KR20080020905A - Chemical amplification type positive photoresist composition - Google Patents

Abstract

A chemically amplified positive resist composition is provided to realize excellent sensitivity, resolution and coatability, to improve a pattern profile even under a thickness condition in which standing waves or reverse tapered portions appear. A chemically amplified positive resist composition comprises: at least one resin selected from the compounds represented by the following formulae 1-4; and a photoacid generator represented by the following formula 5. In formula 1, R1 is H or CH3; R2 is a C1-C10 linear, branched or cyclic alkyl; and a and b represent molar fractions of hydroxystyrene units and (meth)acrylate units, respectively, wherein a + b = 1, 0.50<=(a)/(a + b)<=0.90 or 0.1<=(b)/(a + b)<=0.50. In formula 2, R2 is H, methyl, ethyl, propyl, Br, Cl, F or NO2; and c and d represent molar fractions of the corresponding units, wherein c + d = 1, 0.50<=(c)/(c + d)<=0.90 or 0.1<=(d)/(c + d)<=0.50. In formula 3, R3 is H, methyl, ethyl, propyl, Br, Cl, F or NO2; and e and f represent molar fractions of the corresponding units, wherein e + f = 1, 0.50<=(e)/(e + f)<=0.90 or 0.1<=(f)/(e + f)<=0.50. In formula 4, R3 is H, methyl, ethyl, propyl, Br, Cl, F or NO2; and g and h each represent molar fractions of the corresponding units, wherein g + h = 1, 0.50<=(g)/(g + h)<=0.90 or 0.1<=(g)/(g + h)<=0.50. In formula 5, each of R4 and R5 is hydroxyl-, amino- or a C1-C6 alkoxy-substituted or non-substituted C3-C8 linear alkyl; hydroxyl-, amino- or a C1-C6 alkoxy-substituted or non-substituted C3-C8 branched alkyl; hydroxyl-, amino- or a C1-C6 alkoxy-substituted or non-substituted C3-C8 cyclic alkyl; or alkyl- or alkoxy-substituted C6-C10 aryl.

Description

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

1 is a pattern photograph of a resist according to Example 1.

2 is a pattern photograph of a resist according to Comparative Example 1

FIELD OF THE INVENTION The present invention relates to chemically amplified positive resist compositions, and more particularly to resist compositions suitable for photolithography and the like acting by high energy radiation such as far ultraviolet rays (including excimer lasers, etc.), electron beams, X-rays or radiant light. It is about.

In recent years, as the degree of integration of integrated circuits has increased, submicron pattern formation has been required. In particular, photolithography using an excimer laser from fluoride krypton (KrF) or argon fluoride (ArF) has been noted in that it enables the production of 64M DRAM to 1G DRAM. As a resist suitable for a photolithography process using such an excimer laser, a so-called chemically amplified resist using an acid catalyst and a chemical amplification effect is adopted. 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 pattern or negative pattern.

Chemically amplified positive type resists, particularly positive type resists for KrF excimer laser photolithography, are poly (hydroxystyrene) resins in which some of their phenolic hydroxyl groups are dissociated by the action of an acid. Protected resins are often used in combination with photoacid generators. As a group dissociated by the action of these acids, it was found that resins having a specific structure of adamantane-based polymer units and specific high-polar polymer units were effective in achieving adhesion to the substrate, etching resistance, and good resolution. However, even these resins with good performance have limitations in profiles such as standing waves and reverse tapers at different film thicknesses and conditions.

The present invention provides a chemically amplified positive resist composition having a much improved performance such as sensitivity, resolution, and coating property, and having an improved profile, particularly when forming a pattern in a film thickness condition in which standing waves or reverse tapers appear. It aims to do it. MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the chemically amplified positive resist composition containing a specific resin mixture and a specific photoacid generator has various performances, such as a sensitivity, a resolution, and applicability | paintability, In particular, the present invention has been found to have an improved profile when the pattern is formed under film thickness conditions in which standing waves or reverse tapers appear.

