KR101363725B1 - Chemically amplified positive photoresist composition - Google Patents

Abstract

The present invention relates to a chemically amplified positive photoresist composition comprising (A) a resin represented by Formula 1 and (B) a photoacid emitter. Even when the thickness of the photoresist composition photoresist is thick, the resolution and pattern shape are excellent, and the micropattern is precisely implemented.

Chemical Amplification, Photoresist, Photoacid Generator

Description

Chemically Amplified Positive Photoresist Composition

FIELD OF THE INVENTION The present invention relates to chemically amplified positive photoresist compositions suitable for photolithography or the like acting by ultraviolet radiation, such as excimer lasers, electron beams, X-rays or high energy radiation such as radiant light.

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 is diffused by the subsequent heat treatment in the radiation irradiation unit, and the solubility in the alkaline developer of the irradiation unit is changed by the reaction using the diffused acid as a catalyst. Or a negative type pattern is obtained.

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 protected by a group dissociated by the action of an acid. The used resin is often used in combination with a photoacid generator. As a group dissociated by the action of such an acid, forming an acetal bond between oxygen atoms derived from phenolic hydroxy groups from the viewpoint of resolution and sensitivity, for example, tetrahydro-2-pyranyl, tetra Attention has been paid to a resin having a structure in which hydro-2-furyl or 1-ethoxyethyl is bonded to an oxygen atom. However, even when such a resin is used, there is a limit in that when the resin is used for a metal process or an implanter process, the film is thick and a pattern is formed under conditions specific to the substrate.

In addition, when the film thickness is thick, the permeability is lowered due to the content of the photoacid generator and the thickness of the photoresist resin, thereby reducing the content of the photoacid generator.

Accordingly, the present inventors have made intensive efforts to overcome the above problems, and have completed the present invention by finding a photoacid generator having a long diffusion distance and a high acidity and a resist resin in which such a photoacid generator can be sufficiently dispersed.

Accordingly, an object of the present invention is to provide a chemically amplified positive photoresist composition which is excellent in resolution and pattern shape even when the film thickness of the photoresist is thick, and which can precisely implement a fine pattern.

According to the present invention,

 It relates to a chemically amplified positive photoresist composition comprising (A) a resin represented by the following formula (1) and (B) a photoacid emitter.

Where

R ₁ , R ₂ and R ₃ are each independently hydrogen or a methyl group,

R ₄ and R ₆ are each independently a methyl group or an ethyl group,

R ₅ and R ₇ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 6 or less carbon atoms, provided that R ₅ and R ₇ are not the same.

a, b and c represent the molar ratio of each monomer, Are each a number in the range 0-1, a + b + c = 1, and 0.10≤ [(a + c) / (a + b + c)] ≤0.50 or 0.05≤ [c / (a + b + c) ] ≤0.40.

More preferably, a, b and c have values of 0.20 ≦ [(a + c) / (a + b + c)] ≦ 0.40 or 0.05 ≦ [c / (a + b + c)] ≦ 0.35 Do.

If the value of (a + c) / (a + b + c) is less than 0.10, all of the films are dissolved after development, and if it exceeds 0.50, hydrophobicity is increased and is not dissolved in the developer. In addition, when c / (a + b + c) is less than 0.05, the effect of the present invention is inadequate, and when it exceeds 0.40, hydrophobization is increased and it is not dissolved in the developer.

On the other hand, [(a + c) / (a + b + c)] × 100 is a protection ratio of the resin, and the protection ratio of the resin is preferably 10% to 50%.

The resin represented by the component (A), that is, the formula (1) is a resin which is originally insoluble or poorly soluble in the aqueous alkali solution but becomes soluble in the aqueous alkaline solution after dissociation of the functional group unstable with the acid by the action of the acid. In addition, a cyclohexyloxyethyl group is further introduced in addition to the existing ethoxyethyl protecting group in order to increase the lipophilicity to the resin.

The photoacid generator (B) included in the photoresist composition of the present invention is a compound that generates an acid by the action of light or radiation, and the material itself or a photoresist composition containing such a material is ultraviolet, ultraviolet, electron beam, and X-. It is a substance that generates acid by irradiating high energy radiation such as ray or radiation. The acid generated from the photoacid generator acts on the resin to dissociate functional groups that are unstable in the acid present in the resin.

