative Example 7 A-2 (40.0%) B-1 (7.0 parts) / B-2 (3.0 parts) C-1 (3.0 parts) / C-2 (2.0 parts) D-1 (900 copies) Comparative Example 8 A-2 (30.0%) B-1 (10.0 parts) C-1 (3.0 parts) D-1 (900 copies) Comparative Example 9 A-2 (35.0%) B-2 (20.0 parts) C-2 (10.0 parts) D-1 (900 copies) Comparative Example 10 A-2 (40.0%) B-1 (10.0 parts) / B-2 (10.0 parts) C-1 (5.0 parts) / C-2 (5.0 parts) D-1 (900 copies)

* A-1: Super random copolymer having a 2-alkyl-2-adamantyl (meth) acrylate polymerized unit and a hydroxystyrene polymerized unit as in Chemical Formula 1, a resin having a dispersity of 1.2 (of the present invention) Suzy)

* A-2: Copolymer of a common 2-alkyl-2-adamantyl (meth) acrylate polymerization unit and a hydroxystyrene-based polymerization unit separated by hydrophilicity and hydrophobicity in a molecular unit as in Chemical Formula 4, dispersion degree 1.2 Resin (resist to be compared)

* B-1: R ₅ and R ₆ in Chemical Formula 2 Diazodisulfone type photoacid generator which is this cyclohexyl group

* B-2: triphenylsulfonium type photoacid generator as shown in Chemical Formula 3

* C-1: 2,6-diisopropylaniline

* C-2: tris (2- (2-methoxyethoxy) ethyl) amine

* D-1: Propylene Glycol Monomethyl Ether Acetate

number profile Depth of focus [㎛] resolution Sensitivity (mJ / cm ² ) Example 1 ◎ 1.0 ◎ 64 Example 2 ◎ 1.0 ◎ 66 Example 3 ◎ 0.9 ◎ 72 Example 4 ◎ 0.8 ◎ 82 Example 5 ◎ 1.1 ◎ 62 Example 6 ◎ 1.0 ◎ 66 Example 7 ◎ 1.0 ◎ 64 Example 8 ◎ 0.9 ◎ 58 Example 9 ◎ 0.8 ◎ 72 Example 10 ◎ 1.0 ◎ 66 Comparative Example 1 △ 0.8 △ 72 Comparative Example 2 △ 0.8 △ 76 Comparative Example 3 O 0.7 O 80 Comparative Example 4 O 0.6 O 92 Comparative Example 5 O 0.9 O 66 Comparative Example 6 O 0.6 O 74 Comparative Example 7 Ｘ 0.7 Ｘ 72 Comparative Example 8 Ｘ 0.8 Ｘ 64 Comparative Example 9 △ 0.7 △ 80 Comparative Example 10 △ 0.8 △ 74

As shown in Table 2, the resist composition (Examples 1 to 10) containing the resin component (A-1) having the super random type copolymer structure of the present invention had a conventional profile, depth of focus, resolution and sensitivity. It can be seen that it is superior in comparison with a resist composition containing a resin synthesized by the method.

In addition, although the pattern photograph of FIG. 1 and FIG. 2 showed the pattern photograph of Example 5 and the pattern photograph of Comparative Example 5, as can be seen from a comparative photograph, it can be confirmed that the profile of an Example is more excellent.

As described above, the chemically amplified positive type resist composition of the present invention is suitable for the lithography method of KrF-eximer laser and ArF-eximer laser, and is suitable for various types such as heat resistance, residual film ratio, coating property, dry corrosion resistance and exposure latitude. The performance is excellent, and in particular, in the case of forming a pattern under conditions with specificity of the substrate, the resolution, sensitivity, profile and depth of focus can be further improved to form a more precise resist pattern.

Claims (8)

A chemically amplified positive type resist composition containing at least one resin represented by Formula 1 and a photoacid generator represented by Formula 2 and Formula 3 below: [Formula 1]

(Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.) [Formula 2]

Wherein R ₃ or R ₄ Represents a straight, branched or cyclic alkyl group having 3 to 8 carbon atoms.) [Formula 3]

In which R ₅ , R ₆ or R ₇ Represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.) The resin component according to claim 1, wherein the resin component has a super random copolymer structure in which the 2-alkyl-2-adamantyl (meth) acrylate polymer unit and the hydroxystyrene polymer unit are alternately connected alternately, A chemically amplified positive type resist composition, which is originally a resin which is insoluble or poorly soluble in an aqueous alkali solution, but which is unstable for an acid, is converted to soluble in an aqueous alkali solution after dissociation by the action of acid. The hydrocarbon group according to claim 1, wherein R ₃ or R ₄ Is an alkyl group or cycloalkyl group having 3 to 8 carbon atoms, wherein the alkyl or cycloalkyl is each independently substituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms. According to claim 1 or 3, R ₃ or R ₄ of formula (2) N-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group And a chemically amplified positive type resist composition selected from the group consisting of 2-naphthyl and benzyl groups. The hydrocarbon group according to claim 1, wherein the hydrocarbon group of formula 3 is R ₅ , R ₆ or R ₇ Is an alkyl or cycloalkyl group having 1 to 10 carbon atoms, wherein the alkyl or cycloalkyl is each independently substituted with a hydroxyl group, an amino group or an alkoxy group having 1 to 6 carbon atoms. The compound according to claim 1 or 5, wherein R ₅ , R ₆ or R ₇ of formula (3). Is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-dodecylphenyl group, 4 A chemically amplified positive type resist composition selected from the group consisting of methoxyphenyl group, 2-naphthyl group and benzyl group. The chemically amplified positive type resist composition according to claim 1, wherein the amount of the photoacid generator of the resist composition contains 0.1 to 20 parts by weight based on 100 parts by weight of the resin which is converted into soluble to the aqueous alkali solution by the action of an acid. . The chemically amplified positive type resist composition according to claim 1, comprising a nitrogen-containing basic organic compound synthesized as a quencher.

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