The present invention is a resin of formula (1); At least one resin selected from the group consisting of Formula 2, Formula 3, and Formula 4; And it provides a chemically amplified positive resist composition comprising a photoacid generator represented by the formula (5).

[Formula 1]

R ₁ is a hydrogen atom or a methyl group,

R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms

a, and b are a + b = 1 in the mole fraction of hydroxystyrene polymerized units and (meth) acrylate polymerized units in the resin,

0.50 ≦ (a) / (a + b) ≦ 0.90 or 0.1 ≦ (b) / (a + b) ≦ 0.50.

[Formula 2]

(Wherein R ₃ is hydrogen, methyl group, ethyl group, propyl group, Br, Cl, F or NO ₂ ,

c and d are mole fractions of each polymerized unit, c + d = 1,

0.50≤ (c) / (c + d) ≤0.90 or 0.1≤ (d) / (c + d) ≤0.50.)

[Formula 3]

(Wherein R ₃ is hydrogen, methyl group, ethyl group, propyl group, Br, Cl, F or NO ₂ ,

e and f are the mole fractions of each polymerized unit, e + f = 1,

0.50≤ (e) / (e + f) ≤0.90 or 0.1≤ (f) / (e + f) ≤0.50.)

[Formula 4]

(Wherein R ₃ is hydrogen, methyl group, ethyl group, propyl group, Br, Cl, F or NO ₂ ,

g and h are mole fractions of each polymerized unit, g + h = 1,

0.50≤ (g) / (g + h) ≤0.90 or 0.1≤ (h) / (g + h) ≤0.50.)

[Formula 5]

Wherein R ₄ and R ₅ are each hydroxyl, amino or a straight chain alkyl of 3 to 8 carbon atoms unsubstituted or substituted with alkoxy having 1 to 6 carbon atoms; hydroxyl, amino or alkoxy having 1 to 6 carbon atoms Substituted or unsubstituted branched alkyl of 3 to 8 carbon atoms, hydroxyl, amino or cyclic alkyl of 3 to 8 carbon atoms substituted or unsubstituted, alkoxy of 6 to 8 carbon atoms substituted by alkyl or alkoxy An aryl group of 10.)

The present invention also provides a chemically amplified positive resist composition in which a part of the hydroxy groups of the hydroxystyrene polymerized unit of the general formula (1) is protected with an acid dissociable protecting group.

The present invention also provides a resist film prepared by the chemically amplified positive resist composition.

Hereinafter, the present invention will be described in detail.

In general, chemically amplified resists have a higher light transmittance at an exposure wavelength than the novolak / diazo naphthoquinone type resists used for g-ray and i-ray lithography, and the incident light reflects the reflected light reflected from the substrate. As a cause of standing waves or reverse taper due to interference, dimensional fluctuations such as the line width of the pattern, collapse of shape, etc. are likely to occur. As a method of suppressing such standing waves and reverse taper, in general, an antireflection film is applied to the base of the resist. When there is no use of the base antireflection film in an ion implantation process or the like, a light absorber or the like is used to reduce the light transmittance of the resist. There is a way to. However, when the light transmittance of a resist is reduced, there exists a fault that it is easy to impair basic performances, such as a sensitivity and a resolution.

 The resins of Chemical Formulas 2, 3, and 4 have a benzene ring in themselves, thereby degrading light transmittance upon exposure. Therefore, the present invention is to prevent the standing wave or reverse taper phenomenon caused by the film change of the resist, high sensitivity, high resolution, and in particular to improve the performance of the profile and the depth of focus and improved chemically amplified positive resist composition to provide.

In the resist composition of the present invention, the resin component of formula (1) 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, and unlike a structure in which resins synthesized by the conventional method are separated from each other by hydrophilic and hydrophobic groups in a molecular unit and separated according to their characteristics, they are polymerized with each other from a molecular unit. The uniform distribution of the units plays an important role in improving the various properties of the resist.

[Formula 1]

R ₁ is a hydrogen atom or a methyl group,

R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms

a, and b are a + b = 1 in the mole fraction of hydroxystyrene polymerized units and (meth) acrylate polymerized units in the resin,

0.50 ≦ (a) / (a + b) ≦ 0.90 or 0.1 ≦ (b) / (a + b) ≦ 0.50.