The photoacid generator used in the present invention is characterized in that the diffusion distance is long and the acidity is high because the protecting group dissociation ability of the photoresist resin should be maintained while using a small amount.

In the present invention, the compound (B-1) represented by the following Chemical Formula 2 may be used as the (B) photoacid generator that satisfies the above conditions.

In the above formula, R ₈ and R ₉ are each independently a hydroxy group, an amino group or a C 1-10 linear or branched alkyl group unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; A C3-C10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group or a C1-C6 alkoxy group; Or a C6-C11 aryl group unsubstituted or substituted with a C1-C20 alkyl group, a C1-C6 alkoxy group or a halogen.

In Formula 2, R ₈ and R ₉ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropyl It is preferable that they are a phenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, or benzyl group.

In addition, the photoresist composition of the present invention is more preferably used by mixing a photoacid generator (B-2) having a high acidity and a large lipophilic compound with the photoacid generator (B-1) represented by the above formula (2). Do.

The high acidity and high lipophilic photoacid generators (B-2) include onium salt compounds, s-triazine-based organic halogen compounds, sulfone compounds, sulfonate compounds, etc., which may be used alone or in combination of two or more thereof. Can be.

Specific examples of the photoacid generator (B-2) include diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, and 4-methoxyphenylphenyl iodonium trifluoro Romethanesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluor Roantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoro Methanesulfonate, 4-methylphenyldiphenylsulfonium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4- Methoxyphenyldiphenylsulfonium trifluorome Sulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium trifluoromethane Sulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium hexafluoro Antimonate, 1- (2-naphtolylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naph Tyldimethylsulfonium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthal Imides, and the like,

Among them, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium trifluoric acid having a cationic group of triphenylsulfonium and containing a fluorine group as an anionic group and having high acidity and high lipophilic properties Romethanesulfonate, 4-methylphenyldiphenylsulfonium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4 -Methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4- t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, and 4-phenylthiophenyldiphenylsulfonium hexafluoroantimo The site is preferred.

The photoacid generator (B-2) having a long diffusion distance and high acidity used in the present invention has a higher lipophilicity than the conventional photoacid generator, and thus a problem due to dispersibility should be used by using a resist resin having enhanced lipophilic property. It doesn't work.

The content of the photoacid generator (B) in the photoresist composition of the present invention preferably contains 0.1 to 5 parts by weight based on 100 parts by weight of the resin (A) (in terms of solid content). If the content of the photoacid generator is less than 0.1 part by weight, a poor appearance appears at a resolution such as a development defect, and if it exceeds 5 parts by weight, the pattern shape is collapsed to hardly form a patterned resist layer.

In the case of mixing and using the above-mentioned photo-acid dispersant (B-1) and (B-2), the mixing ratio is preferably 50:50 to 90:10, and when (B-1) is less than 50%, the upper portion of the profile The thickening of the profile causes a problem that the profile collapses, and when it exceeds 90%, the lower part of the profile becomes thicker, which may result in developing defects on the substrate.

The photoresist composition of the present invention may further include an additive for controlling the (C) phenomenon defect.

The additive serves to prevent the resin from being soluble in the aqueous alkali solution due to the acid generated from the photoacid generator at the exposed portion during the semiconductor photo process to become poorly soluble.

The resin, which was poorly soluble in the alkaline aqueous solution in the semiconductor photo process, is changed to soluble by an acid generated from a photoacid generator and is dissolved by receiving light, and fine patterns are realized by washing with ultrapure water. In this process, if the area of the exposed area is large, the developing resin becomes soluble in alkaline water solution and becomes poorly soluble again due to the high hydrophobicity of the resin when washed with ultrapure water. This will occur. At this time, the component (C) is uniformly distributed between the resins to reduce the concentration of the resin to increase the transmittance, thereby preventing the hydrophobic resins from agglomerating again on the substrate during the ultrapure water cleaning process, thereby making it difficult to dissolve. Will inhibit adsorption. Therefore, it is possible to form a profile exhibiting high sensitivity and high resolution and without developing defects.

It is preferable to use 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or a mixture thereof as an additive for controlling the (C) phenomenon defect.

The content of the component (C) in the photoresist composition of the present invention is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the resin (A) (in terms of solid content). If the content of the component (C) is less than 0.1 part by weight, the hydrophobic resin may be resorbed onto the substrate to cause development defects. If the content of the component (C) exceeds 30 parts by weight, the weight ratio of the component (C) may be too large to reduce resolution. There is a problem.

The photoresist composition of the present invention may further contain other organic base compounds, particularly nitrogen-containing basic organic compounds as quencher (D) in an amount that does not adversely affect the effects of the present invention.

Specific examples of the nitrogen-containing basic organic compound include a compound represented by the following structural formula.

In the above structural formula, R ₁₀ and R ₁₁ are each independently hydrogen; C1-C6 linear or branched alkyl group substituted or unsubstituted by the hydroxyl group, the amino group, the C1-C4 alkyl group, or the C1-C6 alkoxy group; A C5-10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; An amino group substituted with a hydroxy group, an amino group, or an alkyl group having 1 to 4 carbon atoms; Or a C6-C10 aryl group unsubstituted or substituted by a C1-C6 alkoxy group,

R ₁₂ , R ₁₃ and R ₁₄ are each independently hydrogen; C1-C6 linear or branched alkyl group substituted or unsubstituted by the hydroxyl group, the amino group, the C1-C4 alkyl group, or the C1-C6 alkoxy group; C5-10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group, the C1-C4 alkyl group, or the C1-C6 alkoxy group; A C1-6 alkoxy group unsubstituted or substituted with a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; Or an amino group substituted with a hydroxy group, an amino group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms,

R ₁₅ is a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; Or an amino group substituted with a hydroxy group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms,

A is a C2-C6 linear or branched alkylene group, carbonyl group, sulfide group, or disulfide group.

In addition, a hindered amine compound having a piperidine skeleton as described in Japanese Patent Laid-Open No. 11-52575 can be further used as a quencher.

In the photoresist composition of the present invention, the (D) quencher preferably contains 0.001 to 10 parts by weight based on 100 parts by weight (A) of the resin (A). If the content of the quencher is less than 0.001 parts by weight, the diffusion of acid is increased so that an abnormality in the exposed area may be developed, and thus the pattern profile may be deteriorated. By causing a change in the profile accordingly, the photosensitivity of the photoresist composition is rather reduced.

In addition, the chemically amplified positive photoresist compositions of the present invention may further contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes, and the like.

The chemically amplified positive photoresist composition is in the form of a resist liquid composition containing components dissolved in a conventional solvent, and is applied onto a substrate such as a silicon wafer by a conventional method.

The solvent used in the present invention preferably dissolves the components, exhibits a suitable drying rate, and provides a uniform and smooth film after solvent evaporation, and those conventionally used in this field can be used. Examples thereof include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve 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? -butyrolactone; Alcohols such as 3-methoxy-1-butanol and the like. These solvents may be used alone or in combination of two or more components.

Using the chemically amplified positive photoresist composition according to the present invention, a method of forming a resist pattern is provided by applying a chemically amplified positive photoresist composition on a substrate, selectively exposing, then heat-treating and developing with an alkaline developer. Including the process.

In more detail, the chemically amplified positive photoresist composition according to the present invention is applied to an etched layer such as a silicon wafer or a chromium substrate by using a spin coater to form a thin film. An electron beam is injected into an exposure source to the formed thin film, and then the exposed resist film is heated as necessary to promote the protecting group removal reaction. The heated resist film is developed with an alkaline developer to form a resist pattern. Alkali developers used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide And various aqueous alkali solutions such as (2-hydroxyethyl) trimethylammonium hydroxide, among which tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (usually choline Is referred to).

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  1: (A) Manufacturing method of resin represented by general formula (1)

30 g of poly (p-vinylphenol) having a weight average molecular weight (Mw) of 13,500 and a polydispersity (Mw / Mn) of 1.15 and 0.023 g of p-toluenesulfonic acid were added to the flask and dissolved in 250 g of 1.4-dioxane. 5.12 g of ethyl vinyl ether and 3.93 g of cyclohexylethyl vinyl ether were added dropwise to the solution, and the mixture was reacted at 25 ° C. for 6 hours. Subsequently, the reaction solution was filtered in ion-exchanged water to obtain a white cake. The cake was again dissolved in a solvent and then dropwise added to ion-exchanged water and filtered. The cake was washed three times again in ion-exchanged water, and then dried under reduced pressure to obtain a resin in which the hydroxyl group of the polyvinylphenol was partially ethoxyethyl etherified and cyclohexyloxyethyl ether ether.