In the resin of Formula 1 of the present invention, a part of the hydroxy group of the hydroxystyrene polymerized unit may be protected with a protecting group capable of dissociating with an acid. Preferred protecting groups for the hydroxy group include t-butyloxycarbonyl, ethyl benzene, tetrahydropyranyl, and 1-ethoxyethyl. To 0.4 is preferred.

In the composition of the present invention, at least one resin selected from Formulas 2 to 4 based on 100 parts by weight of the resin of Formula 1 is preferably included in an amount of 2 to 20 parts by weight. When one or more resins selected from Chemical Formulas 2 to 4 are included in an amount of less than 2 parts by weight, the effect of lowering light transmittance during exposure is insignificant, resulting in the presence of standing waves or reverse taper. This causes problems, making it harder to implement smaller patterns.

The photoacid generator in the resist composition 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 the chemically amplified positive resist composition, the acid generated from the photoacid generator acts on the resin described above to dissociate the group that is unstable in the acid present in the resin.

In the present invention, a compound of the formula 5 is used as a photoacid generator.

[Formula 5]

Wherein R ₄ and R ₅ are each a mole fraction of hydroxy styrene polymerized unit and (meth) acrylate polymerized unit in hydroxyl, amino resin or each having 3 to 8 carbon atoms unsubstituted or substituted with alkoxy having 1 to 6 carbon atoms. Straight chain alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy having 1 to 6 carbon atoms; 3 carbon atoms unsubstituted or substituted with alkoxy having 1 to 6 carbon atoms, hydroxyl or amino Cyclic alkyl of 8 to 8; an aryl group having 6 to 10 carbon atoms substituted with alkyl or alkoxy.)

Examples of the hydrocarbon groups R ₄ to R ₅ in the general formula 5 with an alkoxy group having 3 to 8 carbon atoms the alkyl group or cycloalkyl group of and where alkyl or cycloalkyl is each independently a hydroxyl group, an amino group or having 1 to 6 carbon atoms Can be substituted.

Specific examples of the compound of formula 5 include that R ₄ and R ₅ are n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-tri Compounds of formula (5) are isopropylphenyl groups, 4-dodecylphenyl groups, 4-methoxyphenyl groups, 2-naphthyl groups, benzyl groups.

In the resist composition of the present invention, a photoacid generator other than the photoacid generator of Formula 5 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 are 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, -methoxyphenyldiphenylsulfonium trifluoromethane Sulfonate, p-tolyldiphenylsulfo Trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldi Phenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphtolyl Methyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl- 4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3-5-triazine, 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-trimethoxystyryl) -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-butoxysty Reyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly referred to as benzoin tosylate), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (usually α -Methylolbenzoin tosylate), 1,2,3-bene Gentolyl trimethanesulfonate, 2,6-dinith lobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 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) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, N- (phenylsulfonyloxy ) Succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5- Norbornene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide, 4-methoxy-α -[[[(4-methylphenyl) sulfonyl] oxy] imino] benzeneacetonitrile It includes a reel or the like.

It is preferable that the said photo-acid generator contains 0.1-20 weight part based on 100 weight part (solid content basis) of resin which becomes soluble with respect to aqueous alkali solution by the action of an acid. If the amount of the photoacid generator is less than 0.1 part by weight, the amount of acid generated is not sufficient, so that the resin is not sufficiently soluble and also does not realize the pattern shape we want. For example, pattern shapes such as scum and notching round shapes are produced. If it exceeds 20 parts by weight, the transmittance is deteriorated, so that light is not transmitted to the lower portion of the resist film, so that the resin is not sufficiently soluble. Therefore, to obtain the desired pattern shape, an appropriate amount of photoacid generator is needed.

The resist composition of the present invention may contain other organic base compounds, especially nitrogen-containing basic organic compounds synthesized as Quencher 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, and the like, and further include Japanese Patent Publication JP-A Hindered amine compounds with a piperidine backbone as described in -11-52575 can also be used as Quencher.

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

In addition, the resist compositions of the present invention 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 and dried on the substrate is subjected to an exposure treatment for pattern formation, followed by heat treatment to promote the protective group removal reaction, and then developed 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 more detail with reference to Examples and Comparative Examples, but these Examples are only for illustrating the present invention and do not limit the technical scope of the present invention.

 EXAMPLE

Example  1 to 5 and Comparative example  One

According to the photoacid generator (5 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, and according to the content and type shown in Table 1. The ammonium salt as Quencher was dissolved in 555 parts by weight of propylene glycol monomethyl ether acetate and then filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist solution. The resist solution prepared here comprises a resin containing a degree of protection of 15% to 20%.

When the resist solution described above is applied to a silicon wafer treated with hexamethyldisilazane using a spin coater, the film thickness after drying is 0.65 mu m. After applying the resist solution, preheating is performed for 90 seconds on a hotplate at 110 ° C. The wafer having the resist film thus formed is exposed while the exposure dose is gradually changed using a scanning exposure apparatus ['NSR-S203B', manufactured by Nikon Corp., NA = 0.55, sigma = 0.75] having an exposure wavelength of 248 nm (KrF). To form a space and line pattern. Subsequently, post-exposure heat treatment is performed at 130 ° C. for 90 seconds on the hot plate. In addition, paddle development is performed for 60 seconds using a 2.38% aqueous tetramethylammonium hydroxide solution. After development, the KLA scanning electron microscope is used to measure the depth of focus and profile in 0.3 μm space and line pattern. The results are shown in Table 2.

In addition, the light transmittance of a resist film measured the transmittance | permeability of 248 nm light with the ultraviolet-visible powder meter (the Shimadzu product, UV-2401PC), and the result is shown in Table -1.

A-1: In the formula 1, a 2-ethyl-2-adamantyl methacrylate polymerized unit, that is, a superrandom type copolymer having b of 0.23 and a hydroxystyrene-based polymerizing unit, that is, a of 0.77, 1.2, resin

A-2: Resin having a molecular weight of 10,000 and a dispersity of 1.2 containing a benzoate protecting group having c of 0.85 to 0.95 and d of 0.05 to 0.15 in Chemical Formula 2

A-3: Resin having a molecular weight of 10,000 and a dispersity of 1.2 containing a benzyl protecting group having e of 0.85 to 0.95 and f of 0.05 to 0.15 in Chemical Formula 3.

A-4: Resin having a molecular weight of 10,000 and a dispersity of 1.2 containing a phenyl protecting group having g of 0.85 to 0.95 and h of 0.05 to 0.15 in the general formula (4).

B-1: Diazodisulfone type photoacid generator wherein R ₇ and R ₈ in formula (5) are cyclohexyl groups

C-1: 2,6-diisopropylaniline

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

D-1: Propylene Glycol Monomethyl Ether Acetate

 TABLE 1

number Resin (part by weight) Photoacid Generator (parts by weight) Quencher (part by weight) Solvent (part by weight) Example 1 A-1 (92.6), A-2 (7.4) B-1 (5.18) C-1 (0.22), C-2 (0.074) D-1 (555) Example 2 A-1 (96.3), A-2 (3.7) B-1 (5.18) C-1 (0.22), C-2 (0.074) D-1 (555) Example 3 A-1 (98.2), A-2 (1.8) B-1 (5.18) C-1 (0.22 parts), C-2 (0.074) D-1 (555) Example 4 A-1 (92.6), A-3 (7.4) B-1 (5.18) C-1 (0.22), C-2 (0.074) D-1 (555) Example 5 A-1 (92.6), A-4 (7.4) B-1 (5.18) C-1 (0.22), C-2 (0.074) D-1 (555) Comparative Example 1 A-1 (100 B-1 (5.18) C-1 (0.22), C-2 (0.074) D-1 (555)