As the method for producing the resin, a protecting group can be introduced into an alkali-soluble resin having a phenolic hydroxyl device by a known protecting group introduction reaction. In addition, the said resin can also be obtained by copolymerizing using an unsaturated compound which has such a group as one monomer.

Example  1 to 6 and Comparative Example  1 to 4: Chemically Amplified Positive Photoresist  Preparation of solution

The components shown in Table 1 were mixed at a corresponding composition ratio (in terms of solids), dissolved in 300 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. It was. The prepared resist solution includes a resin containing a degree of protection of 33% to 38%.

A-1: Resin with a molecular weight of 13,000 containing a ethoxyethyl group protecting group and a dispersity of 1.5 with respect to the hydroxy group of hydroxystyrene, a = 0.35, c = 0.00.

(In Formula 1, R ₁ : hydrogen, R ₂ : hydrogen, R ₃ : hydrogen, R ₄ : methyl group, R ₅ : ethyl group, R ₆ : methyl group, R ₇ : ethyl group)

A-2: Resin with a molecular weight of 13,000 and a dispersity of 1.5 containing an ethoxyethyl group / cyclohexyloxoethyl group protecting group with respect to the hydroxy group of hydroxy styrene, a = 0.32, c = 0.03.

(In Formula 1, R ₁ : hydrogen, R ₂ : hydrogen, R ₃ : hydrogen, R ₄ : methyl group, R ₅ : ethyl group, R ₆ : methyl group, R ₇ : cyclohexyl group)

A-3: A = 0.26 and c = 0.09 with a resin having a molecular weight of 13,000 and a dispersity of 1.5 containing an ethoxyethyl group / cyclohexyloxoethyl group protecting group relative to the hydroxy group of hydroxystyrene.

(In Formula 1, R ₁ : hydrogen, R ₂ : hydrogen, R ₃ : hydrogen, R ₄ : methyl group, R ₅ : ethyl group, R ₆ : methyl group, R ₇ : cyclohexyl group)

A-4: a = 0.15 and c = 0.20 with a resin having a molecular weight of 13,000 and a dispersity of 1.5 containing an ethoxyethyl group / cyclohexyloxoethyl group protecting group relative to the hydroxy group of hydroxystyrene.

(In Formula 1, R ₁ : hydrogen, R ₂ : hydrogen, R ₃ : hydrogen, R ₄ : methyl group, R ₅ : ethyl group, R ₆ : methyl group, R ₇ : cyclohexyl group)

B-1: Diazodisulfone type photoacid generator in which R ₈ and R ₉ in Chemical Formula 2 are each cyclohexyl group,

B-2: triphenylsulfonium trifluoromethanesulfonate

C-1: 1,4-cyclohexyl dimethanol

D-1: dicyclohexylmethylamine

Test Example: Performance Test of Chemically Amplified Positive Photoresist Solution

The resist solutions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were applied to a silicon wafer treated with hexamethyldisilazane using a spin coater, so that the film thicknesses after drying were 1.200 μm and 2.600 μm. It was. Then, preheat treatment was performed for 60 seconds on a hot plate at 100 ° 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 = 0.68, sigma == 0.75], 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 an aqueous 2.38% tetramethylammonium hydroxide solution. About the pattern after image development, the development defect was measured in the square space pattern of 50 micrometers using the KLA scanning electron microscope. In addition, the depth of focus and profile were measured in a 1.0 μm line and space pattern.

The results are shown in Table 2 below.

profile Sensitivity (mJ / cm2) Film thickness Example 1 ◎ 38 1.200㎛ Example 2 ◎ 43 2.600㎛ Example 3 ◎ 38 1.200㎛ Example 4 ◎ 43 2.600㎛ Example 5 ◎ 38 1.200㎛ Example 6 ○ 43 2.600㎛ Comparative Example 1 ○ 38 1.200㎛ Comparative Example 2 X 43 2.600㎛ Comparative Example 3 ○ 40 1.200㎛ Comparative Example 4 X 45 2.600㎛

As shown in Table 2, the resist solution of Comparative Examples 1 to 4 had only an ethoxyethyl group as a protecting group, and when the film thickness became thick, the profile was not good and the photoacid generator alone or a high acidity acid generator was mixed. Even when used, it can be seen that no improvement of the profile is seen. However, when the ethoxyethyl group and the cyclohexyl oxoethyl group were used together as the protecting group in the resist solution of Examples 1 to 6, even when the film thickness was increased, the pattern shape was excellent when used with two photoacid generators.