TABLE 2

number profile Transmittance (%) Sensitivity (mJ / cm2) Example 1 ◎ 63.5 20 Example 2 o 61.2 21 Example 3 o 60.7 23 Example 4 o 63.1 21 Example 5 o 62.8 20 Comparative Example 1 △ 74.3 20

As shown in Table 2, the resist composition (Examples 1 to 5) containing the resin component (A-2) having a benzoate protecting group according to the present invention is a resist composition containing only conventional superrandom (Comparative Example 1). It can be seen that the superiority in profile in comparison with the. In addition, as shown in Table 2, it can be seen that Example 1 has a lower transmittance than Comparative Example 1, and it can be seen that the resist absorbed more of the reflected light.

1 and 2 show the pattern photograph of Example 1 and the pattern photograph of Comparative Example 1. As can be seen from the comparative photograph, it can be seen that the profile of the example is better.

The present invention provides an improved chemically amplified positive resist composition which prevents standing waves and reverse taper phenomenon caused by the film change of resist, exhibits high sensitivity and high resolution, and in particular, lowers the performance of profile and depth of focus. .

Claims (8)

To a resin of formula (1); At least one resin selected from the group consisting of Formula 2, Formula 3, and Formula 4; And a chemically amplified positive resist composition comprising a photoacid generator represented by the formula (5). [Formula 1]

R ₁ is a hydrogen atom or a methyl group, R ₂ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms a, and b are a + b = 1 in the mole fraction of hydroxystyrene polymerized units and (meth) acrylate polymerized units in the resin, 0.50 ≦ (a) / (a + b) ≦ 0.90 or 0.1 ≦ (b) / (a + b) ≦ 0.50. [Formula 2]

In the above formula, R ₃ is hydrogen, methyl group, ethyl group, propyl group, Br, Cl, F or NO ₂ , c and d are mole fractions of each polymerized unit, c + d = 1, 0.50 ≦ (c) / (c + d) ≦ 0.90 or 0.1 ≦ (d) / (c + d) ≦ 0.50. [Formula 3]

In the above formula, R ₃ is hydrogen, methyl group, ethyl group, propyl group, Br, Cl, F or NO ₂ , e and f are the mole fractions of each polymerized unit, e + f = 1, 0.50 ≦ (e) / (e + f) ≦ 0.90 or 0.1 ≦ (f) / (e + f) ≦ 0.50. [Formula 4]

Wherein R ₃ is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO ₂ , g and h are mole fractions of each polymerized unit, g + h = 1, 0.50 ≦ (g) / (g + h) ≦ 0.90 or 0.1 ≦ (h) / (g + h) ≦ 0.50. [Formula 5]

In the above formula, R ₄ and R ₅ are each C3 to C8 linear alkyl unsubstituted or substituted with hydroxyl, amino or alkoxy having 1 to 6 carbon atoms; Branched alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy of 1 to 6 carbon atoms; Cyclic alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy of 1 to 6 carbon atoms; An aryl group having 6 to 10 carbon atoms substituted with alkyl or alkoxy. The chemically amplified positive resist composition according to claim 1, wherein at least one resin selected from Formulas 2 to 4 is included in an amount of 2 to 20 parts by weight based on 100 parts by weight of the resin of Formula 1. The chemically amplified positive resist composition according to claim 1, wherein a part of the hydroxy group of the hydroxystyrene polymerized unit of Formula 1 is protected with a dissociable protecting group by an acid. The method according to claim 1, of the formula 5 R ₄ and R ₅ are each independently n- propyl group, n- butyl group, n- octyl group, a toluyl group, a 2,4,6-trimethylphenyl group, 2, 4, A chemically amplified positive resist composition selected from the group consisting of 6-triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group. The chemically amplified positive resist composition according to claim 1, wherein the amount of the photoacid generator is 0.1 to 20 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. The chemically amplified positive resist composition according to claim 1, which contains a photoacid generator other than the compound of the formula (5). The chemically amplified positive resist composition according to claim 1, further comprising a nitrogen-containing organic organic compound synthesized as Quencher. The resist film formed by the resist composition of any one of Claims 1-7.

Images