The present invention provides a chemically amplified positive photoresist composition which is excellent in resolution and pattern shape even when the thickness of the photoresist is thick, and which enables precise implementation of a fine pattern.

Claims (12)

 A chemically amplified positive photoresist composition comprising (A) a resin represented by the following formula (1) and (B) a photoacid emitter: [Formula 1]

Where R ₁ , R ₂ and R ₃ are each independently hydrogen or a methyl group, R ₄ and R ₆ are each independently a methyl group or an ethyl group, R ₅ and R ₇ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 6 or less carbon atoms, provided that R ₅ and R ₇ are not the same. a, b and c represent the molar ratio of each monomer, Are each a number in the range 0-1, a + b + c = 1, and 0.10≤ [(a + c) / (a + b + c)] ≤0.50 or 0.05≤ [c / (a + b + c) ] ≤0.4. The method of claim 1, wherein a, b, and c have a value of 0.20 ≦ [(a + c) / (a + b + c)] ≦ 0.40 or 0.05 ≦ [c / (a + b + c)] ≦ 0.35 A chemically amplified positive photoresist composition having a. The chemically amplified positive photoresist composition of claim 1, wherein the photoacid generator (B) is a compound represented by the following Formula (B-1): (2)

In the above formula, R ₈ and R ₉ are each independently a hydroxy group, an amino group or a C 1-10 linear or branched alkyl group unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; A C3-C10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group or a C1-C6 alkoxy group; Or a C6-C11 aryl group unsubstituted or substituted with a C1-C20 alkyl group, a C1-C6 alkoxy group or a halogen. The photoacid generator according to claim 1, wherein the photoacid generator (B) is a mixture of a compound represented by the following formula (B-1) and a photoacid generator (B-2) having a high acidity and high lipophilicity, wherein the acidity is high and lipophilic This large photoacid generator (B-2) is a chemically amplified type characterized in that one or more mixtures selected from the group consisting of onium salt compounds, s-triazine organic halogen compounds, sulfone compounds and sulfonate compounds. Positive Photoresist Compositions: (2)

In the above formula, R ₈ and R ₉ are each independently a hydroxy group, an amino group or a C 1-10 linear or branched alkyl group unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; A C3-C10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group or a C1-C6 alkoxy group; Or a C6-C11 aryl group unsubstituted or substituted with a C1-C20 alkyl group, a C1-C6 alkoxy group or a halogen. The compound according to claim 3 or 4, wherein R ₈ and R ₉ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6 A chemically amplified positive photoresist composition, which is a triisopropylphenyl group, a 4-dodecylphenyl group, a 4-methoxyphenyl group, a 2-naphthyl group, or a benzyl group. The photoacid generator (B-2) having high acidity and high lipophilic property is triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium trifluoromethane. Sulfonate, 4-methylphenyldiphenylsulfonium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-meth Methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t- 1 selected from the group consisting of butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, and 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate. Species Chemical amplification type positive photoresist composition, characterized in that two or more kinds thereof. The chemically amplified positive photoresist composition according to claim 1, wherein the photoacid generator (B) is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the resin (A). The method according to claim 4, wherein the mixing ratio of the compound represented by the formula (B-1) and a high acidity and high lipophilic photoacid generator (B-2) is 50:50 ~ 90:10, characterized in that A chemically amplified positive photoresist composition. The chemically amplified positive photo according to claim 1, further comprising (C) 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, or a mixture thereof as an additive for controlling the phenomenon defect. Resist composition. The chemically amplified positive photo according to claim 9, wherein the additive (C) for controlling the development defect is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the resin (A) (in terms of solid content). Resist composition. The chemically amplified positive photoresist composition according to claim 1, further comprising (D) a nitrogen-containing basic organic compound as a quencher. Forming a resist pattern comprising applying a chemically amplified positive photoresist composition of claim 1 onto a substrate, prebaking and selectively exposing, followed by heat treatment and developing with an alkaline developer Way.